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    Publication numberCN100567358 C
    Publication typeGrant
    Application numberCN 200580018733
    PCT numberPCT/EP2005/006106
    Publication date9 Dec 2009
    Filing date7 Jun 2005
    Priority date8 Jun 2004
    Also published asCA2567660A1, CA2567660C, CN1965011A, DE502005002170D1, EP1756188A1, EP1756188B1, US7872067, US20080287593, WO2005121201A1
    Publication number200580018733.7, CN 100567358 C, CN 100567358C, CN 200580018733, CN-C-100567358, CN100567358 C, CN100567358C, CN200580018733, CN200580018733.7, PCT/2005/6106, PCT/EP/2005/006106, PCT/EP/2005/06106, PCT/EP/5/006106, PCT/EP/5/06106, PCT/EP2005/006106, PCT/EP2005/06106, PCT/EP2005006106, PCT/EP200506106, PCT/EP5/006106, PCT/EP5/06106, PCT/EP5006106, PCT/EP506106
    InventorsC·克吕格尔, G·奥特, H·克勒, M·布拉茨, M·舍勒尔, N·瓦格纳, R·范格尔德, R·贝格豪斯
    Applicant巴斯福股份公司
    Export CitationBiBTeX, EndNote, RefMan
    External Links: SIPO, Espacenet
    Amphiphilic polymer compositions and their use
    CN 100567358 C
    Abstract  translated from Chinese
    本发明涉及两亲性聚合物组合物,其制备方法及其在制备水不溶性活性化合物,尤其是用于作物保护的活性化合物的含水活性化合物组合物中的用途。 The present invention relates to amphiphilic polymer compositions, their preparation and their water-insoluble active compound in the preparation, in particular an aqueous active compound composition for crop protection active compounds in the use. 该两亲性聚合物组合物可以通过使如下组分反应而得到:a)至少一种疏水性聚合物P1,该聚合物带有对异氰酸酯基团呈反应性的官能基团R<sup>P1</sup>且由包含如下单体的烯属不饱和单体M1构成:a1)基于单体M1的总量为至少10重量%的式(I)的单体M1a,其中X为氧或基团NR<sup>4</sup>,R<sup>1</sup>、R<sup>2</sup>、R<sup>3</sup>和R<sub>4</sub>如权利要求书和说明书所定义;a2)基于单体M1的总量为至多90重量%的中性单烯属不饱和单体M1b,该单体在25℃下在水中的溶解度低于50g/l且不同于单体M1a;和a3)基于单体M1的总量为至多30重量%的烯属不饱和单体M1c,该单体不同于单体M1a和M1b;b)至少一种亲水性聚合物P2,该聚合物带有对异氰酸酯基团呈反应性的官能基团R<sup>P2</sup>;c)至少一种化合物V,该化合物含有异氰酸酯基团且对于异氰酸酯基团而言具有的官能度至少为1.5。 The amphiphilic polymer compositions can be prepared by the reaction components is obtained as follows: a) at least one hydrophobic polymer P1, the polymer having an isocyanate group is in a reactive functional group R <sup> P1 </ sup> and the following monomers containing ethylenically unsaturated monomers M1 constitute: a1) based on the total amount of the monomers M1 is at least 10% by weight of monomers M1a of the formula (I), wherein X is oxygen or a group group NR <sup> 4 </ sup>, R <sup> 1 </ sup>, R <sup> 2 </ sup>, R <sup> 3 </ sup> and R <sub> 4 </ sub> Book specification and defined in claim; a2) based on the total amount of the monomers M1 is at most 90% by weight of neutral monoethylenically unsaturated monomers M1b, which monomer at 25 ℃ solubility in water is less than 50g / l and different from the monomers M1a; and a3) based on the total amount of monomers M1 is at most 30% by weight of ethylenically unsaturated monomers M1c, and the monomer is different from the monomers M1a M1b; b) at least one hydrophilic polymer P2, the polymer having an isocyanate group is in a reactive functional group R <sup> P2 </ sup>; c) at least one compound V, the compound containing isocyanate groups and isocyanate groups in terms of having a functionality of at least 1.5.
    Claims(28)  translated from Chinese
    1.一种通过使如下组分反应而得到的两亲性聚合物组合物: a)至少一种疏水性聚合物P1,该聚合物带有对异氰酸酯基团呈反应性的官能基团RP1且由包含如下单体的烯属不饱和单体M1构成: a1)基于单体M1的总量为至少10重量%的式I的单体M1a: 其中X为氧或基团N-R4; R1为C1-C10烷基、C5-C10环烷基、苯基或苯基-C1-C4烷基; R2为氢或C1-C4烷基; R3为氢或C1-C4烷基;和R4为氢或C1-C4烷基; a2)基于单体M1的总量为至多90重量%的中性单烯属不饱和单体M1b,该单体在25℃下在水中的溶解度低于50g/l且不同于单体M1a, 其中单体M1a和M1b的总量为单体M1的至少95重量%;和a3)基于单体M1的总量为不超过5重量%的烯属不饱和单体M1c,该单体不同于单体M1a和M1b, b)至少一种亲水性聚合物P2,该聚合物带有对异氰酸酯基团呈反应性的官能基团RP2, c)至少一种化合物V,该化合物含有异氰酸酯基团且对于异氰酸酯基团而言具有的官能度为1.5-4.5, 其中所述疏水性聚合物P1在所述两亲性聚合物组合物中的比例为20-68重量%,所述亲水性聚合物P2在所述两亲性聚合物组合物中的比例为30-78重量%且所述化合物V在所述两亲性聚合物组合物中的比例为2-20重量%,在每种情况下基于聚合物P1、聚合物P2和化合物V的总重量。 A component of the reaction by the following obtained amphiphilic polymer composition: a) at least one hydrophobic polymer P1, the polymer having an isocyanate group is in a reactive functional group, and RP1 from ethylenically unsaturated monomers M1 comprise as monomers constituting: a1) based on the total amount of the monomers M1 is at least 10% by weight of monomers M1a of the formula I: wherein X is oxygen or a group N-R4; R1 is C1-C10 alkyl, C5-C10 cycloalkyl, phenyl or phenyl -C1-C4 alkyl; R2 is hydrogen or C1-C4 alkyl; R3 is hydrogen or C1-C4 alkyl; and R4 is hydrogen or C1-C4 alkyl; a2) based on the total amount of the monomers M1 is at most 90% by weight of neutral monoethylenically unsaturated monomers M1b, which at 25 ℃ monomer solubility in water is less than 50g / l and distinct the monomer M1a, wherein the total amount of monomers M1a and M1b of monomer M1 is at least 95 wt.%; and a3) based on the total amount of the monomers M1 is not more than 5% by weight of ethylenically unsaturated monomers M1c, the monomer different from monomers M1a and M1b, b) at least one hydrophilic polymer P2, the polymer having an isocyanate group is in a reactive functional groups RP2, c) at least one compound V, the compound containing isocyanate groups and for the purposes of the isocyanate groups having a functionality of 1.5 to 4.5, wherein the hydrophobic polymer P1 proportion of the amphiphilic polymer composition in an amount of 20-68% by weight, the the proportion of hydrophilic polymer P2 in the amphiphilic polymer composition in an amount of 30-78% by weight and the proportion of compound V in the amphiphilic polymer composition in an amount of 2-20% by weight, In each case the total weight of polymer based P1, P2 and the compound V in a polymer.
    2.根据权利要求l的聚合物组合物,其中疏水性聚合物对于官能基团RP1而言具有的官能度Fl为0.5-1.5。 According to claim l polymer composition, wherein the functionality of the hydrophobic polymer Fl for the purposes of having a functional group of 0.5 to 1.5 RP1.
    3. 根据权利要求1的聚合物组合物,其中疏水性聚合物Pl的数均分子量为500-20 000道尔顿。 3. The polymer composition according to claim 1, wherein the hydrophobic polymer Pl number-average molecular weight of 500-20000 daltons.
    4. 根据权利要求2的聚合物组合物,其中疏水性聚合物Pl的数均分子量为500-20 000道尔頓。 4. The polymer composition according to claim 2, wherein the hydrophobic polymer Pl number-average molecular weight of 500-20000 daltons.
    5. 根据权利要求1-4中任一项的聚合物组合物,其中亲水性聚合物不具有离子基团。 5. The polymer composition according to claim any one of 1-4, wherein the hydrophilic polymer has no ionic groups.
    6. 根据权利要求5的聚合物组合物,其中亲水性聚合物P2为脂族聚醚,其中至少70重量%的脂族聚醚由氣化乙烯基团构成。 6. The polymer composition according to claim 5, wherein the hydrophilic polymer P2 is an aliphatic polyether, wherein at least 70% by weight of aliphatic polyethers constituted by the gasification of vinyl groups.
    7. 根据权利要求1-4中任一项的聚合物组合物,其中亲水性聚合物P2 对于官能基团RP2而言具有的官能度F2为0.5-3.0。 7. A polymer composition according to claim any one of 1-4, wherein the hydrophilic polymer P2 for the purposes of functional groups RP2 having a functionality of 0.5 to 3.0 F2.
    8. 根据权利要求6的聚合物组合物,其中亲水性聚合物P2对于官能基团RP2而言具有的官能度F2为0.5-3.0。 8. A polymer composition according to claim 6, wherein the hydrophilic polymer P2 for the purposes of functional groups RP2 having a functionality of 0.5 to 3.0 F2.
    9. 根据权利要求1-4中任一项的聚合物组合物,其中亲水性聚合物P2 的数均分子量为500-20 000道尔顿。 9. A polymer composition according to claim any one of 1-4, wherein the hydrophilic polymer P2 number-average molecular weight of 500-20000 daltons.
    10. 根据权利要求8的聚合物组合物,其中亲水性聚合物P2的数均分子量为500-20 000道尔顿。 10. The polymer composition according to claim 8, wherein the hydrophilic polymer P2 number-average molecular weight of 500-20000 daltons.
    11. 根据权利要求1-4中任一项的聚合物组合物,其中疏水性聚合物Pl和亲水性聚合物P2以1:4-2.2:1的重量比Pl:P2^f吏用。 11. The polymer composition according to claim any one of 1-4, wherein the hydrophobic polymer and the hydrophilic polymer P2 Pl 1: 4-2.2: 1 weight ratio Pl: P2 ^ f with officials.
    12. 根据权利要求10的聚合物组合物,其中疏水性聚合物Pl和亲水性聚合物P2以1:4-2.2:1的重量比P1:P2使用。 12. The polymer composition according to claim 10, wherein the hydrophobic polymer and the hydrophilic polymer P2 Pl 1: 4-2.2: 1 weight ratio P1: P2 used.
    13. —种制备根据权利要求1-12中任一项的两亲性聚合物组合物的方法,该方法包括使组分i)和ii)与iii)反应:i) 至少一种由烯属不饱和单体M1构成且带有对异氛酸酯基团呈反应性的官能基团RP1的疏水性聚合物Pl,ii) 至少一种带有对异氦酸酯基团呈反应性的官能基团R"的亲水性聚合物P2,iii) 至少一种含有异氛酸酯基团且对于异氛酸酯基团而言具有的官能度为1.5-4.5的化合物V。 13. - The method for preparing seed amphiphilic polymer composition according to any one of claims 1-12 claim, which comprises reacting components i) and ii) and iii) reaction of: i) at least one ethylenically the genus unsaturated monomer M1 constituted and with a different atmosphere to the ester groups were hydrophobic polymer Pl functional groups RP1 reactivity, ii) at least one ester with helium to different reactive functional group was group R "of hydrophilic polymer P2, iii) at least one ester groups contain different atmosphere and different compounds 1.5-4.5 atmosphere for the purposes of ester groups having a functionality of V.
    14. 根据权利要求13的方法,其中使聚合物Pl和聚合物P2依次与化合物v^^。 14. The method according to claim 13, wherein the polymer Pl and P2 sequentially with the polymer compound v ^^.
    15. 根据权利要求13的方法,其中使聚合物Pl和聚合物P2在一步中与化合物V反应。 15. The method according to claim 13, wherein the polymer Pl and P2 in step a polymer is reacted with compound V.
    16. 根据权利要求1-12中任一项的两亲性聚合物组合物在将在25r /1013毫巴下在水中的溶解度低于10g/l的活性化合物和/或有效物质稳定在含水介质中的用途,其中所述活性化合物选自除草剂、杀真菌剂、杀线虫剂、杀螨刑、杀虫剂、调节植物生长的活性化合物、水不溶性维生素和维生素原,所述有效物质选自染料和UV吸收剂。 16. The claim amphiphilic polymer composition according to any one of 1-12 in 25r / 1013 mbar solubility in water of less than 10g / l of the active compound and / or stabilizing the active substance in an aqueous medium The use, wherein said active compound is selected from herbicides, fungicides, nematocides, acaricidal punishment, insecticides, plant growth regulating active compounds, water insoluble vitamins and provitamins, said active substance is selected from dyes and UV absorbers.
    17. 根据权利要求1-12中任一项的两亲性聚合物组合物在制备在25X: /1013毫巴下在水中的溶解度低于10g/l的活性化合物和/或有效物质的配制剂中的用途,其中所述活性化合物选自除草剂、杀真菌剂、杀线虫剂、杀螨剂、杀虫剂、调节植物生长的活性化合物、水不溶性维生素和维生素原, 所述有效物质选自染料和UV吸收剂。 17. The claim amphiphilic polymer composition in the preparation of any one of claims 1 to 12 in 25X: / 1013 mbar solubility in water is lower than the active compound 10g / l and / or formulation of the active substance The use, wherein said active compound is selected from herbicides, fungicides, nematocides, acaricides, insecticides, plant growth regulating active compounds, water insoluble vitamins and provitamins, said active substance is selected from dyes and UV absorbers.
    18. 根据权利要求1-12中任一项的两亲性聚合物组合物在制备在25X: /1013毫巴下在水中的溶解度低于10g/l的活性化合物和有效物质的含水配制剂中的用途,其中所述活性化合物选自除草剂、杀真菌剂、杀线虫刑、 杀螨剂、杀虫刑、调节植物生长的活性化合物、水不溶性维生素和维生素原,所述有效物质选自染料和UV吸收剂。 Claim 18. The amphiphilic polymer composition according to any one of 1-12 in the manufacture of the 25X: / 1013 mbar lower than the solubility in water of the aqueous formulation 10g / l of the active compound and the active substance The use wherein the active compound is selected from herbicides, fungicides, nematicides punishment, miticides, insecticides punishment, plant growth regulating active compounds, water insoluble vitamins and provitamins, the effective material selected from dyes and UV absorbers.
    19. 一种活性化合物组合物,包含至少一种在25t:/1013毫巴下在水中的溶解度低于10g/l的活性化合物和/或有效物质和至少一种根据权利要求1-12中任一项的两亲性聚合物組合物,其中所述活性化合物选自除草剂、 杀真菌剂、杀线虫剂、杀螨剂、杀虫剂、调节植物生长的活性化合物、水不溶性维生素和维生素原,所述有效物质选自染料和UV吸收剂。 19. An active compound composition comprising at least one 25t: / 1013 mbar solubility in water of less than 10g / l of the active compound and / or at least one active substance as claimed in any one of claim 1-12 one amphiphilic polymer composition, wherein said active compound is selected from herbicides, fungicides, nematocides, acaricides, insecticides, plant growth regulating active compounds, water insoluble vitamins and provitamins , said active substance is selected from dyes and UV absorbers.
    20. —种含水活性化合物组合物,包含作为连续相的含水介质和至少一个包含至少一种在25"C/1013毫巴下在水中的溶解度低于10g/l的活性化合物和/或有效物质和至少一种根据权利要求1-12中任一项的两亲性聚合物组合物的^t相,其中所述活性化合物选自除草剂、杀真菌剂、杀线虫剂、杀螨剂、杀虫剂、调节植物生长的活性化合物、水不溶性维生素和维生素原,所述有效物质选自染料和UV吸收剂。 20. - Species aqueous active compound composition comprising an aqueous medium as continuous phase and at least one comprises at least one 25 "C / 1013 mbar lower than the solubility in water of the active compound 10g / l and / or active substances and at least one claim amphiphilic polymer composition according to any one of 1-12 ^ t phase, wherein the active compound is selected from herbicides, fungicides, nematicides, acaricides, pesticides, plant growth regulating active compounds, water insoluble vitamins and provitamins, said active substance is selected from dyes and UV absorbers.
    21. 根据权利要求20的活性化合物组合物,其中^ft相的颗粒具有的平均粒度通过动态光散射测定不超过300nm。 21. The active compound composition according to claim 20, wherein the average size of the particles have a ^ ft phase by dynamic light scattering measurement does not exceed 300nm.
    22. 根据权利要求19-21中任一项的活性化合物组合物,以1:10-3:1 的重量比包含活性化合物和/或有效物质和两亲性聚合物组合物。 22. A compound according to claim active composition according to any one of 19-21, 1: 10-3: 1 weight ratio comprising the active compound and / or the active substance and the amphiphilic polymer composition.
    23. 根据权利要求19-21中任一项的活性化合物组合物,其中挥发性有机化合物的含量基于该组合物的总重量低于10重量%。 23. A compound according to claim active composition according to any one of 19-21, wherein the content of volatile organic compounds based on the total weight of the composition is less than 10% by weight.
    24. 根据权利要求22的活性化合物组合物,其中挥发性有机化合物的含量基于该组合物的总重量低于10重量%。 24. The active compound composition of claim 22, wherein the amount of volatile organic compound based on the total weight of the composition is less than 10% by weight.
    25. —种制备根据权利要求19-24中任一项的活性化合物组合物的方法,包括制备包含两亲性聚合物组合物和至少一种活性化合物和/或有效物质的均相非水混合物。 25. - A method of producing an active compound composition according to any of claims 19-24, comprising preparing a mixture comprising amphiphilic polymer composition and active compound A and / or homogeneous non-aqueous mixture of at least the active substance .
    26. —种制备根据权利要求20-24中任一项的含水活性化合物组合物的方法,该方法包括:混合物,和b)用水^t所得混合物。 26. - preparation methods of aqueous active compound composition according to any one of 20-24 claims, the method comprising: a mixture, and b) the resulting mixture was washed with water ^ t.
    27. —种制备根据权利要求20-24中任一项的含水活性化合物组合物的方法,该方法包括:a) 制备活性化合物和/或有效物质和任选两亲性聚合物组合物在沸点低于水的沸点的有机溶剂中的溶液,和b) 将活性化合物和/或有效物质的溶液与水或两亲性聚合物组合物的水溶液混合,和c) 除去有机溶刑。 27. - preparation methods of aqueous active compound composition according to any one of 20-24 claims, the method comprising: a) preparing active compounds and / or active substances and optionally amphiphilic polymer composition having a boiling point lower than the boiling point of water an organic solvent solution, and b) the active compound and / or a mixed solution with water or amphiphilic polymer composition of an aqueous solution of the active substance, and c) removing the organic solvent sentence.
    28. —种制备根据权利要求20-24中任一项的含水活性化合物组合物的方法,该方法包括在活性化合物的熔点以上的温度下将活性化合物和/ 或有效物质掺入两亲性聚合物组合物的水'溶液中。 28. - preparation methods of aqueous active compound composition according to any one of 20-24 claims, the method comprising at a temperature above the melting point of the active compound The active compound and / or amphiphilic active substances incorporated into the polymerization aqueous composition of 'solution.
    Description  translated from Chinese

    两亲性聚合物组合物及其应用 Amphiphilic polymer composition and its application

    本发明涉及两亲性聚合物组合物,其制备方法及其在制备水不溶性活性化合物,尤其是用于作物保护的活性化合物的含水活性化合物组合物中的用途。 The present invention relates to amphiphilic polymer compositions, their preparation and their water-insoluble active compound in the preparation, in particular an aqueous active compound composition for crop protection active compounds in the use.

    通常以含水活性化合物制剂形式配制活性化合物,即能够甚至在低浓度下发挥生理作用的物质。 Usually in the form of an aqueous preparation of the active compound preparation of active compound, i.e., can play a physiological role of substance even at low concentrations. 因此,例如在作物保护中用于防治害虫的活性化合物,即杀虫剂、杀真菌剂和除草剂,还有生长调节剂通常以含水浓缩物配制和销售,所述浓缩物在施用之前通过加入大量水而稀释到所需应用浓度("喷雾液,,)。还已证明含水活性化合物制剂本身可以用于药物和化妆品活性物质以及食品添加剂,例如维生素、维生素原等。同样的情形适 Thus, for example active compounds for controlling pests in crop protection, namely, insecticides, fungicides and herbicides, and growth regulators typically aqueous concentrate formulation and sales, the concentrate prior to administration by the addition of a large number of water diluted to the desired application concentration ("spray solution ,,). It has also been proved that the aqueous preparation of active compound per se may be used in pharmaceutical and cosmetic active substances and food additives, such as vitamins, provitamins, etc. The same situation applicable

    用于有效物质(effect substance),即甚至在4氐施用率下发挥规定的技术作用的低分子量化合物,例如着色剂和UV稳定剂的配制剂。 For the active substance (effect substance), namely even at 4 Di application rates low molecular weight compounds play the role of technical provisions, such as the formulation colorants and UV stabilizers.

    有不良溶解度,该溶解度在23'C/1013毫巴下通常低于10g/l。 Adverse solubility, the solubility 23'C / 1013 mbar typically below 10g / l. 因此,该类活性化合物的含水配制剂是非均相体系,其中活性化合物以乳化和/或* 相存在于连续水相中。 Therefore, aqueous formulations of such active compounds are heterogeneous systems, wherein the active compound with emulsifying and / or * phase present in the continuous aqueous phase. 为了稳定这些本身呈亚稳态的体系,通常使用乳化剂或M剂。 In order to stabilize these metastable system itself was generally used emulsifiers or M agent. 然而,它们的稳定作用通常并不令人满意,因而活性化合物可能分离出来,例如分层或沉降,尤其在含水配制剂在高温和成高度可变的温度下或接近凝固点下储存较长时间时。 However, they are generally not satisfactory stabilizing effect, and thus the active compound may be isolated, e.g., layering or sedimentation, in particular in the aqueous formulation at a high temperature and a highly variable temperatures or longer when stored at near the freezing point . 该问题在活性化合物具有结晶倾向时尤其显著。 When the problem was particularly notable in the active compound has a crystal orientation.

    有机溶剂也通常用于制备水不溶性活性化合物的含水配制剂。 Organic solvents are also commonly used for preparing aqueous formulations of water-insoluble active compound. 因此, 通常将水溶混性溶剂用作增溶剂,即增加活性化合物或有效物质在水相中 Thus, typically a water-miscible solvent is used as a solubilizer, an increase of the active compound or active substances in the aqueous phase

    的溶解度。 Solubility. 水不溶混性溶剂则用于将在应用温度下为固体的活性化合物转化成随后可以更容易乳化的液相。 Water-immiscible solvent is used as the solid active compound can then be more easily converted to liquid emulsion at application temperature. 与固体活性化合物的悬浮液相反,在乳液中活性化合物以分子形式溶于溶剂液滴中并因此更易利用且在施用时更有效。 And the suspension of the solid active compound contrast, in the emulsion of the active compound molecularly dissolved in the solvent droplets and thus easier to use and more effective when administered. 然而,由于由VOC引起的已知问题,较大量的有机溶剂的使用因 However, since the known problems caused by the VOC, a greater amount of the organic solvent by

    6与工作卫生相关的原因以及环境原因和在某些情况下还因毒理学原因是不希望的。 6 and the work of health-related reasons and environmental reasons and in some cases also due to toxicological reasons is undesirable.

    常规含水活性化合物制剂的另一缺点是分别在水相中悬浮和乳化的活 Another disadvantage of conventional aqueous active compound is suspended in the aqueous phase were alive and emulsified

    性化合物颗粒和活性化合物液滴具有较大的粒度,其尺寸通常为几个)um。 Compound particles and active compound droplets having a larger particle size, which size is usually a few) um. 然而,需要的是其中活性化合物以尽可能最高度的分散形式存在的含水配制剂,从而首先确保在配制剂中的均匀分布并因此确保更好的处理和定量给料性能以及同时增加配制剂中活性化合物的生物利用度。 However, it is one of the most active compounds as highly dispersed form of aqueous formulations, so first ensure uniform distribution in the formulation and thus ensure better handling and dosing properties and to increase simultaneously the formulation bioavailability of the active compound. 这里需要的是其中包含活性化合物的相的平均粒度低于500nm,尤其低于300nm的配制剂。 Here is where the average particle size of the required phase containing the active compound is less than 500nm, less than 300nm particular formulation.

    有各种使用两亲性嵌段共聚物来在含水赋形剂中增溶水不溶性活性化合物的建议。 There are various use amphiphilic block copolymer in an aqueous excipient for solubilizing water-insoluble active compounds proposal. 术语"增溶"指通过^f吏用溶解性传递物质(辅助剂)实现水不溶性活性化合物或有效物质的稳定、均匀分布,其中活性化合物*相的颗粒通常小到4艮难散射可见光且因此该混合物看起来或多或少呈透明。 The term "solubilized" refers to ^ f Officials passed substance (adjuvant) to achieve a water-insoluble with the solubility of the active compound or stabilizer of the active substance, evenly distributed, in which the active compound particles * phase is generally small to scatter visible light 4 and therefore difficult Gen The mixture looks more or less transparent. 这里的两亲性嵌段共聚物通常包含至少一个亲水性聚合物嵌段和至少一个疏水性聚合物嵌段。 Amphiphilic block copolymers herein generally comprise at least one hydrophilic polymer block and at least one hydrophobic polymer block.

    因此,例如US 2003/0009004提出了用于该目的的两亲性嵌段共聚物, 该共聚物包含亲水性聚乙烯亚胺嵌段和可生物降解的脂族聚酯的疏水性嵌段。 Thus, for example, US 2003/0009004 proposes amphiphilic block copolymers for this purpose, the copolymer comprises a hydrophilic polyethyleneimine block and a biodegradable hydrophobic aliphatic polyester block. 然而,这所具有的缺点是为获得稳定的含水活性化合物制剂基于活性化合物需要较大量的聚合物。 However, this has the disadvantage that in order to obtain a stable aqueous preparation of the active compound requires a greater amount of the active compound based on a polymer.

    US 2003/0157170描述了不含水的活性化合物组合物,该组合物包含具有聚酯作为疏水性组分的两亲性二嵌段共聚物和添加剂。 US 2003/0157170 describes a non-aqueous active compound composition, the composition comprising a polyester as a hydrophobic component having amphiphilic diblock copolymer and additives. 当用水稀释时, 该組合物形成含活性化合物的胶束。 When diluted with water, the composition forms micelles containing the active compound. 这些组合物也具有的缺点是基于活性化合物需要较大量的聚合物。 These compositions also have the disadvantage that require a greater amount of the active compound based on a polymer.

    剂的含水悬浮液。 Agent is an aqueous suspension. 所用嵌段共聚物可以通过烯属不饱和单体的"活,,或"受控"自由基嵌段共聚而得到。除了该类方法较复杂这一事实外,含水活性化合物配制剂包含较大量的水溶性有机溶剂。此外,该方法要求使用残留在产物中的有毒过渡金属催化剂。此外,嵌段共聚物的颜色倾向于变成棕色。 The block copolymer can be obtained by an ethylenically unsaturated monomer "living ,, or" controlled "radical block copolymerization. In addition to the fact that such a method is more complex, the aqueous active compound formulation comprises a relatively large amount water-soluble organic solvent. In addition, this method requires the use of toxic residues in the product transition metal catalyst. In addition, the color of the block copolymer tends to become brown.

    7US 4,888,389描述了具有聚异丁烯嵌段和亲水嵌段如聚醚嵌段的嵌段共聚物。 7US 4,888,389 describes a polyisobutylene block and a hydrophilic block such as block copolymers having polyether blocks. 然而,申请人自己的研究已经表明该申请中所述的嵌段共聚物不适于制备细碎的活性化合物制剂。 However, the applicant's own research has shown that the application of the block copolymer suitable for the preparation of finely divided preparation of active compound.

    总之,应注意的是尽管两亲性嵌段共聚物对水不溶性活性化合物和有效物质在水或含水介质中的配制剂提供了常规优点,但由现有技术已知的嵌段共聚物并不完全令人满意,这或者是因为其制备非常复杂,含水活性化合物制剂的稳定性并不令人满意,活性化合物的活性受到不利影响或者是基于活性化合物需要大量聚合物,这除了使成本更高外还可能在使用该制剂时造成不利。 In short, it is noted that although the amphiphilic block copolymer water-insoluble active compounds and active substances in water or aqueous media formulation provides general advantages, but the art is not known block copolymer completely satisfactory, either because their preparation is very complicated, the aqueous active compound formulation stability is not satisfactory, the activity of the active compound or adversely affected by active compounds requires a lot based polymer, except that it more costly It may also adversely outside when using this preparation.

    因此,本发明的目的是提供能够使水不溶性活性化合物在含水介质中有效增溶的物质。 Accordingly, an object of the invention to provide a capable water-insoluble active compounds in an aqueous medium efficiently solubilized material. 具体而言,这些物质应适于提供水不溶性活性化合物的含水活性化合物组合物,该组合物的挥发性有机化合物含量非常低,若有的话。 Specifically, these materials should be adapted to provide a water-insoluble active compound aqueous active compound composition, a volatile organic compound content of the composition is very low, if any. 此外,希望使用这些物质制备的含水活性化合物组合物对长期储存时、加入电解质时和用水稀释过程中的破坏具有高稳定性。 In addition, we want to use an aqueous active compound preparation of the composition of matter of long-term storage, when the electrolyte is added and diluted with water in the process of destruction has high stability.

    惊人的是,该目的由一种可以通过使如下组分反应而得到的聚合物组合物实现: Surprisingly, this object is achieved by a component can be obtained by the following reaction obtained polymer composition to achieve:

    a)至少一种疏水性聚合物Pl,该聚合物带有对异氰酸酯基团呈反应性的官能基团RP1且由包含如下单体的烯属不饱和单体Ml构成: al)基于单体M1的总量为至少10重量。 a) at least one hydrophobic polymer Pl, the polymer having an isocyanate group is in a reactive functional group RP1 and contains the following monomer ethylenically unsaturated monomer Ml constitution: al) based on the monomer M1 The total amount of at least 10 wt. /。 /. 的式I的单体Mla: Formula I monomer Mla:

    其中X为氧或基团N-R4; W为Crd()烷基、Cs-d。 Wherein X is oxygen or a group N-R4; W is Crd () alkyl, Cs-d. 环烷基、苯基或苯基-d-C4烷基; W为氢或Crd烷基; W为氢或Crd烷基;和R4为氢或CrQ烷基; a2)基于单体Ml的总量为至多卯重量%的中性单烯属不饱和单体Mlb,该单体在25。 Cycloalkyl, phenyl or phenyl -d-C4 alkyl;) based on total amount of monomer Ml a2; W is hydrogen or Crd alkyl group; W is hydrogen or Crd-alkyl; and R4 is hydrogen or an alkyl group CrQ Mao wt% at most neutral monoethylenically unsaturated monomer Mlb, the monomer 25. C下在水中的溶解度低于50g/l且不同于单体Mla;和a3)基于羊体Ml的总量为至多30重量%的烯属不饱和单体Mlc,该单体不同于单体Mla和Mlb, C and solubility in water of less than 50g / l and is different from monomers Mla; and a3) based on the total amount of sheep body Ml is at most 30% by weight of an ethylenically unsaturated monomer Mlc, different from the monomer monomer Mla and Mlb,

    b) 至少一种亲水性聚合物P2,该聚合物带有对异氰酸酯基团呈反应性的官能基团RP2, b) at least one hydrophilic polymer P2, the polymer having an isocyanate group is in a reactive functional group RP2,

    c) 至少一种化合物V,该化合物含有异氰酸酯基团且对于异氰酸酯基团而言具有的官能度至少为1.5。 c) at least one compound V, the compound containing isocyanate groups and for the purposes of the isocyanate groups having a functionality of at least 1.5.

    因此,本发明涉及本文所述的两亲性聚合物组合物及其制备方法。 Accordingly, the present invention relates to an amphiphilic polymer composition and preparation methods described herein.

    以有利的方式,本发明的两亲性聚合物组合物适于在水相中稳定不良水溶性或水不溶性活性化合物和有效物质,从而使得可以制备该类活性化合物和有效物质的含水配制剂。 In an advantageous manner, amphiphilic polymer composition of the present invention is adapted to poor stability in an aqueous phase-soluble or water-insoluble active compounds and active substances, so that the kind of the active compounds may be prepared and an aqueous active substance formulations. 与现有技术中所述的嵌段共聚物相反,它们可以用于在水相中基于该聚合物增溶大量活性化合物。 According to the prior art block copolymers Instead, they can be used in the aqueous phase of the polymer based on a number of active compound solubilized.

    因此,本发明还提供了这里和下文所述的两亲性聚合物组合物在将不良水溶性或水不溶性活性化合物和/或有效物质稳定在含水介质中的用途。 Accordingly, the present invention further provides here and amphiphilic polymer composition described below will be poor in water-soluble or water-insoluble active compound and / or a stabilizing effective substance in an aqueous medium in use.

    因此,本发明还提供了这里所述的两亲性聚合物组合物在制备水不溶性或不良水溶性活性化合物和有效物质的配制剂(下文也称为活性化合物组合物或有效物质组合物)中的用途。 Accordingly, the present invention also provides herein amphiphilic polymer composition is insoluble or poorly water-soluble active compound in the preparation of the water and the active substance formulation (hereinafter also referred to as the active compound composition or active substance composition) It uses. 就此而言,不良溶解性是活性^f匕合物或有效物质在25。 In this regard, poor solubility of the active compound or dagger ^ f active substance in 25. C和1013毫巴下在水中的溶解度低于10g/l,常常低于5g/l,尤其低于lg/1,特别是低于0.1g/1。 C and 1013 mbar solubility in water of less than 10g / l, often less than 5g / l, in particular less than lg / 1, especially less than 0.1g / 1.

    本发明进一步提供了活性化合物组合物或有效物质组合物,该组合物包含至少一种不良水溶性或水不溶性活性化合物和/或有效物质和至少一种这里和下文所述的两亲性聚合物组合物。 The present invention further provides a composition of the active compound or active substance compositions, the composition comprises at least one water-soluble or water-insoluble bad active compound and / or the active substance and at least one amphiphilic polymer herein and described below composition.

    本发明的活性化合物组合物或有效物质组合物可以是固体或液体。 The composition of the active compound or active substance compositions of the invention can be either solid or liquid. 该组合物的优选实施方案涉及含水的,即液态活性化合物组合物,该组合物包含作为连续相的含水介质以及至少一个分敉相,该分歉相包含至少一种在25°C/1013毫巴下在水中的溶解度低于10g/l的活性化合物和/或有效物质和至少一种两亲性聚合物组合物。 A preferred embodiment of the composition relates to aqueous, ie liquid active compound composition, said composition comprising an aqueous medium as the continuous phase and at least one sub-Mi phase, the sub apologized phase comprises at least one 25 ° C / 1013 ml Pakistan under water solubility of less than 10g / l of active compounds and / or active substance and at least one amphiphilic polymer composition.

    使用本发明的两亲性嵌段共聚物制备的不良水溶性或水不溶性活性化合物和/或有效物质的含水活性化合物组合物除了作为连续相的含水介质之外还包含至少一个包含活性化合物或有效物质的相,在该相中活性化合物或有效物质和两亲性聚合物组合物以活性化合物或有效物质和两亲性聚合物组合物的聚合物组分的聚集体形式存在。 Use of the present invention the amphiphilic block copolymer adverse-soluble or water-insoluble active compound and / or an aqueous active compound composition as the active substance in addition to the aqueous medium outside of the continuous phase further comprises at least one compound containing active or effective phase material, in this phase, the active compound or active substance and the amphiphilic polymer composition in the form of aggregates of active compound or active substance and amphiphilic polymer composition in the presence of the polymer component. 因此,包含活性化合物或有效物质的该相形成M相,该分ft相包含活性化合物或有效物质和至少一种本发明的两亲性聚合物组合物。 Therefore, containing the active compound or active substance of the phase formation of M phase, the sub-ft phase containing the active compound or active substance and the amphiphilic polymer composition comprising at least one of the present invention. 在这些组合物中,M相极为细碎,即 In these compositions, M is extremely crushing phase, namely

    分散相的颗粒具有的粒度显著小于ljim。 Dispersed phase particles having a particle size significantly smaller than ljim. 通常而言,可以通过光散射测定的平均粒径不超过500nm,常常不超过300nm,通常为10-300nm,优选10-250nm,尤其是20-200nm或20-150nm,特别优选30-100nm。 Generally, the average particle size can be measured by light scattering is not more than 500nm, often no more than 300nm, normally 10-300nm, preferably 10-250nm, particularly 20-200nm or 20-150nm, particularly preferably 30-100nm. 原则上讲,相颗粒可以具有甚至更小的平均直径直至粒度低于光散射可检测到的极限(例如〉10nm)的基本分子分散分布。 In principle, phase particles may have an even smaller diameter until the particle size is less than the average light scattering detectable limit (e.g.,> 10nm) substantially molecularly dispersed distribution.

    本发明的另一优选实施方案涉及非水的,通常为固态或半固态的活性化合物组合物,该组合物包含至少一种在25°C/1013毫巴下在水中的溶解度低于10g/l的活性化合物和/或有效物质和至少一种两亲性聚合物组合物, 该组合物基本不含水,或仅含少量,即<10重量%的水。 Another preferred embodiment of the present invention relates to a non-aqueous, usually solid or semi-solid compositions of the active compound, which composition comprises at least one at 25 ° C / 1013 mbar solubility in water of less than 10g / l The active compounds and / or active substances and at least one amphiphilic polymer composition, the composition is substantially free of water, or only a small amount, i.e., <10 wt.% of water. 作为其他组分, 这些组合物可以包含具体预定应用常用的辅助剂和添加剂。 As the other components, such compositions may contain common predefined application specific adjuvants and additives.

    在稀释时,本发明組合物,即含水和非水组合物均提供活性化合物或有效物质的含水制剂,该制剂包含连续水相和至少一个平均粒度显著小于1^im,通常不超过500mn,常常不超过300nm,例如为10-300nm,优选10-250nm,尤其为20-200nm或20-150nm,特别优选30-100nm的包含活性化合物或有效物质的相。 When diluted, the compositions of the present invention, i.e., aqueous and non-aqueous compositions offer the active compound or aqueous preparation of the active substance, the formulation comprising a continuous aqueous phase and at least one of an average particle size significantly less than 1 ^ im, usually not more than 500mn, often not more than 300nm, for example 10-300nm, preferably 10-250nm, in particular 20-200nm or 20-150nm, particularly 30-100nm preferably comprises the active compound or with the active substance.

    所述粒度为可以通过动态光散射测定的重均粒度。 The particle size measured by dynamic light scattering of weight average particle size. 本领域熟练技术人员例如由如下文献熟知获得该粒度的方法:H.Wiese, D.Distler, W5ssrige Polymerdispersionen【聚合物水綠体l, Wiley-VCH 1999,第4.2.1章,第40页及随后各页以及其中引用的文献,还有H. Auweter, D. Horn, J. Colloidlnterf.Sci. 105(1985)399, D.Lilge, D.Horn, Colloid Polym. Sci. 269(1991) 704或H.Wiese, D.Horn, J. Chem. Phys. 94(1991) 6429。 Those skilled in the art, for example by the following well-known literature methods to obtain this size: H.Wiese, D.Distler, W5ssrige Polymerdispersionen polymer Shuilv body [l, Wiley-VCH 1999, Chapter 4.2.1, page 40, and then pages and references cited therein, as well as H. Auweter, D. Horn, J. Colloidlnterf.Sci. 105 (1985) 399, D.Lilge, D.Horn, Colloid Polym. Sci. 269 (1991) 704 or H .Wiese, D.Horn, J. Chem. Phys. 94 (1991) 6429.

    这里和下文中,术语"含水介质"和"水相"包括水、基于混合物含有至多10重量%水溶混性有机溶剂的水的含水混合物和固体在水或该含水混合物中的溶液。 Here and hereinafter, the term "aqueous medium" and "aqueous phase" include water, based on the mixture containing up to 10% by weight of water-miscible organic solvent, water and an aqueous mixture of a solid solution in water or in the aqueous mixture. 水溶混性溶剂的实例包括C3-Q酮如丙酮和甲基乙基酮,环状醚如二^悉烷和四氢呋喃,C广C4链烷醇如甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇,多元醇及其单-和二甲醚,如乙二醇、丙二醇、 乙二醇单甲醚、二甘醇、二甘醇单甲醚、二甘醇二曱酸、甘油,此外还有 Examples of water-miscible solvents include C3-Q ketones such as acetone and methyl ethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran noted two ^, C wide C4 alkanol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, polyols and single - and dimethyl ether, such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl Yue acid , glycerol, in addition

    CrC3腈如乙腈和丙腈,二甲亚砜,二甲基甲酰胺,甲酰胺,乙酰胺,二甲基乙酰胺,丁内酯,2-吡咯烷酮和N-甲基吡咯烷酮。 CrC3 nitriles such as acetonitrile and propionitrile, dimethylsulfoxide, dimethylformamide, formamide, acetamide, dimethylacetamide, butyrolactone, 2-pyrrolidone and N- methylpyrrolidone.

    这里和下文中,术语"官能度"表示每分子或每聚合物链各官能基团的平均数目。 Here and below, the term "functionality" represents the average number per molecule or per polymer chain various functional groups.

    本发明的含水活性化合物组合物对破坏具有极高的稳定性。 The aqueous active compound compositions of the present invention has a very high stability of the damage. 不发生破坏的话,它们甚至可以在高温和/或高度可变温度下储存几个月的较长时间。 Damage does not occur, they can be stored for a long time and even months at a high temperature and / or highly variable temperatures. 另外,还可以无任何问题地用水稀释更浓缩的分散体而不发生任何破坏现象,如凝结、结晶、絮凝或沉降。 In addition, problems can be diluted with water without any more concentrated dispersion without any damage phenomena, such as condensation, crystallization, flocculation or sedimentation. 此外,该組合物对电解质具有高度耐受性。 In addition, the composition having a high degree of tolerance to the electrolyte. 再有,由于^IM目的粒径非常小而具有极细的分布,活性化合物的活性与常规含水配制剂相比增加。 Further, since ^ IM object having a very small particle size distribution of very fine, increasing activity of the active compound in comparison with a conventional aqueous formulation. 本发明含水活性化合物组合物的另一优点是它们还可以配制成低溶剂含量的组合物(挥发性溶剂的含量<10重量°/。,基于活性化合物组合物的重量)或甚至配制成不含溶剂的组合物(挥发性溶剂含量<1重量%,基于活性化合物组合物的重量)。 Another advantage of aqueous compositions of the active compound of the present invention is that they may also be formulated as a low-solvent composition (volatile solvent content <10 wt ° /., Based on the weight of the active compound composition) or even formulated without The composition of the solvent (volatile solvent content of <1 wt.%, based on the weight of the active compound composition).

    用于制备本发明两亲性聚合物组合物的疏水性聚合物pi和亲水性聚 Used in preparing the amphiphilic polymer composition of hydrophobic and hydrophilic polymer poly pi

    合物P2均分别具有对异氰酸酯基团呈反应性且与化合物V的异氰酸酯基团反应形成键的官能基团RP1和RP2。 P2 were each compound having an isocyanate group is reactive and the reaction with the compound V isocyanate groups form a bond functional groups RP1 and RP2. 合适官能基团的实例是幾基、巯基(SH) 以及伯和仲氨基。 Examples of suitable functional groups are few, thiol (SH) and primary and secondary amino group. 优选的官能基团是羟基,尤其是连接于脂族或环脂族碳原子上的羟基。 Preferred functional groups are hydroxyl groups, especially hydroxyl groups attached to aliphatic or cycloaliphatic carbon atoms.

    因为含异氰酸酯基团的化合物V每分子平均具有至少1.5个异氰酸酯基团,因此在V与聚合物Pl和聚合物P2的反应中形成至少一些包含至少一个衍生于疏水性聚合物Pl的疏水性聚合物嵌段和至少一个衍生于亲水性聚合物P2的亲水性聚合物嵌段二者的嵌段共聚物。 Because the compound V containing isocyanate groups per molecule having an average of at least 1.5 isocyanate groups, thus forming at least some comprising at least one derivative in the hydrophobic polymer Pl of hydrophobic polymer in V with the polymer Pl and polymer P2 reactions material and at least one block derived from a hydrophilic polymer P2 hydrophilic polymer block of a block copolymer of both. 与现有技术的两亲性嵌段共聚物相反,这些嵌段不直接相互连接,而是经由具有至少两个尿烷和/或脲基的连接基连接。 Instead, these blocks are not directly connected to each other with the amphiphilic block copolymer of the prior art, but is connected via a connecting group having at least two urethane and / or urea groups. 与现有技术的嵌段共聚物相反,得到的两亲性聚合物组合物通常还包含少量的未反应聚合物Pl和/或P2以及对称反应产物,所述对称反应产物具有仅衍生于聚合物Pl的聚合物嵌段或仅衍生于聚合物P2的聚合物嵌段。 Block copolymers of the prior art and opposite, resulting amphiphilic polymer composition typically also contain minor amounts of unreacted polymer Pl and / or P2 and the reaction product of the reaction product of symmetry, the symmetry is derived from a polymer having only Pl polymer block or polymer derived from only a polymer block P2. 然而,确保了聚合物组合物的有利两亲性能。 However, to ensure that the favorable properties of the amphiphilic polymer composition. 合适的疏水性聚合物P1原则上是所有由烯属不饱和单体M1构成的聚合物,该聚合物基于单体Ml的总量包含至少10重量%,优选至少30重量%,尤其至少50重量%,特别优选至少60重量。 Is a suitable hydrophobic polymers P1 principle all polymers from ethylenically unsaturated monomers M1 constructed, based on the total amount of monomers Ml polymer comprises at least 10 wt%, preferably at least 30 wt%, especially at least 50 wt. %, particularly preferably at least 60 wt. /o的单体Mla且具有所需数目的反应性基团RP1。 / O Mla monomers and having the desired number of reactive groups RP1.

    优选的单体Mla是其中式I中W为氢的那些。 Preferred monomers Mla are those of formula I wherein W is hydrogen. R"-优选为氢或甲基。 X优选为O、亂NCH3ANC2H5。 R "-. Preferably hydrogen or methyl X preferably is O, chaos NCH3ANC2H5.

    W优选为: W is preferably:

    -dd。 -dd. 烷基如曱基、乙基、正丙基、异丙基、正丁基、2-丁基、异丁基、 叔丁基、l-戊基、2-戊基、新戊基、正己基、2-己基、正辛基、2-乙基己基、2-丙基庚基或正癸基,其中对于R^H, W尤其不为甲基; -Cs-d()环烷基如环戊基、环己基或甲基环己基,或-苯基-C广Q烷基如千基,l-或2-苯基乙基,l-、 2-或3-苯基丙基。 An alkyl group such as Yue, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, l- pentyl, 2-pentyl, neopentyl, n-hexyl , 2-hexyl, n-octyl, 2-ethylhexyl, heptyl, 2-propyl or n-decyl, wherein the R ^ H, W is not in particular methyl; -Cs-d () cycloalkyl such as pentyl, cyclohexyl or methylcyclohexyl, or - phenyl wide -C Q alkyl group such as one thousand, l- or 2-phenylethyl, l-, 2-, or 3-phenylpropyl. W尤其为d-do烷基,其中对于R^H, W尤其不为甲基。 W in particular d-do-alkyl, wherein the R ^ H, W is not in particular methyl. 因此,特别优选的单体Mla为丙烯酸与Crdc链烷醇的酯—丙烯酸Crd。 Accordingly, particularly preferred monomers are acrylic acid and Crdc Mla alkanol ester - acrylic Crd. 烷基酯),如丙烯酸乙酯、丙烯酸正丁基酯、丙烯酸异丁基酯、丙烯酸叔丁基酯、丙烯酸正己酯、丙烯酸2-乙基己基酯和丙烯酸3-丙基庚基酯, 曱基丙烯酸与d-do链烷醇的酯,如甲基丙烯酸甲酯、甲基丙烯酸乙酯、 甲基丙烯酸正丁基酯、甲基丙烯酸异丁基酯、曱基丙烯酸叔丁基酯和曱基丙烯酸正己基酯。 Alkyl esters), such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and 3-propyl-heptyl acrylate, Yue methacrylic acid with d-do alkanol esters, such as methyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, Yue group and Yue yl acrylate, n-hexyl acrylate. 优选的单体Mla此外还是丙烯酸和曱基丙烯酸的N-(Crdo烷基)酰胺,以及丙烯酸和甲基丙烯酸N-(CrC2烷基)-N-(C2-CK) 烷基)酰胺,例如N-乙基丙烯酰胺、N,N-二乙基丙烯酰胺、N-丁基丙烯酰胺、N-甲基-N-丙基丙烯酰胺、N-(正己基)丙烯酰胺、N-(正辛基)丙烯酰胺以及对应的曱基丙烯酰胺。 Further preferred monomer is acrylic acid and Yue Mla based acrylic N- (Crdo-alkyl) amides, and acrylic and methacrylic acid N- (CrC2-alkyl) -N- (C2-CK) alkyl) amides, e.g., N - ethyl acrylamide, N, N- diethyl-acrylamide, N- butyl acrylamide, N- methyl -N- propyl acrylamide, N- (n-hexyl) acrylamide, N- (n-octyl ) acrylamide, and corresponding Yue acrylamide. 基于单体Mla的总量,单体Mla尤其包含至少50重量%,特别是至少70重量%的至少一种曱基丙烯酸dQ烷基酯(R^CrC4烷基,R、CH3和R、H),其中特别优选甲基丙烯酸甲酯。 Based on the total amount of monomer Mla, Mla monomer comprising at least 50% by weight, especially, in particular at least 70 wt% of at least one acrylate group 曱 dQ alkyl ester (R ^ CrC4 alkyl group, R, CH3, and R, H) wherein methyl methacrylate is particularly preferred.

    除了单体Mla外,疏氷性聚合物Pl还可以包含不同于单体Mla的单体Mlb,其量基于单体M1的总量为至多90重量%,优选至多70重量%, 尤其至多50重量%,特别优选至多40重量%。 In addition to the monomers Mla, the hydrophobic polymer Pl ice may also contain a monomer different from the monomer Mla Mlb, based on the total amount of monomer M1 is at most 90% by weight, preferably up to 70 wt.%, In particular at most 50 wt. %, particularly preferably at most 40% by weight. 这些单体是在25。 These monomers are at 25. C和1013 毫巴下在水中的溶解度〈50g/1,通常〈20g/1的单烯属不饱和单体。 C and 1013 mbar solubility in water of <50g / 1, typically <monoethylenically 20g / 1 unsaturated monomer. 该类单体 Such monomer

    12Mlb的实例是乙烯基芳族单体如苯乙烯、a-甲基苯乙烯、乙烯基甲苯等, 具有2-10个碳原子的烯烃,优选具有3-10个碳原子的a-烯烃如丙烯、1-丁烯、l-戊烯、l-己烯、l-辛烯和l-癸烯,脂族羧酸的乙烯基酯如乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯、壬酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯和硬脂酸乙烯酯,不饱和腈如丙烯腈和甲基丙烯腈,卣代烯烃如氯乙烯, 优选具有3-6个碳原子的单烯属不饱和单羧酸的C『C2o烷基酯如丙烯酸 Examples 12Mlb are vinyl aromatic monomers such as styrene, a- methylstyrene, vinyltoluene, olefins having 2 to 10 carbon atoms, preferably a- olefin having 3-10 carbon atoms, such as propylene , 1-butene, l- pentene, l- hexene, l- l- octene and decene, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl laurate, nonyl vinyl acetate, vinyl neodecanoate, vinyl laurate and vinyl stearate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, wine container-olefin such as vinyl chloride, preferably a single alkylene of 3-6 carbon atoms, unsaturated monocarboxylic C "C2o alkyl esters such as acrylic acid

    Cu-C20烷基酯和曱基丙烯酸Cn-C20烷基酯,如丙烯酸月桂基酯、甲基丙 Cu-C20 alkyl esters of methacrylic acid and Yue Cn-C20 alkyl esters, such as lauryl acrylate, methacrylic

    烯酸月桂基酯、丙烯酸异十三烷基酯、甲基丙烯酸异十三烷基酯、丙烯酸硬脂基酯、甲基丙烯酸硬脂基酯,优选具有4-8个碳原子的烯属不饱和二羧酸的二-CrC20烷基酯如富马酸和马来酸的二-d-C2c烷基酯,如富马酸二甲酯、马来酸二甲酯、富马酸二丁酯和马来酸二丁酯,优选具有3-6个碳原子的单烯属不饱和单羧酸的缩水甘油酯如丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯。 Acid lauryl acrylate, isotridecyl methacrylate, isotridecyl acrylate, stearyl methacrylate, stearyl methacrylate, preferably 4-8 carbon atoms, alkenyl not belong Second -CrC20 alkyl esters of unsaturated dicarboxylic acids such as fumaric acid and maleic acid di -d-C2c alkyl esters such as dimethyl fumarate, dimethyl maleate, dibutyl fumarate monoethylenically and dibutyl maleate, preferably 3-6 carbon atoms, unsaturated monocarboxylic acids such as glycidyl acrylate and glycidyl methacrylate. 优选的单体Mlb是乙烯基芳族单体,其中尤其优选苯乙烯。 Mlb Preferred monomers are vinyl aromatic monomer, wherein styrene is particularly preferred. 在一个实施方案中,单体Mlb的比例基于单体M1的总量为1-90重量%, 优选5-70重量%,尤其是7-50重量%,特别优选10-40重量%。 In one embodiment, the ratio of the monomers based on the total monomer Mlb M1 is 1-90% by weight, preferably 5-70% by weight, in particular 7-50% by weight, particularly preferably 10 to 40% by weight. 优选单体Mla和Mlb的总量为单体Ml的至少80重量%,尤其至少90重量%, 特别优选至少95重量%。 Preferably the total amount of the monomers is a monomer Mla and Mlb Ml is at least 80% by weight, especially at least 90% by weight, particularly preferably at least 95 wt%.

    除了单体Mla和合适的话Mlb外,聚合物Pl基于单体Ml的总量可以包含至多30重量%,通常不超过20重量%,尤其不超过10重量%或不超过5重量%不同于单体Mla和Mlb的烯属不饱和单体Mlc。 In addition, if appropriate, monomers Mla and Mlb outside, based on the total monomer Ml Pl polymer may contain up to 30 wt.%, Usually not more than 20% by weight, in particular not more than 10% by weight or not more than 5% by weight of a monomer different from Mla and Mlb ethylenically unsaturated monomer Mlc.

    单体Mlc优选选自在25'C下在水中的溶解度为至少50g/l,尤其是至少100g/l的中性单烯属不饱和单体Mlc.l和带有至少一个离子性或可离子化基团的单烯属不饱和单体Mlc.2。 Mlc monomer is preferably selected from a solubility in water at 25'C is at least 50g / l, especially at least 100g / l of neutral monoethylenically unsaturated monomers Mlc.l and having at least one ionic or ionizable group of monoethylenically unsaturated monomer Mlc.2.

    单体Mlc.l的实例是上述烯属不饱和羧酸的酰胺,尤其是丙烯酰胺和甲基丙烯酰胺,还有上述烯属不饱和羧酸的N-幾基烷基酰胺,特别是N-幾甲基酰胺,尤其是N-羟曱基丙烯酰胺和N-羟甲基甲基丙烯酰胺,烯属不饱和腈如甲基丙烯腈和丙烯腈,上述a,P-烯属不饱和C3-Cs单羧酸和CrC8二羧酸的羟烷基酯,尤其是丙烯酸羟乙基酯、甲基丙烯酸羟乙基酯、 丙烯酸2 和3-羟基丙基酯、甲基丙烯酸2-和3-羟基丙基酯,聚乙二醇或烷基聚乙二醇的乙烯基醚和烯丙基醚,上述单烯属不饱和单羧酸和二羧酸与 Examples of the above-mentioned monomer Mlc.l ethylenically unsaturated carboxylic acid amides, especially acrylamide and methacrylamide, and the above-described ethylenically unsaturated carboxylic acid N- alkylamides several groups, in particular N- several methylamide, especially N- hydroxyalkyl Yue acrylamide and N- methylol methacrylamide, ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile, said a, P- ethylenically unsaturated C3- CrC8 Cs monocarboxylic acid and dicarboxylic acid hydroxyalkyl esters, in particular hydroxyethyl acrylate, hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 2 and methacrylate, 2- and 3-hydroxy- propyl ester, polyethylene glycol or polyethylene glycol alkyl vinyl ether and allyl ether, said monoethylenically unsaturated monocarboxylic and dicarboxylic acids and

    C2-C4聚亚烷基二醇的酯,尤其是那些羧酸,特别是丙烯酸或甲基丙烯酸与聚乙二醇或烷基聚乙二醇的酯,其中在该类酯和醚中的(烷基)聚乙二醇基团通常具有100-3000的分子量。 Poly C2-C4 alkylene glycol esters, especially those carboxylic acids, particularly acrylic or methacrylic acid with polyethylene glycol or polyethylene glycol alkyl esters, wherein the esters and ethers of the class ( alkyl) polyethylene glycol radical usually has a molecular weight of 100-3000. 单体Mlc.l进一步包括N-乙烯基酰胺, 如N-乙烯基曱酰胺、N-乙烯基吡咯烷酮和N-乙烯基己内酰胺。 Further comprising the monomer Mlc.l N- vinyl amides, such as N- vinyl Yue carboxamide, N- vinyl pyrrolidone and N- vinyl caprolactam. 单体Mlc.l 进一步包括带有脲基的单体,如N-(2-丙烯酰氨基乙基)咪唑啉-2-酮和N-(2-甲基丙烯酰氨基乙基)咪唑啉-2-酮,以及含有搭基或酮基的单体,如3-(丙烯酰氨基)-3-甲基丁-2-酮(双丙酮丙烯酰胺)、3-(甲基丙烯酰氨基)-3-甲基丁-2-酮、丙烯酸2,4-二氧杂戊基酯和甲基丙烯酸2,4-二氧杂戊基酯。 Mlc.l further monomers include monomers having ureido groups, such as N- (2- acrylamido ethyl) imidazolin-2-one and N- (2- acrylamido-methyl-ethyl) imidazoline - keto, and take-containing group or a ketone group-containing monomer, such as 3- (acrylamido-yl) -3-methylbutan-2-one (diacetone acrylamide), 3- (acrylamido methyl) - 3-methylbut-2-one, 2,4-dioxa-amyl acrylate, methacrylate and 2,4-dioxa-pentyl ester. 单体Mlc.l的比例基于单体Ml的总量优选不超过20重量%,尤其不超过10 重量%,例如0.1-10重量%,尤其0.5-5重量%。 Based on the ratio of monomer Mlc.l the total amount of the monomers Ml is preferably not more than 20% by weight, in particular not more than 10% by weight, e.g., 0.1 to 10% by weight, in particular 0.5 to 5% by weight.

    单体Mlc.2尤其包括含有至少一个酸基团或至少一个阴离子基团的单烯属不饱和单体Mlc.2s,尤其是含有磺酸基团、膦酸基团或1或2个羧酸基团的单体,以及该类单体的盐,尤其是碱金属盐如钠或钾盐和铵盐。 Mlc.2 monomers include, in particular at least one acid group or at least one anionic group monoethylenically unsaturated monomer Mlc.2s, particularly those containing sulfonic acid group, phosphonic acid group or one or two carboxylic acid monomeric groups, and salts of such monomers, especially alkali metal salts such as sodium or potassium and ammonium salts. 这些包括烯属不饱和磺酸,尤其是乙烯基磺酸、2-丙烯酰M-2-曱基丙磺酸、 2-丙烯酰氧基乙磺酸和2-曱基丙烯酰氧基乙磺酸、3-丙烯酰氧基-和3-甲基丙烯酰氧基丙磺酸、乙烯基笨磺酸及其盐,烯属不饱和膦酸,如乙烯基膦酸和乙烯基膦酸二甲酯及其盐,以及a,l3-烯属不饱和QpC8单-和CrCr二羧酸,尤其是丙烯酸、甲基丙烯酸、巴豆酸、马来酸、富马酸和衣康酸。 These include ethylenically unsaturated sulfonic acids, especially vinyl sulphonic acid, 2-acrylamido-M-2- yl Yue propanesulfonic acid, 2-acryloyloxy acetic acid and 2-acryloxy ethyl Yue sulfo group acid, 3-acryloxy - and 3-methacryloxy propane sulfonic acid, vinyl stupid acid and its salts, ethylenically unsaturated phosphonic acids, such as vinylphosphonic acid and vinylphosphonic acid dimethyl esters and salts thereof, and a, l3- ethylenically unsaturated QpC8 single - and CrCr dicarboxylic acids, especially acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid. 单体Mlc.2s的比例基于单体Ml的总量通常不超过20重量%,例如0.1-20 重量%,尤其0.5-15重量%。 Based on the ratio of the total amount of monomers of monomer Ml Mlc.2s usually not more than 20% by weight, e.g., 0.1 to 20% by weight, in particular 0.5 to 15% by weight. 在优选实施方案中,聚合物P1不包含或包含低于0.1重量%的单体Mlc.2s。 In a preferred embodiment, the polymer P1 does not contain or contains less than 0.1% by weight of the monomer Mlc.2s.

    单体Mlc.2此外包括具有至少一个阳离子基团和/或至少一个可以在含水介质中质子化的基团的单烯属不饱和单体Mlc.2k。 Also included Mlc.2 monomer having at least one cationic group and / or at least one can be protonated group in an aqueous medium monoethylenically unsaturated monomer Mlc.2k. 单体Mlc.2k尤其包括具有可质子化氨基、季铵基、可质子化亚氨基或季铵化亚氨基的那些。 Mlc.2k monomers include, in particular having a protonated amino group, quaternary ammonium group, an imino group can be protonated or quaternized imino those. 具有可质子化亚氨基的单体实例是N-乙烯基咪唑和乙烯基吡啶。 Examples of monomers having a protonatable imino group is N- vinyl imidazole and vinyl pyridine. 具有季铵化亚氨基的单体的实例是N-烷基乙烯基吡咬错盐和N-烷基-N,-乙烯基咪唑啉饋盐,如N-甲基-N,-乙烯基咪唑啉镛氯化物或曱基硫酸盐。 Examples of alkylene having quaternized amino alkyl vinyl monomers are N- bite error salts and N- pyridin-alkyl -N, - feeding a vinyl imidazoline salts, such as N- methyl -N, - vinylimidazole Yong Yue group morpholino chloride or sulfate. 在单体Mlc,2k中特别优选式II的单体:、—N+-R7 z- In the monomer Mlc, 2k particularly preferred monomer of formula II:, - N + -R7 z-

    6 6

    其中 Among them

    RS为氢或CVC4烷基,尤其是氢或甲基, R6、 W相互独立地为d-C4烷基,尤其是甲基,和R8为氢或CrC4烷基,尤其是氢或甲基, Y为氧、NH或NR9,其中R、CH:4烷基, CVC4 RS is hydrogen or alkyl, especially hydrogen or methyl, R6, W are independently a d-C4 alkyl, especially methyl, and R8 is hydrogen or CrC4 alkyl, especially hydrogen or methyl, Y It is oxygen, NH or NR9, wherein R, CH: 4 alkyl,

    A为CrC8亚烷基,例如l,2-亚乙基、1,2-或1,3-亚丙基、1,4-亚丁基或2-甲基-l,2-亚丙基,其可以被l、 2或3个非相邻氧原子间隔,和z一为阴离子等价物,例如cr、 HS04—、 ^SO?—或CH3OS03—等, 以及对于RS-H,还有式II单体的游离碱。 A is CrC8 alkylene, e.g. l, 2- ethylene, 1,2- or 1,3-propylene, 1,4-butylene or 2-methyl -l, 2- propylene, which can be l, 2, or 3 non-adjacent oxygen atoms, and z is an anion equivalent, e.g. cr, HS04-, ^ SO -? CH3OS03- or the like, as well as the RS-H, as well as the monomer of formula II free base.

    该类单体Mlc.2k的实例是丙烯酸2-(N,N-二甲氨基)乙基酯、甲基丙烯酸2-(N,N-二甲餘)乙基酯、2-(N,N-二甲絲)乙基丙烯酰胺、3-(N,N-二甲氨基)丙基丙烯酰胺、3-(N,N-二甲氨基)丙基甲基丙烯酰胺、2-(N,N-二甲氨基)乙基甲基丙烯酰胺、丙烯酸2-(N,N,N-三甲基铵)乙基酯氯化物、2-甲基丙烯酸(N,N,N-三甲基铵)乙基酯氯化物、:2-(N,N,N-三甲基铵)乙基曱基丙烯酰胺氯化物、3-(N,N,N-三甲基铵)丙基丙烯酰胺氯化物、3-(N,N,N-三甲基铵)丙基甲基丙烯酰胺氯化物、2-(N,N,N-三甲基铵)乙基丙烯酰胺氯化物, 以及对应的甲基硫酸盐和硫酸盐。 Examples of such monomers are acrylic Mlc.2k 2- (N, N- dimethylamino) ethyl methacrylate, 2- (N, N- dimethylamino I) ethyl acrylate, 2- (N, N - Wire dimethyl) ethyl acrylamide, 3- (N, N- dimethylamino) propyl acrylamide, 3- (N, N- dimethylamino) propyl methacrylamide, 2- (N, N - dimethylamino) ethyl methacrylamide, acrylate, 2- (N, N, N- trimethylammonium) ethyl acrylate chloride, methacrylic acid 2- (N, N, N- trimethylammonium) ethyl chloride,: 2- (N, N, N- trimethylammonium) ethyl Yue acrylamide chloride, 3- (N, N, N- trimethylammonium) propyl acrylamide chloride , 3- (N, N, N- trimethylammonium) propyl methacrylamide chloride, 2- (N, N, N- trimethylammonium) ethyl acrylamide chloride, and the corresponding methyl sulfates and sulfates. 其他合适的单体Mlc.2k是乙烯基吡啶和乙烯基咪唑及其季铵化产物。 Mlc.2k other suitable monomers are vinyl pyridine and vinyl imidazole and quaternized product.

    单体Mlc.2k的比例基于单体Ml的总量有利的是不超过20重量%, 例如0.1-20重量%,尤其是0.5-15重量%,特别是1-10重量%。 Based on the ratio of monomer Mlc.2k advantageous that the total amount of the monomers Ml not more than 20% by weight, e.g., 0.1 to 20% by weight, in particular 0.5 to 15% by weight, in particular 1-10 wt%. 在优选实施方案中,聚合物P1不包含或包含不超过Ol重量。 In a preferred embodiment, the polymer P1 does not contain or contains no more than Ol wt. /。 /. 的单体Mlc.2k。 Monomers Mlc.2k.

    单体Mlc还包括具有两个或更多个非共轭烯属不饱和双键的单体Mlc.3。 Mlc also include monomers having two or more non-conjugated ethylenically unsaturated double bond of a monomer Mlc.3. 该类单体Mlc.3的比例基于单体M1的总量通常不超过2重量%, 尤其不超过0.5重量%。 Based on the ratio of such monomers Mlc.3 total amount of monomers M1 usually not more than 2% by weight, in particular not more than 0.5% by weight. 这些单体的实例是单烯属不饱和羧酸的乙烯基和烯丙基酯,如丙烯酸烯丙基酯和甲基丙烯酸烯丙基酯,二元醇或多元醇的二-和多丙烯酸酯,如乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、丁二醇 Examples of such monomers are monoethylenically unsaturated vinyl and allyl esters of carboxylic acids, such as allyl acrylate and allyl methacrylate, diol or polyol di - and polyacrylates , such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol

    15二丙烯酸酯、丁二醇二甲基丙烯酸酯、己二醇二丙烯酸酯、己二醇二甲基丙烯酸酯、三甘醇二丙烯酸酯、三甘醇三甲基丙烯酸酯、三(羟曱基)乙烷三丙烯酸酯和三(羟甲基)乙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯和季戊四醇三甲基丙烯酸酯,此外还有多官能羧酸的烯丙基和甲代烯丙基酯如马来酸二烯丙基酯、富马酸二烯丙基酯、邻笨二曱酸二烯丙基酯。 15 diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol trimethacrylate, tris (hydroxyethyl Yue yl) ethane triacrylate and tris (hydroxymethyl) ethane trimethacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate, addition of polyfunctional acid allyl and methallyl esters such as diallyl maleate, fumarate, diallyl phthalate, diallyl esters stupid two Yue. 典型的 Typical

    单体Mlc,3还是诸如二乙烯基苯、二乙烯基脲、二烯丙基脲、氰脲酸三烯丙基酯、N,N,-二乙烯基-和N,N,-二烯丙基咪唑烷-2-酮以及亚甲基二丙烯酰胺和亚甲基二曱基丙烯酰胺的化合物。 Monomer Mlc, 3 or such as divinyl benzene, divinyl urea, diallyl urea, cyanuric acid triallyl ester, N, N, - divinyl - and N, N, - diallyl yl imidazolidin-2-one, and methylene bis acrylamide and methylene bis acrylamide 曱 group.

    根据本发明,聚合物Pl带有与异氰酸酯基团反应形成键的反应性官能基团RP1。 According to the present invention, the polymer Pl with reactive functional groups RP1 isocyanate group reacts with the formation of bonds. 每个聚合物分子该类基团的平均数(官能度)通常不超过2,优选为0.3-1.8,尤其为0.5-1.5,特别是0.6-1.4。 Each polymer molecule the average number of such groups (functionality) is usually not more than 2, preferably 0.3-1.8, in particular 0.5-1.5, especially 0.6-1.4. 官能基团RP1可以位于聚合物链中,优选位于聚合物链末端。 RP1 functional groups may be located in the polymer chain, preferably located in the polymer chain end.

    考虑到本发明两亲性聚合物组合物在配制活性化合物中的用途,疏水聚合物Pl优选具有的数均分子量为500-20 000道尔顿,尤其是1500-15 000 道尔顿。 Considering the amphiphilic polymer composition of the present invention in the formulation of the active compound in the use, Pl hydrophobic polymer preferably has a number average molecular weight of 500-20000 Dalton, especially 1500-15000 Daltons.

    原则上讲,聚合物Pl由现有4支术已知,例如由US 5,556,918和EP-A 742 238已知。 In principle, it is known from the prior art polymer Pl 4, for example US 5,556,918 and EP-A 742 238 are known. 它们通常通过单体M1在引发剂和合适的话调节剂存在下的自由基引发溶剂聚合而制备,条件是引发剂在分解时含有羟基自由基('OH 自由基)和/或调节剂含有OH基团或NH2基团。 They are generally prepared by monomer M1 in the initiator and, if appropriate, in the presence of a radical initiator modifier solvent polymerization, with the proviso that a radical initiator containing a hydroxyl group ('OH radical) in the decomposition and / or modifiers containing OH groups group or NH2 group. 合适的引发剂是有机氢过氧化物,如氢过氧化+又丁基、氢过氧化四氢呋喃、氢过氧化枯烯或2,2,-偶氮二(2-甲基-N-(2-羟基乙基)丙酰胺)。 Suitable initiators are organic hydroperoxides, such as hydrogen peroxide and butyl +, tetrahydrofuran hydroperoxide, cumene hydroperoxide, or 2,2 - azobis (2-methyl -N- (2- hydroxyethyl) propionamide). 合适的调节剂是氨基醇、氨基酚和尤其是硫代链烷醇,如3-羟基丙硫醇、2-羟乙基-3-巯基丙酸酯和尤其是2-羟基乙硫醇(巯基乙醇)。 Suitable modifiers are amino alcohols, aminophenols and particularly thio alkanols, such as 3-hydroxy-propanethiol, 2-hydroxyethyl-3-mercapto propionate and especially 2-hydroxyethane thiol (mercapto ethanol). 若使用该类调节剂,聚合还可以在常规引发剂存在下进行,所迷引发剂例如为常规偶氮引发剂或有机过氧化物,如偶氮二(异丁腈)、过氧化二(叔丁基)、过氧化二癸酰、过氣化二苯曱酰、过乙酸叔丁酯或2-甲基过丙酸叔丁酯。 The use of such modifiers, polymerization initiators may also be in the presence of conventional under, the fans initiators such as organic peroxide initiator or azo routine, such as azobis (isobutyronitrile), peroxide (t butyl), decanoyl peroxide, vaporized over diphenyl Yue acid, tert-butyl peracetate or tert-butyl 2-methyl perpropionic acid. 若聚合在上述调节剂之一存在下进行,则该调节剂基于单体M1的总量通常以0.1-5重量%,常常为0.2-4重量%,尤其是0.5-3重量%的量使用。 When polymerized in the presence of the adjusting agent, based on the total amount of monomers M1 modifiers are generally 0.1 to 5% by weight, usually 0.2 to 4% by weight, in particular from 0.5 to 3% by weight of the amount of use. 引发剂基于待聚合单体Ml通常以0.05-5重量%,常常为0.1-4重量%,特别优选0.2-3重量%的量使用。 Initiator based on the monomers to be polymerized Ml typically 0.05 to 5% by weight, usually 0.1-4% by weight, particularly preferably 0.2 to 3 wt% of the amount. 进一步的细节尤其参考EP 742 238的第3页,其公开内容在此作为参考引入。 For further details with reference to EP 742 238, especially the first three, the disclosure of which is hereby incorporated by reference.

    本领域熟练技术人员原则上熟知具有反应性基团RP2的亲水性聚合物P2。 The skilled person familiar with the principles of RP2 having a reactive group of the hydrophilic polymer P2. 这些聚合物通常为本身可溶于水中的聚合物。 These polymers are generally water-soluble polymer itself. 该聚合物在水中的溶解度可以通过中性亲水性基团如羧酰胺基团、醚基、内酰胺基团、噁唑烷基团,通过阴离子基团或通过酸性基团如羧酸盐基团、磺酸盐基团或磷酸盐基团,通过碱性基团如伯或仲氨基、咪唑基、吡啶基,或通过阳离子基团如季铵化铵基、季铵化吡啶基或季铵化咪唑基调节。 The polymer solubility in water can be neutral hydrophilic groups such as carboxyl amide group, an ether group, a lactam group, oxazolidinyl group, by anionic groups or by acidic groups such as carboxylic acid salt groups, sulfonate groups or phosphate groups, by basic groups such as primary or secondary amino group, imidazolyl, pyridyl, or by a cationic quaternary ammonium groups such as ammonium groups, quaternary ammonium or quaternary ammonium pyridyl of imidazole regulation. 因此,取决于基团的性质,区分为非离子亲水性聚合物P2、阴离子或酸性聚合物P2和碱性或阳离子聚合物P2。 Thus, depending on the nature of the group, to distinguish between non-ionic hydrophilic polymer P2, anionic or basic or acidic polymer and a cationic polymer P2 P2. 聚合物P2优选为非离子聚合物,即离子基团或酸性或碱性基团的比例不超过0.5mol/kg聚合物P2,尤其不超过0.1mol/kg 聚合物P2。 P2 is preferably a non-ionic polymer polymer, i.e. the proportion of ionic groups or acidic or basic groups is not more than 0.5mol / kg polymer P2, in particular not more than 0.1mol / kg of polymer P2.

    非离子聚合物P2的实例是: -含有至少50重量%,尤其是至少70重量%氧化乙烯单元的脂族聚醚, -基于单体M2的总量包含至少50重量%,尤其是至少70重量%至少一种单烯属不饱和亲水性单体M2a的烯属不饱和单体的均聚物和共聚物, 所述单体M2a在25X:/1013毫巴下在水中的溶解度〉50g/1,尤其〉100g/1。 Examples of non-ionic polymer P2 is: - at least 50 wt.%, In particular at least 70 wt% oxyethylene units aliphatic polyethers, - based on the total amount of monomers M2 comprise at least 50 wt.%, In particular at least 70 wt. % of at least one monoethylenically unsaturated hydrophilic monomer M2a ethylenically unsaturated monomers, homopolymers and copolymers, the monomers M2a in 25X: / 1013 mbar solubility in water> 50g / 1, in particular> 100g / 1. 合适的单体M2a是作为单体Mlc.l提到的单体,尤其是N-乙烯基内酰胺,如N-乙烯基吡咯烷酮和N-乙烯基己内酰胺,单烯属不饱和单羧酸的上述酰胺,如曱基丙烯酰胺、丙烯酰胺,单烯属不饱和单羧酸的上述羟烷基酯,如丙烯酸羟乙基酯和甲基丙烯酸羟乙基酯,聚乙二醇和烷基聚乙二醇的乙烯基酯和烯丙基酯,以及丙烯酸和甲基丙烯酸与聚乙二醇或烷基聚乙二醇的酯, -聚(2-甲基嗜、唑啉)和聚(2-乙基嗝唑啉),和-聚(a-羟基羧酸)酯,如聚乙交酯和聚丙交酯。 Suitable monomers are monomers as monomer M2a Mlc.l mentioned, in particular the N- vinyl lactams, such as N- vinyl pyrrolidone and N- vinyl caprolactam, monoethylenically unsaturated monocarboxylic acids described above amides, such as acrylamide Yue, acrylamides, monoethylenically unsaturated monocarboxylic acid esters of the above-described hydroxyalkyl, such as hydroxyethyl acrylate and hydroxyethyl methacrylate, polyethylene glycol, and alkyl polyethylene vinyl esters and allyl alcohol esters, and acrylic and methacrylic acid with polyethylene glycol or polyethylene glycol alkyl esters, - poly (2-methyl-addicted, oxazoline) and poly (2-ethyl group belch oxazoline), and - poly (a- hydroxy acid) esters, such as polyglycolide and polylactide.

    合适阴离子聚合物P2的实例是基于聚合物P2的总重量包含至少30 重量,优选至少50重量。 Examples of suitable anionic polymers P2 are based on the total weight of the polymer P2 comprises at least 30 wt., Preferably at least 50 wt. /。 /. 带有,如羧tt团、磺tt团、磷酸酯基团或膦酰基团的单烯属不饱和单体M2b的那些。 With, such as carboxyl group tt, tt sulfonamide group, a phosphate group or phosphono group monoethylenically unsaturated monomer M2b of those. 合适单体M2b的实例是就聚合物Pl提到的单体Mlc.2s,例如a,P-烯属不饱和单-和二羧酸,如丙烯酸、 甲基丙烯酸、乙烯基乙酸,单烯属不饱和磺酸,如乙烯基磺酸、曱代烯丙基磺酸、苯乙烯磺酸、2-丙烯酰^-2-甲基丙磺酸和2-丙烯酰氧乙基磺酸, 烯属不饱和膦酸,如膦酸乙烯酯、膦酸烯丙酯、膦酸甲代烯丙酯、2-丙烯酰M-2-甲基丙烷膦酸和膦酸2-丙烯酰氧乙基酯。 Examples of suitable monomers M2b are the monomers Mlc.2s polymer Pl referred to, such as a, P- ethylenically unsaturated mono - and dicarboxylic acids, such as acrylic acid, methacrylic acid, vinyl acetate, monoethylenically unsaturated sulfonic acids such as vinylsulfonic acid, Yue methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and ^ 2- acryloyloxyethyl sulfonic acid, olefinic unsaturated acid, such as vinyl phosphonate, allyl phosphonic acid, acid methallyl ester, 2-acrylamido-M-2- methyl propane acid and phosphonic acid 2-acryloyloxyethyl ester. 除了上述羊体M2b以外,合适的阴离子聚合物P2可以包含至多50重量%,尤其至多30重量%的单体Mla和Mlb以及至多70重量%的单体M2a。 In addition to the above-described sheep body M2b, P2 suitable anionic polymers may contain up to 50% by weight, in particular at most 30% by weight of the monomer Mla and Mlb and up to 70% by weight of monomers M2a.

    合适阳离子聚合物P2的实例是上述单烯属不饱和单体Mlc.2k的均聚物和共聚物以及单体Mlc.2k与单烯属不饱和中性单体Mlc.l的共聚物。 Examples of suitable cationic polymers P2 is the above monoethylenically unsaturated monomer Mlc.2k and homopolymers and copolymers with monomers Mlc.2k monoethylenically unsaturated neutral monomers Mlc.l copolymer.

    在聚合物P2中特别优选的是对于官能基团RM而言具有的官能度F2 为0.5-3,尤其是0.6-2.5的那些。 In particularly preferred polymers P2 functionality for the purposes of having a functional group F2 of RM 0.5-3, especially 0.6-2.5 those.

    根据常规方法由GPC测定的聚合物P2的数均分子量优选为500-20 000道尔顿,尤其是800-15 000道尔顿。 The polymer P2 according to a conventional method of average molecular weight determined by GPC is preferably 500-20000 Dalton, especially 800-15000 daltons.

    在聚合物P2中尤其优选基于其总重量含有至少50重量%,尤其是至少70重量%,特别优逸至少90重量%氧化乙烯单元的脂族聚醚。 In particularly preferred polymer P2 based on the total weight of at least 50% by weight, in particular at least 70% by weight, particularly preferably at least 90 wt% Yat aliphatic polyethers of ethylene oxide units. 此外, 脂族聚醚可以具有衍生于QrC4烯化氧的结构单元。 In addition, the aliphatic polyethers may have derived from QrC4 alkylene oxide structural units. 聚醚还可以具有不为氢的端基。 Polyethers may also have terminal groups other than hydrogen. 特别优选的聚醚尤其为式III的那些: Particularly preferred polyethers in particular those of formula III:

    Ra-X-(CHRb-CH2-0)pH (III) Ra-X- (CHRb-CH2-0) pH (III)

    其中 Among them

    Ra为氢、d-C2。 Ra is hydrogen, d-C2. 烷基或千基, X为氧或NH, Alkyl or kilobytes group, X is oxygen or NH,

    Rb为氢或甲基,其中至少50mol%,尤其至少70mol%,优选至少90mol% 基团R2为氢, Rb is hydrogen or methyl, wherein at least 50mol%, especially at least 70mol%, preferably at least 90mol% group R2 is hydrogen,

    p为平均值为10-500,优选20-250,尤其是25-100的整数(数均)。 p is an average of 10-500, preferably 20-250, particularly 25-100 integer (number average).

    本领域熟练技术人员熟知合适的亲水性聚合物P2且它们中的大多数 Skilled personnel familiar with suitable hydrophilic polymers P2 and most of them

    可以市购,例如以商品名Plurio^和Pluronic逸(BASF Aktiengesellschaft的 It is commercially available, for example under the trade name Plurio ^ and Pluronic Yat (BASF Aktiengesellschaft of

    聚醚)、Sokalan®、 Kollidon⑧(单体M2a、 M2b和Mlc.2k的均聚物和共聚 Polyether), Sokalan®, Kollidon⑧ (monomers M2a, M2b and Mlc.2k of homopolymers and copolymers

    物)市购,或者它们可以通过标准方法制备。 Thereof) are commercially available, or they can be prepared by standard methods.

    疏水性聚合物Pl在两亲性聚合物组合物中的总比例,即反应的和未 Pl total proportion of hydrophobic polymers in the amphiphilic polymer composition, namely the reaction and not

    反应的聚合物P1的总量,基于聚合物P1、聚合物P2和化合物V的总重 The total reaction volume of polymer P1-based polymer P1, polymer P2 and the total weight of the compound V

    量优选为9-卯重量%,尤其是20-68重量%。 Preferably 9-% d wt, especially 20-68 wt%. 亲水性聚合物P2在两亲性聚合物组合物中的总比例,即反应的和未反应的聚合物P2的总量,基于聚合物P1、聚合物P2和化合物V的总重量优逸为9-90重量%,尤其是30-78重量%。 The total proportion of the hydrophilic polymer P2 in the amphiphilic polymer composition that the total amount of the reaction and unreacted polymer P2 based on the total weight of the polymer preferably Plaza P1, P2, and polymer compounds for V 9-90% by weight, in particular 30-78 wt%.

    化合物V在两亲性聚合物组合物中的总比例,即化合物V的总用量, 基于聚合物Pl、聚合物P2和化合物V的总重量优选为1-20重量%,尤其是2-15重量%。 The total proportion of compound V in the amphiphilic polymer composition, i.e., the total amount of the compound V, based on the total weight of the polymer Pl, P2, and polymer compound V is preferably 1 to 20% by weight, in particular 2-15 wt. %.

    聚合物Pl和P2在两亲性聚合物组合物中的重量比优选为1:10-10:1, 尤其是1:4-2.2:1,在每种情况下以用于制备的聚合物的总量计算。 By weight of polymer Pl and P2 in the amphiphilic polymer composition is preferably from 1: 10-10: 1, especially 1: 4-2.2: 1, in each case for the preparation of the polymer total calculations.

    对于异氛酸酯基团而言具有的官能度为至少1.5,尤其是1.5-4.5,特别是1.8-3.5的合适化合物V包括脂族、环脂族和芳族二-和多异氰酸酯以及脂族、环脂族和芳族二异氰酸酯的异氰脲酸酯、脲基甲酸酯、缩脲二酮(uretdione)和缩二脲。 For different atmosphere ester groups having a functionality of at least 1.5, in particular 1.5 to 4.5, in particular 1.8 to 3.5 V Suitable compounds include aliphatic, cycloaliphatic and aromatic di - and polyisocyanates and aliphatic isocyanurate cycloaliphatic and aromatic diisocyanate of isocyanurate, allophanate, uretdione (uretdione) and biuret.

    化合物V优选平均每分子具有1.8-3.5个异氛酸酯基团。 Compound V is preferably 1.8 to 3.5 per molecule ester groups a different atmosphere. 合适化合物V 的实例是芳族二异氰酸酯,如曱苯-2,4-二异氛酸酯,曱苯-2,6-二异氛酸酯, 曱苯-2,4-和2,6-二异氰酸酯的市购混合物(TIM), n-亚苯基二异氛酸酯,3,3,-二苯基-4,4,-亚联苯基二异氰酸酯,4,4,-亚联苯基二异氛酸酯,4,4,-二笨基甲烷二异氰酸酯,3,3,-二氯-4,4,-亚联笨基二异氛酸酯,枯烯2,4-二异氛酸酯,1,5-萘二异氛酸酯,对苯二亚甲基二异氰酸酯,对亚苯基二异氛酸酯, 4-甲氧基-l,3-亚苯基二异氛酸酯,4-氯-l,3-亚苯基二异氰酸酯,4-乙氧基-1,3-亚苯基二异氰酸酯,2,4-二亚甲基-1,3-亚苯基二异氰酸酯,5,6-二曱基-1,3-亚苯基异氰酸酯,2,4-二异氰酸酯基二苯基醚,脂族二异氛酸酯,如乙撑二异氰酸酯,乙叉二异氰酸酯,亚丙基l,2-二异氰酸酯,1,6-六亚甲基二异氰酸酯,1,4-四亚曱基二异氰酸酯,1,10-十亚甲基二异氰酸酯,以及环脂族二异氛酸酯,如异佛尔酮二异氰酸酯(IPDI)、亚环己基1,2-二异氰酸酉旨、亚环己基l,4-二异氛酸酯和二(4,4,-异氰酸酯基环己基)甲烷。 Examples of suitable compounds V are aromatic diisocyanates, such as benzene-2,4-diisocyanate atmosphere 曱 ester, 曱 benzene-2,6-diisocyanate atmosphere ester, 2,4 and 2,6-benzene 曱commercially available mixture of diisocyanate (TIM), n- phenylene diisocyanate atmosphere ester, 3,3 - diphenyl-4,4, - biphenylene diisocyanate, 4,4 - biphenylene base diisocyanate atmosphere ester, 4,4 - bis stupid methane diisocyanate, 3,3 - dichloro-4,4 - stupid group biphenylene diisocyanate atmosphere ester, 2,4-di-cumene atmosphere ester, 1,5-naphthalene diisocyanate atmosphere esters of xylylene diisocyanate, p-phenylene diisocyanate atmosphere ester, 4-methoxy -l, 3- phenylene diisocyanate atmosphere ester, 4-chloro -l, 3- phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4-methylene-1,3-diphenyl isocyanate, 5,6-Yue-1,3-phenylene diisocyanate, 2,4-diphenyl ether diisocyanate, aliphatic diisocyanate atmosphere esters, such as ethylene diisocyanate, ethylidene diisocyanate, trimethylene l, 2- diisocyanate, hexamethylene diisocyanate, tetramethylene 1,4-diisocyanate Yue group, 1,10 decamethylene diisocyanate, and cycloaliphatic diisocyanates atmosphere esters, such as isophorone diisocyanate (IPDI), 1,2-cyclohexylene diisocyanate unitary purpose, cyclohexylidene l, 4- diisocyanate atmosphere ester and bis (4,4 - isocyanate cyclohexyl) methane. 在这些二异氰酸酯中优选其异氰酸酯基团的反应性不同的那些,如甲苯-2,4-二异氛酸酯、甲苯-2,6-二异氛酸酯、其混合物以及顺式-和反式-异佛尔酮二异氰酸酯。 In these two isocyanate preferably isocyanate groups of different reactivity of those, such as toluene-2,4-diisocyanate atmosphere ester, toluene-2,6-diisocyanate atmosphere ester, mixtures thereof, and cis - and trans - For isophorone diisocyanate.

    在本发明的另一优选实施方案中,将脂族或环脂族二异氰酸酯化合物 In another preferred embodiment of the present invention, the aliphatic or cycloaliphatic diisocyanate compound

    19的缩二脲或异氰脲酸酯,例如四亚甲基二异氰酸酯或六亚甲基二异氰酸酯的氰脲酸酯用于制备本发明的两亲性聚合物组合物。 19 biuret or isocyanurate, such as cyanurate tetramethylene diisocyanate or hexamethylene diisocyanate is used in preparing the amphiphilic polymer composition.

    为了制备本发明的两亲性聚合物组合物,使疏水性聚合物Pl和亲水 To prepare the amphiphilic polymer composition of the present invention, the hydrophobic and hydrophilic polymer Pl

    性聚合物P2依次或同时与化合物V在其中基团RP1和/或RP2与异氰酸酯基团反应形成键的反应条件下反应。 Polymer P2 sequentially or simultaneously with the compound V in which the radicals RP1 and / or RP2 with isocyanate groups under the reaction conditions to form bonds.

    该反应可以在不存在或存在少量促*烷或脲形成的常规催化剂下进行。 The reaction can be carried in the absence or presence of a small amount of conventional catalyst to promote * alkoxy or urea formation were. 合适的催化剂例如是叔胺,如三乙胺、三正丙胺、N-甲基吡咯烷、N-甲基哌啶和二氮杂双环辛烷(DABCO),有机锡化合物,尤其是脂族羧酸的二烷基锡(IV)盐,如二月桂酸二丁基锡和二辛酸二丁基锡,二链烷酸锡(II), 如二辛酸锡,以及铯盐,如乙酸铯。 Suitable catalysts, for example tertiary amines, such as triethylamine, tri-n-propylamine, N- methylpyrrolidine, N- methylpiperidine and diazabicyclooctane (DABCO), organotin compounds, in particular aliphatic carboxylic acid dialkyl tin (IV) salts, such as dibutyltin dilaurate and dibutyltin dioctoate, di alkanoic acid tin (II), such as titanium, tin octylate, and cesium salt, such as cesium acetate. 需要的话,该催化剂基于化合物V以不超过0.1重量%,例如0.01-0.1重量%,尤其至多0.05重量%的量使用。 If necessary, based on the catalyst compound V to not more than 0.1% by weight, e.g., 0.01 to 0.1% by weight, in particular at most 0.05 wt% of amount.

    所需反应温度当然取决于官能基团RW或RP2的反应性以及异氰酸酯化合物V以及若使用话还有所用催化剂的类型和用量。 Of course, depending on the desired reaction temperature RW or RP2 functional groups reactive and isocyanate compound V and the type and amount of use words if there is the catalyst used. 所述温度通常为10-120'C,尤其是15-85匸。 The temperature is usually 10-120'C, especially 15-85 Xi.

    不言而喻的是聚合物Pl和P2与异氰酸酯化合物V的反应在不存在水分下进行(水含量优选<10 OOOppm,尤其〈2000ppm)。 It goes without saying that the polymer Pl and P2 reacted with an isocyanate compound V is carried out in the absence of moisture (water content preferably <10 OOOppm, in particular <2000ppm).

    该反应可以以纯的形式进行或在对化合物V的异氛酸酯基团呈惰性的有机溶剂中进行。 This reaction can be carried out or in the exclusive atmosphere of compound V ester groups inert organic solvent in pure form. 合适溶剂的实例是脂族酮,如丙酮、曱基乙基酮、环己酮,脂族羧酸的烷基酯,如乙酸曱酯、乙酸乙酯、丙酸曱酯、丙酸乙酯、 乙酸正丁酯,脂环族和环状醚,如乙醚、二异丙醚、甲基叔丁基醚、四氩呋喃,芳族、脂族和脂环族烃,如甲苯、二甲苯、己烷、环己烷,还有N-烷基内酰胺,如N-甲基吡咯烷酮,以及这些溶剂的混合物。 Examples of suitable solvents are aliphatic ketones, such as acetone, 曱 ethyl ketone, cyclohexanone, alkyl esters of aliphatic carboxylic acids, such as acetic acid 曱 acetate, ethyl acetate, propionate 曱 acetate, ethyl propionate, n-butyl acetate, alicyclic and cyclic ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetraethylene argon furans, aromatic, aliphatic and alicyclic hydrocarbons, such as toluene, xylene, hexane dioxane, cyclohexane, and the N- alkyl amide, such as methylpyrrolidone, N- and mixtures of these solvents.

    聚合物Pl和聚合物P2与化合物V的反应可以依次或同时进行,即聚合物Pl和P2可以一个接一个与化合物V反应或二者同时与化合物V反应。 Polymer Pl and P2 with the compound V reacted polymer can sequentially or simultaneously, namely a polymer Pl and P2 can take a while to react with compound V with a compound V reaction or both.

    若聚合物Pl和P2 —个接一个与化合物V反应,则可以首先使聚合物P1与化合物V反应,然后使聚合物P2与化合物V反应,反之亦然。 If the polymer Pl and P2 - a contact reaction with the compound V, the polymer may be first reacted with Compound V P1 and the polymer P2 is reacted with compound V, and vice versa.

    若聚合物Pl和P2依次与化合物V反应,则该反应的进行优选应使得在与第一聚合物Pl或P2的反应结束之后,V中的异氰酸酯基团至少10-90mol%,尤其是20-80molY。 If the polymer Pl and P2 in turn is reacted with compound V, then the reaction is preferably carried out such that after completion of the reaction with the first polymer Pl or P2, V of the isocyanate groups of at least 10-90mol%, especially 20- 80molY. 已经与官能基团W和/或I^反应,且存在的异氰酸酯基团中10-90mol%,尤其是20-80mol。 We have functional groups W and / or I ^ reacted with isocyanates and there groups 10-90mol%, especially 20-80mol. /。 /. 仍可利用。 Still available. 然后与第二聚合物P1或P2反应。 And then reacted with a second polymer P1 or P2. 因此,第一聚合物P1或P2的用量优选应佳反应性基团R"和/或R"与每分子V的异氰酸酯基团数的摩尔比为0.1:1-0.9:1, 尤其是0.2:1-0.8:1。 Therefore, the molar ratio of the first polymer P1 or P2 should preferably be a good amount of reactive group R "and / or R" and each molecule V isocyanate number of ester groups of 0.1: 1 - 0.9: 1, especially 0.2: 1 to 0.8: 1. 然后使以此方式得到的产物与第二聚合物反应,其中第二聚合物Pi或P2的用量优选应^良应性基团RP1+RP2的总量至少对应于化合物V的异氰酸酯基团数。 Then the product obtained in this way with a second polymer reaction, wherein the second polymer used is preferably Pi or P2 should be ^ good group RP1 + RP2 corresponds to the total amount of compound V at least the number of isocyanate ester groups. 优选RP1+RP2与异氰酸酯基团的总量之比不超过1.2:1的值。 Preferably RP1 + RP2 than the total amount of the isocyanate groups of no more than 1.2: 1 value.

    若使聚合物Pl和P2同时与异氰酸酯化合物V反应,则聚合物Pl和P2的用量优选应使反应性基团RW+RP2与异氰酸酯基团的摩尔比为至少1:1。 Ruoshi polymer Pl and P2 simultaneously reacted with the isocyanate compound V, the amount of polymer Pl and P2 should preferably be so reactive groups RW + molar ratio RP2 with isocyanate groups is at least 1: 1. 优选RW+RW与异氛酸酯基团的总量之比不超过1.2:1的值。 Preferably RW + RW than the total amount of ester groups and different atmosphere does not exceed 1.2: 1 value.

    在该反应中,异氰酸酯化合物V可以直接使用。 In this reaction, the isocyanate compound V can be used directly. 然而,还可以以其中部分异氰酸酯基团被保护性基团可逆封闭的形式使用异氰酸酯化合物V。 However, it may also be some of the isocyanate groups are reversible protective group closed form isocyanate compound V. 文献中已经描述了许多具有封闭(封端或保护)的异氰酸酯基团的化合物(例如参见ZW Wicks, Prog. Org. Coat. 3(1975) 73-99和9(1981) 3-28或Houben-Weyl, Methoden der Organischen Chemie【有机化学方法j,第XIV/2巻,第61页及随后各页,GeorgThieme Verlag, Stuttgart 1963)。 Many have been described in the literature with a closed (capped or protected) isocyanate group of the compound (see, for example ZW Wicks, Prog. Org. Coat. 3 (1975) 73-99 and 9 (1981) 3-28 or Houben- Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry j, Section XIV / 2 Volume, page 61 and subsequent pages, GeorgThieme Verlag, Stuttgart 1963). 可以提到的异氰酸酯基团封闭试剂的实例是酚类,己内酰胺,咪唑类,吡唑类,吡唑啉酮类,1,2,4-三唑类,二酮基哌溱类,丙二酸酯类和將类。 It may be mentioned isocyanate group blocking reagent examples are phenols, caprolactam, imidazoles, pyrazoles, pyrazolones, 1,2,4-triazole, diketo-piperazine Qin class, malonate esters and class. 然而,为了实现本发明的结果,并不必须使用以可逆方式部分封闭的异氰酸酯。 However, to achieve the results of the present invention, not necessarily use a reversible manner partially closed isocyanate.

    在本发明的特别优选实施方案中,在第一反应步骤中以上述方式通过自由基溶剂聚合制备疏水性聚合物Pl并在所得液体反应混合物中以本文所述方式进行与异氰酸酯V的反应,而不预先分离聚合物P1。 In a particularly preferred embodiment of the present invention, in a first reaction step in the manner described above hydrophobic polymer Pl polymerization by radical solvent and the resultant liquid reaction mixture in the manner described herein react with isocyanates V, and without prior separation of polymer P1. 然后使所得反应混合物与聚合物P2反应,优选与聚醚反应。 The resulting reaction mixture is then reacted polymer P2, is preferably reacted with a polyether. 或者可以将所需量的聚合物P2加入以该方式制备的聚合物Pl中,然后与化合物V反应。 Or may be added to the required amount of polymer P2 Pl polymer prepared in this manner, and then reacted with compounds V.

    为了制备含水活性化合物配制剂,可以将根据本发明得到的聚合物组合物与反应混合物分离。 To prepare an aqueous active compound formulation, according to the present invention can be separated polymer composition obtained from the reaction mixture. 然而,还可以直接使用该反应混合物。 However, it also can be used directly in the reaction mixture.

    在本发明的优选实施方案中,将用于制备聚合物组合物的溶剂部分或完全用水置换,得到两亲性聚合物组合物的水分軟体。 In a preferred embodiment of the present invention, a part of the solvent for the preparation of the polymer composition or completely replaced with water to give the amphiphilic polymer composition water software. 这例如可以通过首 This example can be the first

    以将水加入聚合物组合物的溶液中并在加入水之后或同时除去溶刑。 Water was added to the polymer composition of the solution and solvent removed punishment or after the addition of water at the same time.

    本发明的活性化合物或有效物质组合物可以通过不同途径制备。 Active compound or active substance compositions of the invention may be prepared by different routes. 通常 General

    亲性聚合物组合物和至少一种活性化合物和/或有效物质的均相非水混合物。 Amphiphilic polymer composition and at least one active compound and / or homogeneous non-aqueous mixture of active substance.

    在本发明的第一实施方案中,含水活性化合物组合物通过首先制备包含两亲性聚合物组合物和活性化合物和/或有效物质的均相非水混合物并 In a first embodiment of the present invention, the aqueous active compound composition is prepared by first comprising amphiphilic polymer composition of the active compound and / or a non-aqueous homogeneous mixture of the active substance and

    随后将所得混合物^Ht在水或含水介质中而制备。 The resulting mixture is then ^ Ht in water or an aqueous medium is prepared. 为了制备均相非水混合物,通常将活性化合物掺入两亲性聚合物组合物的液态形式如熔体或优选在有机溶剂中的溶液中。 For preparing a homogeneous nonaqueous mixture, the active compound is generally incorporated in the form of liquid amphiphilic polymer composition as a melt or preferably in an organic solvent solution. 若使用溶剂,则随后基本上,优选完全除去该溶剂,得到活性化合物在两亲性聚合物组合物中的固溶液。 If a solvent is used, it is then substantially, preferably completely removing the solvent, to give a solid solution of the active compound in the amphiphilic polymer composition. 适于该目的的溶剂原则上是能够溶解活性化合物和聚合物二者的那些,例如脂族腈类如乙 On principle suitable for this purpose are solvents capable of dissolving both the active compound and the polymer that, for example, aliphatic nitriles such as acetic

    腈和丙腈,脂族羧酸的N,N-二烷基酰胺如二甲基甲酰胺和二甲基乙酰胺, N-烷基内酰胺如N-甲基吡咯烷酮,上述脂族和脂环族醚,例如四氩吹喃, 囟代烃类如二氯甲烷、二氯乙烷,以及上述溶剂的混合物。 Nitrile and propionitrile, aliphatic carboxylic acids of N, N- dialkylamides such as dimethylformamide and dimethylacetamide, the alkyl amides such as N- N- methylpyrrolidone, said aliphatic and alicyclic aliphatic ethers, e.g., four blow argon furans, halogenated hydrocarbons such as dichloromethane, dichloroethane, and mixtures of the above solvents. 为了制备本发明的含水组合物,然后通过在含水介质中搅拌而分散所得活性化合物在两亲性聚合物组合物中的固溶液。 To prepare the aqueous compositions of the present invention, and then by stirring in an aqueous medium and dispersing the resulting solution of the active compound in solid amphiphilic polymer composition. 搅拌可以在室温或升温下进行,例如在10-8(TC,尤其是20-50'C的温度下进行。 Stirred at room temperature or elevated temperatures may be, for example, 10-8 (especially 20-50'C temperatures TC conducted.

    在本发明的第二实施方案中,通过将活性化合物和/或有效物质掺入两 In a second embodiment of the present invention, by incorporating the active compound and / or the incorporation of two active substances

    通常通过在高于活性化合物或有效物质的熔点的温度下,优选在其中活性化合物或有效物质熔体具有低粘度,即粘度为l-1000mPa.s(根据DIN 53019-2, 25。C)的温度下进行掺入而实现。 Typically by at temperatures above the active compound or active substance of melting point, preferably in which the active compound or the active substance having a low melt viscosity, i.e. a viscosity of l-1000mPa.s (according to DIN 53019-2, 25.C) of It is achieved at a temperature of incorporation. 掺入优选使用强剪切力进行, 例如在Ultraturrax中进行。 Incorporation is preferred to use a strong shearing force, for example in the Ultraturrax.

    在本发明的第三实施方案中,通过包括包括下列步骤ac的方法制备含水活性化合物组合物: In a third embodiment of the present invention, by a process comprising a method comprising the steps ac for preparing an aqueous active compound composition:

    a)制备活性化合物和/或有效物质和合适的话两亲性聚合物组合物在沸点 a) Preparation of active compounds and / or active substances and, if appropriate, amphiphilic polymer composition at the boiling point

    22低于水的沸点的有机溶剂中的溶液, b)将活性化合物和/或有效物质的溶液与水或两亲性共聚物的水溶液混合, 22 below the boiling point of water an organic solvent solution, b) an aqueous solution of active compounds and / or active substance solution with water or a mixture of amphiphilic copolymer,

    And

    C)除去溶剂。 C) the solvent was removed.

    或者这可以以如下方式进行,其中活性化合物的溶液包含两亲性聚合物组合物,并将该溶液与水混合,或者其中活性化合物的溶液仅包含部分两亲性聚合物组合物或不包含两亲性聚合物组合物,并将该溶液与两亲性聚合物组合物的水溶液或水M体混合。 Alternatively it may be carried out in the following manner, wherein the solution containing the active compound amphiphilic polymer composition, and the solution was mixed with water, or a solution in which the active compound comprises only part of the amphiphilic polymer composition comprises two or amphiphilic polymer composition, and the solution was mixed with the amphiphilic polymer composition M aqueous solution or water bodies. 混合可以在合适的搅拌容器中进行,其中可以首先加入水或两亲性聚合物组合物的水溶液并加入活性化合物或有效物质的溶液,或者首先加入活性化合物或有效物质的溶液并加入水或两亲性聚合物组合物的水溶液。 The mixing can be carried out in an appropriate mixing container, which can be added first water solution or amphiphilic polymer composition and added to the solution of the active compound or the active substance, or by first adding the active compound solution or the active substance and water or both an aqueous solution of amphiphilic polymer composition. 然后例如通过蒸馏除去有机溶剂,其中合适的话加入水。 For example, the organic solvent is then removed by distillation, where appropriate, the addition of water.

    在该实施方案的优选方案中,将活性化合物溶液和水或两亲性聚合物组合物的水溶液连续加入混合区,并将随后从中除去溶剂的混合物从该混合区中连续取出。 In a preferred embodiment of this embodiment, the active compound solution and water or an aqueous solution of an amphiphilic polymer composition continuously into a mixing zone, and then the solvent was removed therefrom mixture continuously withdrawn from the mixing zone. 混合区可以按需设计。 Mixing zones can be designed on demand. 原则上讲,所有允许液体料流连 In principle, all allow liquid material to hang around

    续混合的设备适于该目的。 Continued mixing device suitable for this purpose. 该设备例如由Continuous Mixing of Fluids(J,H. Henzler), Ullmann,s Encyclopedia,第5版(CD-Rom), Wiley-VCH已知。 The device, for example by a Continuous Mixing of Fluids (J, H. Henzler), Ullmann, s Encyclopedia, 5th edition (CD-Rom), Wiley-VCH known. 混合区可以设计成静态或动态混合器或其混合形式。 Mixing zones can be designed into a static or dynamic mixer or mixed form. 合适的混合区尤其还有喷射混合器或具有喷嘴的类似混合器。 Suitable mixing zone in particular, there have jet mixer or similar mixer nozzle. 在优选实施方案中,混合区为"Handbook of Industrial Crystallization ,, (AS Myerson , 1993 Butterworth-Heinemann,第139页,ISBN 0-7506-9155-7)中所述的设备或类似设备。 In a preferred embodiment, the mixing zone to "Handbook of Industrial Crystallization ,, (AS Myerson, 1993 Butterworth-Heinemann, p. 139, ISBN 0-7506-9155-7) in the device or the like.

    活性化合物溶液与水或两亲性聚合物组合物的水溶液的体积比可以在宽范围内变化且优选为10:1-1:20,尤其是5:1-1:10。 The volume ratio of aqueous solutions of the active compound with water or a solution of amphiphilic polymer composition may vary within wide limits and is preferably 10: 1-1: 20, in particular 5: 1-1: 10.

    溶剂的性质应使得两亲性聚合物组合物和活性化合物以所需比例溶解。 Amphiphilic polymer composition and active compound such that the nature of the solvent to dissolve the desired ratio. 本领域熟练技术人员可以通过标准试验确定合适的溶剂。 Those skilled in the art can determine a suitable solvent by standard tests. 合适溶剂的实例是CVC4链烷醇,如乙醇、正丙醇、正丁醇、异丁醇,上述脂族和脂环族醚,如乙醚、二异丙醚、甲基叔丁基醚、二喷、烷、四氩呋喃,酮类如丙酮、甲基乙基酮。 Examples of suitable solvents are CVC4 alkanols, such as ethanol, n-propanol, n-butanol, isobutanol, said aliphatic and cycloaliphatic ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, di spray, alkoxy, four argon furan, ketones such as acetone, methyl ethyl ketone. 在本发明的另一实施方案中,通过制备两亲性聚合物组合物和活性化 In another embodiment of the present invention by amphiphilic polymer composition and activation

    该組合物不含任何液体組分,;它通常为固体。 The composition does not contain any liquid component; it is usually as a solid. 对于该类組合物的制备, 上面就制备包含两亲性聚合物组合物和活性化合物和/或有效物质的均相 For preparing such compositions, above it prepared comprising amphiphilic polymer compositions containing the active compound and / or homogeneous and the active substance

    非水混合物的第一实施方案所作的描述以类似方式适用;然而,在该阶段合适的话可以以本身已知的方式将所需添加剂和辅助剂掺入该组合物中。 Description of the first embodiment of the non-aqueous mixture made applicable in a similar manner; however, at this stage, if appropriate, may be required in a manner known per se additives and adjuvants incorporated into the composition. 该方案特别适于制备非水组合物。 This solution is particularly suitable for preparing non-aqueous composition.

    有效物质与两亲性聚合物组合物的重量比为1:10-3:1,尤其是1:5-2:1。 By weight of the active substance and the amphiphilic polymer composition ratio is 1: 10-3: 1, especially 1: 5-2: 1.

    活性化合物和/或有效物质的含量可以在宽范围内变化。 Content of the active compound and / or the active substance can vary within a wide range. 具体而言,使用两亲性聚合物组合物可以制备活性化合物浓缩物,其基于组合物的总重量以至少5重量%,例如5-50重量%,尤其是5-20重量%的量包含活性化合物。 Specifically, the use of an amphiphilic polymer composition concentrates the active compound may be prepared, based on the total weight of the composition of at least 5% by weight, e.g., 5-50 wt.%, Particularly 5-20 wt% of an amount comprising active compound.

    有利的是,本发明組合物,尤其是含水活性化合物组合物可以配制成无溶剂或低溶剂组合物,即挥发性组分在活性化合物组合物中的比例基于该组合物的总重量通常不超过10重量%,尤其是不超过5重量%,特别是不超过1重量%。 Advantageously, the compositions of the present invention, in particular an aqueous active compound composition can be formulated as solvent-free or low-solvent composition, i.e., the proportion of volatile components in the composition of the active compound based on the total weight of the composition, usually not more than 10% by weight, particularly not more than 5% by weight, particularly not more than 1 wt%. 这里的挥发性组分为其在大气压力下的沸点低于200'C 的那些。 Here's its boiling point volatile components at atmospheric pressure is lower than 200'C those.

    可以在本发明组合物中配制大量不同的活性化合物和有效物质。 It can be prepared a number of different active substances and active compounds in the compositions of the present invention. 本发明的特殊实施方案涉及用于作物保护的活性化合物如除草剂、杀真菌剂、 杀线虫剂、杀螨剂、杀虫剂以及调节植物生长的活性化合物的配制。 Particular embodiments of the present invention relates to active compounds for crop protection, such as herbicides, fungicides, formulated nematicides, miticides, insecticides and plant growth regulating active compounds.

    可以配制成本发明活性化合物组合物的杀真菌活性化合物的实例包 Examples packet invention the active compound may be formulated into compositions fungicidally active compound

    括: Including:

    -酰基丙氨酸类,例如苯霜灵(benalaxyl)、甲霜灵(metalaxyl)、曱呋酰胺 - Acylalanines, such as benalaxyl (benalaxyl), metalaxyl (metalaxyl), Yue ofurace

    (ofurace)、巧悉霜灵(oxadixyl), '胺衍生物,例如4-十二烷基-2,6-二甲基吗啉(aldimorph)、多果定(dodine)、 (Ofurace), Qiao noted Cream Spirit (oxadixyl), 'amine derivatives, such as 4-dodecyl-2,6-dimethyl morpholine (aldimorph), Dodine (dodine),

    吗菌灵(dodemorph)、 丁苯吗淋(fenpropimorph)、苯锈淀(fenpropidin)、 It benomyl (dodemorph), styrene-butadiene you pour (fenpropimorph), fenpropidin lake (fenpropidin),

    双胍盐(guazatine)、 双胍辛醋酸盐(iminoctadine)、 螺嗜、茂胺 Guazatine (guazatine), Iminoctadine acetate (iminoctadine), Lo addicted, Mao amine

    (spiroxamine)、 克琳菌(tridemorph),苯胺基嘧咬类,例如二甲嘧菌胺(pyrimethanil)、嘧菌胺(m印anipyrim) 或环丙嘧啶(cyprodinil), (Spiroxamine), Jacqueline bacteria (tridemorph), aniline ethyl bite classes, such as dimethyl mepanipyrim (pyrimethanil), mepanipyrim (m India anipyrim) or cyproterone pyrimidine (cyprodinil),

    抗菌素,例如放线菌酮(cycloheximide)、灰黄霉素(griseofulvin)、春雷素(kasugamycin)、多马霉素(natamycin)、多氧霉素(polyoxin)、链霉素(streptomycin)或井冈霉素(validamycin A), Antibiotics, such as CHX (cycloheximide), griseofulvin (griseofulvin), Jubilee hormone (kasugamycin), Thomas ADM (natamycin), Polyoxins (polyoxin), streptomycin (streptomycin) or Jinggangmycin mold Su (validamycin A),

    唑类,例如双苯三唑醇(bitertanol)、糠菌哇(bromoco眼ole)、氰霜唑(cyazofamid)、 环峻醇(cyproconazole)、 鳴醜峻(difenoconazole)、 烯峻醇(dinitroconazole)、氧峻菌(epoxiconazole)、氯峻灵(etridazole)、腈苯喳(fenbuconazole)、奮峻菌酮(fluquinconazole)、氟珪峻(flusilazole)、粉哇醇(flutriafoi)、麦穗宁(fuberidazole)、己唑醇(hexaconazole)、 土菌消(hymexazole)、烯菌灵(imizalil)、环戊唑醇(ipconazole)、酰胺唑(imibenconazole)、环戊峻菌(metconazole)、腈菌哇(myclobutanil)、戊菌喳(penconazole) 、 perfuazorate 、 丙环峻(propiconazole)、 丙氯灵(prochloraz)、丙硫菌峻(prothioconazole)、珪氟峻(simeconazole)、戊喳醇(tebuconazole)、氟醚喳(tetraconazole)、弟必灵(thiabendazole)、三峻酮(triadimefon)、唑菌醇(triadimenol)、氟菌唑(triflumizole)、戊叉唑菌(triticonazole)、 2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、N,N-二甲基-3-(3-澳-6_氟_2-曱基吲哚-1-磺酰基)-[1,2,4】三唑-1-磺酰胺; Azoles, such as bitertanol (bitertanol), bran bacteria wow (bromoco eye ole), Cyazofamid (cyazofamid), ring Jun alcohol (cyproconazole), Ming ugly Jun (difenoconazole), Jun-ene-ol (dinitroconazole), Oxygen Jun bacteria (epoxiconazole), chlorine Jun Ling (etridazole), nitrile benzene twitter (fenbuconazole), Fen Jun cycloheximide (fluquinconazole), fluorine Gui Jun (flusilazole), powder wow alcohol (flutriafoi), fuberidazole (fuberidazole), Hexaconazole (hexaconazole), hymexazol (hymexazole), ene benomyl (imizalil), cyclopentyl Hexaconazole (ipconazole), amide azole (imibenconazole), cyclopentyl Jun bacteria (metconazole), myclobutanil wow (myclobutanil), E bacteria twitter (penconazole), perfuazorate, propiconazole Jun (propiconazole), prochloraz (prochloraz), prothioconazole Jun (prothioconazole), fluorine Gui Jun (simeconazole), amyl alcohol cha (tebuconazole), isoflurane twitter (tetraconazole ), brother Weibiling (thiabendazole), three Jun ketone (triadimefon), Triadimenol (triadimenol), triflumizole (triflumizole), E fork azole bacteria (triticonazole), 2- butoxy-6-iodo-3 propyl-benzopyran-4-one, N, N- dimethyl-3- (3-fluoro-O -6_ _2- Yue-yl-indol-1-sulfonyl) - [1,2,4] triazol-1-sulfonamide;

    .在EP-A 897904中以式I描述的2-甲氧基二苯甲酮,例如苯菌酮(metrafenone); . 2-Methoxy in EP-A 897904 to formula I as described benzophenones, e.g. metrafenone (metrafenone);

    -二羧酰亚胺类,如异丙定(iprodione)、曱菌利(myclozolin)、杀菌利(procymidone)、烯菌5同(vinclozolin), - Dicarboximide class, such as isopropyl set (iprodione), Yue bacteria Lee (myclozolin), procymidone (procymidone), 5-ene with bacteria (vinclozolin),

    -二硫代氨基甲酸盐类,如福美铁(ferbam)、代森钠(nabam)、 «森锰(maneb)、代森锰锌(mancozeb)、威百亩(metam)、代森联(metiram)、 甲基代森锌(propineb)、福代锌(polycarbamate)、福美双(thiram)、福美锌(ziram)、代森锌(zineb), - Dithiocarbamate salts such as ferbam (ferbam), Dyson sodium (nabam), «Sen manganese (maneb), mancozeb (mancozeb), metam sodium (metam), metiram (metiram ), methyl zineb (propineb), zinc Fordyce (polycarbamate), thiram (thiram), ziram (ziram), Zineb (zineb),

    •杂环化合物,如敌菌灵(anilazine)、苯菌灵(benomyl)、啶酰菌胺(boscalid)、 多菌灵(carbendazim)、萎锈灵(carboxin)、氧化萎锈灵(oxycarboxin)、 氰霜唑(cyazofamid)、棉隆(dazomet)、 二噻农(dithianon)、乙菌定(ethirimol)、甲菌定(dimethirimol)、 ^悉唑酮菌(famoxadone)、咪i菌酮(fenamidone)、 异嘧菌醇(fenarimol)、 麦穗宁(fuberidazole)、 氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、稻瘟灵(isoprothiolane)、丙氧灭綉胺(mepronil)、氟苯嘧咬醇(nuarimol)、异镶菌酮(octhiUnone)、氟吡菌胺(picobenzamid)、逸菌灵(probenazole)、丙氧会淋(proquinazid)、咬斑將(pyrifenox)、咯壹酮(pyroquilon)、会氧灵(quinoxyfen)、硅塞菌胺(silthiofam)、弟必灵(thiabendazole)、溴氟唑菌(thifluzamide)、曱基托布津(thi叩hanate-methyl)、漆酰菌胺(tiadinil)、三环唑(tric》clazok)、唤氨灵(triforine) 、 3-[5-(4-氯苯基)-2,3-二甲基异喷'唑烷-3-基l吡啶和磺嘧菌灵(b叩irimate); • heterocyclic compounds, such as anilazine (anilazine), benomyl (benomyl), boscalid (boscalid), carbendazim (carbendazim), carboxin (carboxin), the oxidation carboxin (oxycarboxin), Cyazofamid (cyazofamid), dazomet (dazomet), dithianon (dithianon), acetic bacteria fixed (ethirimol), A bacteria fixed (dimethirimol), ^ noted trazodone bacteria (famoxadone), Mi i cycloheximide (fenamidone) , different triarimol (fenarimol), fuberidazole (fuberidazole), flutolanil (flutolanil), furosemide pyrazole Spirit (furametpyr), Isoprothiolane (isoprothiolane), propoxyphene off embroidered amine (mepronil), fluorophenyl ethyl bite alcohol (nuarimol), different inserts cycloheximide (octhiUnone), Fluopicolide (picobenzamid), Yi benomyl (probenazole), propoxyphene would drench (proquinazid), the bite spot (pyrifenox), slightly One ketone (pyroquilon), Ling will be oxygen (quinoxyfen), silicon plug bacteria amine (silthiofam), brother Weibiling (thiabendazole), thifluzamide (thifluzamide), Zadjituobu Jin (thi knock hanate-methyl), paint acid bacteria amine (tiadinil), tricyclazole (tric "clazok), call ammonia Ling (triforine), 3- [5- (4- chlorophenyl) -2,3-dimethyl-iso spray 'oxazolidine-3-yl l pyridine and pyrimidine sulfonamide benomyl (b knock irimate);

    .硝基苯基衍生物,如乐杀螨(binapacryl)、敌螨普(dinocap)、敌螨通(dinobuton)、异丙消(nitrophthal-isopropyl); Nitrobenzene derivatives, such as binapacryl (binapacryl), dinocap (dinocap), enemy mites through (dinobuton), isopropyl elimination (nitrophthal-isopropyl);

    .苯基吡咯类,如拌种咯(fenpiclonil)和氟嗜'菌(fludioxonil); Phenyl azoles, such as fenpiclonil (fenpiclonil) and fluorine addicted 'bacteria (fludioxonil);

    .不属于任何其他类别的杀真菌剂,如噻二唑素(acibenzolar-S-methyl)、 苯噢菌胺(benthiavalicarb)、 氯环丙酰胺(carpropamid)、 百菌清(chlorothalonil)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、歧菌清(didomezine)、双氯氰菌胺(diclocymet)、乙霉威(diethofencarb)、克瘟散(edifenphos)、嚷唑菌胺(ethaboxam)、环酰菌胺(fenhexamid)、薯瘟锡(fentin-acetate)、氰菌胺(fenoxanil)、嘧菌腙(ferimzone)、氟啶胺(fluazinam)、 藻菌磷(fosetyl)、 乙膦铝(fosetyl-alu minum)、异丙菌胺(iprovalicarb)、六氣笨(hexachlorobenzol)、苯菌酉同(tnetrafenone)、戊菌隆(pencyeuron)、百维灵(propamocarb)、四氯苯酞(phthalide)、甲基立枯磷(toldofos國methyl)、五氯硝基苯(quintozene)、苯酰菌胺(zoxamide)、 稻瘟灵(isoprothiolane) 、 fluopicolide(氟p比菌胺);氯环丙酰胺(carpropamid)、双炔酰菌胺(mandipropamid)、 ]\-(2-{4-[3-(4-氯苯基)丙-2-炔基氧基】-3-甲氧苯基}乙基)-2-甲基磺酰氨基-3-甲基丁酰胺、 3\-(2-{4-[3-(4-氯苯基)丙-2-炔基氧基】-3-甲氧苯基}乙基)-2-乙基磺酰氨基-3-甲基丁酰胺;吹吡唑灵(furametpyr)、溴氟唑菌(thifluzamide)、吡绻菌胺(penthiopyrad)、环酰菌胺(fenhexamid)、 N-(2-氰基苯基)-3,4-二氯 Not belonging to any other class of fungicides, such as acibenzolar (acibenzolar-S-methyl), benzene Oh bacteria amine (benthiavalicarb), chlorine cyclopropane amide (carpropamid), chlorothalonil (chlorothalonil), ring fluorine bacteria amine (cyflufenamid), cymoxanil (cymoxanil), manifold bacteria Qing (didomezine), double cyanuric bacteria amine (diclocymet), diethofencarb (diethofencarb), g blast scattered (edifenphos), cried bacteria yl amine (ethaboxam), fenhexamid (fenhexamid), potato plague tin (fentin-acetate), Fenoxanil (fenoxanil), azoxystrobin hydrazone (ferimzone), Fluazinam (fluazinam), phycomycetes phosphorus (fosetyl), fosetyl aluminum (fosetyl -alu minum), iprovalicarb (iprovalicarb), six gas stupid (hexachlorobenzol), benomyl unitary with (tnetrafenone), pencycuron (pencyeuron), Broadway Ling (propamocarb), four chlorobenzene phthalate (phthalide), tolclofos (toldofos country methyl), PCNB (quintozene), zoxamide (zoxamide), Isoprothiolane (isoprothiolane), fluopicolide (p-fluoro amine than bacteria); chlorine cyclopropane amide (carpropamid ), diacetylene amine acid bacteria (mandipropamid),] \ - (2- {4- [3- (4- chlorophenyl) prop-2-yn-yloxy] -3-methoxy phenyl} ethyl) -2-methyl-3- methylbutanamide, 3 \ - (2- {4- [3- (4-chlorophenyl) prop-2-yn-yloxy] -3-methoxy benzene yl} ethyl) -2-ethyl-3- methylbutanamide; blow-pyrazol spirit (furametpyr), thifluzamide (thifluzamide), topiramate quan bacteria amine (penthiopyrad), fenhexamid ( fenhexamid), N- (2- cyanophenyl) -3,4-dichloro-

    26异噢唑-5-甲酰胺、flubenthiavalicarb、 3-(4-氯苯基)-3-(2-异丙氧羰基氨基-3-甲基丁酰氨基)丙酸甲酯、{2-氯-5-【1-(6-甲基吡啶-2-基甲氧亚氨基) 乙基】苄基}氨基甲酸甲酯、{2-氯-5-[1-(3-甲基苄氧亚氨基)乙基】苄基}氨基曱酸甲酯、磺菌胺(flusulfamide)、下式的酰胺: 26 different Oh-5-carboxamide, flubenthiavalicarb, 3- (4- chlorophenyl) -3- (2-isopropoxycarbonyl-amino-3-methylbutyrylamino) propionate, {2-chloro -5- [1- (6-methyl-pyridin-2-yl-methoxy imino) ethyl] benzyl} carbamic acid methyl ester, {2-chloro-5- [1- (3-methyl-benzyloxyimino amino) ethyl] benzyl} amino Yue methyl flusulfamide (flusulfamide), amides of the formula:

    R1, R2 其中 R1, R2 wherein

    X为CHF2或CH3;和 X is CHF2 or CH3; and

    R1、 RM目互独立地为卤素、甲基或卤代曱基,例如CF3; 由WO 03/075663以通式I描述的嗜球果伞素类(strobilurins),如腈嘧菌酉旨(azoxystrobin)、醜菌胺(dimoxystrobin)、 氟嗜菌酉旨(fluoxastrobin)、 亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、辨醚菌胺(orysastrobin)、咬氧菌酉旨(picoxystrobin)、峻菌胺酉旨(pyraclostrobin)和將菌酉旨(trifloxystrobin), R1, RM head independently of each other halogen, methyl or halo 曱 group, e.g., CF3; strobilurin class (strobilurins) WO 03/075663 by the general formula I described, such as nitrile azoxystrobin unitary purpose (azoxystrobin ), ugly fungus amine (dimoxystrobin), fluorine bacteriophora unitary purpose (fluoxastrobin), imide bacteria (kresoxim-methyl), fork benzamide (metominostrobin), identified bacteria ether amine (orysastrobin), bite aerobic bacteria unitary purpose (picoxystrobin ), Jun bacteria amine unitary purpose (pyraclostrobin) and the bacteria unitary purpose (trifloxystrobin),

    次磺酸衍生物,如敌菌丹(captafol)、克菌丹(captan)、抑菌灵(dichlofluanid)、灭菌丹(folpet)、对甲抑菌灵(tolylfluanid); 肉桂酰胺及类似化合物,如烯酰吗啉(dimethomorph)、氟联苯菌(flumetover)、 氟吗淋(flumorph); Sulfenic acid derivatives, such as captafol (captafol), captan (captan), antibacterial Ling (dichlofluanid), folpet (folpet), for tolylfluanid (tolylfluanid); cinnamide and similar compounds, As Dimethomorph (dimethomorph), flurbiprofen bacteria (flumetover), flumorph leaching (flumorph);

    例如在每种情况下由WO 98/46608、 WO 99/41255或WO 03/004465以式I描述的6-芳基[l,2,4I三唑并[l,5-a】嘧啶,例如5-氯-7-(4-曱基哌咬-1-基)-6-(2,4,6-三氟苯基)-[l,2,41三唑并[l,5-a】嘧啶; 酰胺杀真菌剂,如cyclofenamid以及(Z)-N-[oK环丙基曱氧亚氛基)-2,3-二氟-6-(二氟甲氧基)千基j-2-苯基乙酰胺。 For example, in each case by the WO 98/46608, WO 99/41255 or WO 03/004465 formula I described 6-aryl [l, 2,4I triazolo [l, 5-a] pyrimidine, 5 e.g. - chloro-7- (4-yl piperazine Yue bite-yl) -6- (2,4,6-trifluoro-phenyl) - [l, 2,41 triazolo [l, 5-a] pyrimidine ; amide fungicides, such as cyclofenamid and (Z) -N- [oK cyclopropyl Yue oxyalkylene atmosphere yl) -2,3-difluoro-6- (difluoromethoxy) phenyl j-2- one thousand group acetamide.

    1,3,4-噢二唑类,如草噢咪(buthidazole)和环唑草胺(cyprazole); 酰胺类,如草毒死(allidochlor)、新燕灵(benzoylprop-ethyl)、溴丁酰草胺(bromobutide)、草克乐(chlorthiamid)、 p底草丹(dimepiperate)、嚷喻草胺(dimethenamid)、草乃敌(diphenamid)、 乙苯酰草(etobenzanid)、 甲氟燕灵(flamprop-methyl)、膦铵素(fosamine)、异恶草胺(isoxaben)、 吡草胺(metazachlor)、杀草利(monalide)、抑草生(naptalam)、拿草特(pronamide)、敌稗(propanil); Oh, 1,3,4-oxadiazole class, such as grass Oh Mi (buthidazole) and Epoxiconazole alachlor (cyprazole); amides, such as grass poisoned (allidochlor), the new Yan Ling (benzoylprop-ethyl), bromine butyrylcholinesterase metolachlor (bromobutide), grass Kele (chlorthiamid), p bottom Caodan (dimepiperate), Yu shouted alachlor (dimethenamid), grass is the enemy (diphenamid), ethylbenzene acid grass (etobenzanid), mefloquine Yan Ling (flamprop -methyl), phosphine ammonium hormone (fosamine), isoxaben (isoxaben), metazachlor (metazachlor), herbicide Lee (monalide), naptalam (naptalam), take special grass (pronamide), propanil (propanil );

    .氨基磷酸类,如双丙氨酰膦(bilanafos)、特克草(buminafos)、草铵膦(glufosinate-ammonium)、草甘膦(glyphosate)、草石克膦(sulfosate); . Amino phosphoric acids, such as bialaphos phosphine (bilanafos), Turk grass (buminafos), glufosinate (glufosinate-ammonium), glyphosate (glyphosate), grass-grams of phosphine (sulfosate);

    .氨基三唑类,如杀草强(amitrole); . Amino triazoles, such as amitrole (amitrole);

    .酰替苯胺类,如莎稗磷(anilofos)、苯噢草胺(mefenacet); . Anilide class, such as anilofos (anilofos), benzene Oh alachlor (mefenacet);

    .芳氧基链烷酸,如2,4滴(2,4-D)、 2,4-滴丁酸(2,4-DB)、稗草胺(clomeprop)、 2,4-滴丙酸(dichlorprop)、高2,4-滴丙酸(dichlorpr叩-P)、 2,4,5-滴丙酸(fenoprop)、氟草烟(fhiroxypyr)、 2甲4氯(MCPA)、 2甲4氯丁酸(MCPB)、 2甲4氯丙酸(mecoprop)、高2甲4氯丙酸盐(mecoprop-P)、 草萘胺(napropamide)、敌草胺(napropanilide)、定草酯(tHclopyr); . Aryloxy alkanoic acids, such as 2,4-D (2,4-D), 2,4- drop butyric acid (2,4-DB), barnyard grass amine (clomeprop), 2,4- Dichlorprop (dichlorprop), high dichlorprop (dichlorpr knock -P), 2,4,5- Dichlorprop (fenoprop), fluroxypyr (fhiroxypyr), 2 MCPA (MCPA), 2 A 4 Neoprene acid (MCPB), 2 mecoprop (mecoprop), 2 A 4-chloropropyl high salt (mecoprop-P), Napropamide (napropamide), Napropamide (napropanilide), fixed-mexyl (tHclopyr );

    .苯甲酸类,如草灭平(chloramben)、麦草畏(dicamba); . Benzoic acid, such as grass off level (chloramben), dicamba (dicamba);

    .苯并漆二唤酮类,如嚷草平(bentazone); Benzo paint two call ketones, such as shouting grass flat (bentazone);

    '漂白剂,如异恶草酮(clomazone)、吡氟草胺(diflufenican)、氟咯草酮 'Bleaching agents, such as clomazone (clomazone), diflufenican (diflufenican), fluorine slightly oxadiazon

    (fluorochloridone)、胺草唑(flupoxam)、氟草同(fluridone)、吡唑特 (Fluorochloridone), amine grass azole (flupoxam), fluoride grass with (fluridone), pyrazolate

    (pyrazolate)、磺草酉同(sulcotrione); .氨基甲酸酯类,如长杀草(carbetamide)、氯草灵(chlorbufam)、氯苯胺 (Pyrazolate), sulcotrione unitary with (sulcotrione);. Carbamates, such as long-herbicide (carbetamide), chlorine grass Ling (chlorbufam), chloroaniline

    灵(chlorpropham)、异苯敌草(desmedipham)、苯敌草(phe證edipham)、 Ling (chlorpropham), different phenmedipham (desmedipham), phenmedipham (phe card edipham),

    灭草猛(vernolate); .会啉酸类,如二氯全啉酸(quinclorac)、全草酸(quinmerac); .二氟丙酸类,如茅草枯(dalapon); .二氢苯并吹喃类,如乙呋草黄(ethofumesate); -二氢呋喃-3-酮类,如呋草酮(flurtamone); Herbicides Meng (vernolate);. Will morpholino acids, such as methylene full Quinclorac (quinclorac), full of oxalic acid (quinmerac);. Difluoromethyl propionic acids, such as dry grass (dalapon);. Dihydrobenzofuran blow furans class, such as ethylene furosemide grass yellow (ethofumesate); - dihydrofuran-3-ones, such as flurtamone (flurtamone);

    -二硝基苯胺类,如氟草胺(benefin)、地乐胺(butralin)、敌乐胺(dinitramine)、 丁氟消草(ethalfluralin)、氟消草(fluchloralin)、异乐灵(isopropalin)、 橫乐灵(nitralin)、 黄草消(oryzalin)、 胺辨草(pendimethalin)、 ^^丙氟灵(prodiamine)、卡乐施(profluralin)、 氟乐灵(trifluralin); - Dinitroanilines, such as fluorine alachlor (benefin), Butralin (butralin), Le enemy amine (dinitramine), Ding fluorine eliminate grass (ethalfluralin), fluorine eliminate grass (fluchloralin), different music Ling (isopropalin) cross trifluralin (nitralin), oryzalin (oryzalin), amine distinguish grass (pendimethalin), ^^ prop F Ling (prodiamine), card Oxfam (profluralin), Treflan (trifluralin);

    '二贿基酚类,如杀草全(bromofenoxim)、地乐酚(dinoseb)、地乐酯(dinoseb-acetate)、地乐消酚(dinoterb) 、 二硝甲酚(腿OC)、 minoterb-acetate; 'Two bribe-based phenols such as herbicide-wide (bromofenoxim), dinoseb (dinoseb), to music ester (dinoseb-acetate), to eliminate phenol music (dinoterb), dinitramide cresol (leg OC), minoterb- acetate;

    '二苯基醚类,如氟锁草醚(acifluorfen-sodium)、苯草醚(adonifen)、治草醚(bifenox)、草枯醚(chlornitrofen)、枯莠隆(difenoxuran)、氟乳醚(ethoxyfen)、消草醚(fluorodifen)、乙羧氟草醚(fluoroglycofen-ethyl)、 氟黄胺草醚(化mesafen)、氟呋草醚(furyloxyfen)、乳氟禾草灵(lactofen)、 除草醚(nitrofen)、硝氟草醚(nitrofluorfen)、氟硝草醚(oxyfluorfen); 'Diphenyl ethers such as acifluorfen (acifluorfen-sodium), aclonifen (adonifen), Bifenox (bifenox), CNP (chlornitrofen), dry herbicide Long (difenoxuran), fluorine milk ether ( ethoxyfen), eliminate grass ether (fluorodifen), B fluoroglycofen (fluoroglycofen-ethyl), fluoro yellow grass ether amine (of mesafen), furosemide fluorine grass ether (furyloxyfen), Lactofen (lactofen), nitrofen (nitrofen), nitric fluoroglycofen (nitrofluorfen), flunitrazepam grass ether (oxyfluorfen);

    '联p比咬类,如莎草快(cyperquat)、苯敌快(difenzoquat-methyl sulfate)、 敌草快(diquat)、对草快(paraquat-dichloride); 'Union p class than bite, such as sedge fast (cyperquat), benzene enemy fast (difenzoquat-methyl sulfate), diquat (diquat), paraquat (paraquat-dichloride);

    •咪唑类,如丁环隆(isocarbamid); • imidazole class, such as Ding USI (isocarbamid);

    咪峻淋酮类,如imazamethapyr、灭草烟(imazapyr)、灭草会(imazaquin)、 咪草酯(imazethabenz-methyl)、咪草烟(imazethapyr)、甲咪唑烟酸(imazapic)、咪草咬酸(imazamox); Mi Jun shower ketones, such as imazamethapyr, imazapyr (imazapyr), herbicides will (imazaquin), imazethapyr ester (imazethabenz-methyl), imazethapyr (imazethapyr), imazapic (imazapic), imazethapyr bite acid (imazamox);

    '巧悉二唑类,如灭草定(methazole)、炔丙巧悉唑草(oxadiargyl)、恶草灵(oxadiazon); 'Qiao noted two azoles, such as methazole (methazole), propargyl Qiao noted carfentrazone (oxadiargyl), oxadiazon (oxadiazon);

    环氧乙烷类,如灭草环(tridiphane); '酚类,如溴苯腈(bromoxynil)、捵苯腈(ioxynU); Ethylene oxide type, such as herbicides ring (tridiphane); 'phenols, such as bromoxynil (bromoxynil), Chen benzonitrile (ioxynU);

    -苯氧基苯氧基丙酸酯类,如炔草酯(dodinafop)、氰氟草酯(cyhalofop-butyl)、 禾草灵(diclo化p-methyl)、,噪唑禾草灵(fenoxaprop-ethyl)、高哺、唑禾草灵(fenoxaprop-p-ethyl)、噻唑禾草灵(fenthiaprop-ethyl)、吡氟禾草灵(fluazifop-butyl)、精吡氟禾草灵(fluazifop-p-butyl)、吡氟氯禾灵(haloxyfop-ethoxyethyl)、吡氟氯禾灵(haloxyfop-methyl)、精吡氟氯禾灵(haloxyfop-p-methyl)、恶草醚(isoxapyrifop)、鬼草酉旨(propaquizafop)、唾禾灵(quizalofop-ethyl)、精喹禾灵(quizalofop-p-ethyl)、喹禾灵四氢糠基酯(quizalofop-tefuryl); - Phenoxyphenoxy acid esters, such as clodinafop-propargyl (dodinafop), cyhalofop (cyhalofop-butyl), diclofop (diclo of p-methyl) ,, noise oxazole diclofop (fenoxaprop- ethyl), high feeding, oxazole diclofop (fenoxaprop-p-ethyl), thiazole diclofop (fenthiaprop-ethyl), fluazifop (fluazifop-butyl), fine fluazifop (fluazifop-p- butyl), haloxyfop (haloxyfop-ethoxyethyl), haloxyfop (haloxyfop-methyl), fine haloxyfop (haloxyfop-p-methyl), cockle ether (isoxapyrifop), ghost grass aims Unitary (propaquizafop), saliva Wo Ling (quizalofop-ethyl), Quizalofop (quizalofop-p-ethyl), quizalofop tetrahydrofurfuryl ester (quizalofop-tefuryl);

    .苯基乙酸类,如伐草克(chlorfenac); Phenyl acetic acids, such as cutting the grass g (chlorfenac);

    •苯基丙酸类,啧o chlorophenprop-methyl; • phenyl propionic acids, tsk o chlorophenprop-methyl;

    29'ppi-活性化合物,如p比草酮(benzofenap)、酰亚胺苯氧乙酸戊酉旨(flumiclorac-pentyl)、氟嗜漆酮(flumioxazin)、炔草胺(flumipropyn)、 flupropacil、千草唑(pyrazoxyfen)、碌胺草唾(sulfentrazone)、嚷二峻草胺(thidiazimin); 29'ppi- active compounds, such as p ratio oxadiazon (benzofenap), flumiclorac amyl unitary purpose (flumiclorac-pentyl), fluorine addicted to paint one (flumioxazin), flumipropyn (flumipropyn), flupropacil, Chigusa azole (pyrazoxyfen), busy amine grass saliva (sulfentrazone), cried two Jun alachlor (thidiazimin);

    .吡唑类,如吡氯草胺(nipyradofen); Pyrazole class, such as chlorine topiramate alachlor (nipyradofen);

    ■碳漆类,如杀草敏(chloridazon)、抑芽丹(maleic hydrazide)、达草灭 ■ carbon paint, such as herbicide-sensitive (chloridazon), maleic hydrazide (maleic hydrazide), norflurazon

    (norflurazon)、达草止(pyridate); .吡吱羧酸类,如二氯皮考啉酸(cl叩yralid)、氟硫草定(dithiopyr)、毒莠 (Norflurazon), up grass only (pyridate);. Pyridine squeak carboxylic acids, such as dichloro picolinic acid (cl knock yralid), dithiopyr (dithiopyr), picloram

    定(picloram)、噢氟咬草(thiazopyr); '嘧啶基醚类,如嘧硫笨甲酸(pyrithiobac-acid)、嘧硫笨甲酸钠 Set (picloram), oh fluorine bite grass (thiazopyr); 'pyrimidine ethers, such as formic acid pyrithiobac stupid (pyrithiobac-acid), sodium stupid pyrithiobac

    (pyrithiobac-sodium)、双嘧苯甲酸(KIH-2023)、肟啶草(KIH-6127); '磺酰胺类,如氟唑咬草(flumetsulam)、唑草磺胺(metosulam); •三哇羧酰胺类,如triazofenamide; (Pyrithiobac-sodium), bispyribac (KIH-2023), pyridine oxime grass (KIH-6127); 'sulfonamides, such as fluorine-yl bite grass (flumetsulam), carfentrazone sulfonamides (metosulam); • three wow carboxylase amides, such as triazofenamide;

    .尿嘧咬类,如除草定(bromadl)、环草定(lenacil)、特草定(terbacil); . Uracil bite type, such as bromacil (bromadl), grass ring set (lenacil), terbacil (terbacil);

    .此外还有草除灵(benazolm)、呋草黄(benfuresate)、地散磷(bensulide)、 氟磺胺草(benzofluor)、噻草平(bentazon)、草胺磷(butamifos)、苯砜唑(cafenstrole)、敌草索(chlorthal-dimethyl)、环庚草酸(cinmethylin)、敌草腈(dichlobenil)、草藻灭(endothall) 、 fluorbentranil 、 氟草磺(mefluidide)、氟草磺胺(perfluidone)、派草磷(piperophos)、 topramezone 和环己酉同酸4丐(prohexadione-calcium); In addition there are Benazolin (benazolm), furosemide grass yellow (benfuresate), bensulide (bensulide), fomesafen (benzofluor), thiophene grass flat (bentazon), glufosinate (butamifos), benzene sulfone azole (cafenstrole ), diuron cable (chlorthal-dimethyl), cycloheptyl oxalic acid (cinmethylin), diuron nitrile (dichlobenil), grass algae off (endothall), fluorbentranil, fluorine grass sulfonamide (mefluidide), fluroxypyr sulfonamides (perfluidone), send grass phosphorus (piperophos), topramezone and ring Jiyou with acid 4 beggar (prohexadione-calcium);

    .碌酰脲类,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron-methyl)、氯嘧黄隆(chloriimiron-ethyl)、绿黄隆(chlorsulfuron)、醜黄隆(cinosulfuron)、环丙黄隆(cydosulfamuron)、 胺笨黄隆(ethametsulfuron-methyl)、啶嘧黄隆(flazasulfuron)、吡氯黄隆(halosulfuron-methyl)、 啶咪黄隆(imazosulfuron)、 甲黄隆(metsulfuron-methyl)、 烟嘧黄隆(nicosulfuron)、 氟嘧黄隆(primisulfuron)、 氟丙黄隆(prosulfuron)、 吡嘧黄隆(pyrazosulfuron-ethyl)、 玉嘧黄隆(rimsulfuron)、 嘧黄隆(sulfometuron-methyl)、 噢黄隆(thifensulfuron-methyl)、 链笨黄隆(triasulfuron)、 苯黄隆(tribenuron-methyl)、 氟胺黄隆(triflusulfuron-methyl)、三氟曱磺隆(tritosulfuron); . Bunk ureide class, such as acesulfame Huang Long (amidosulfuron), tetrazole Huang Long (azimsulfuron), bensulfuron (bensulfuron-methyl), chlorimuron-ethyl (chloriimiron-ethyl), chlorsulfuron (chlorsulfuron), Ugly Huang Long (cinosulfuron), cyproterone Huang Long (cydosulfamuron), amine stupid Huang Long (ethametsulfuron-methyl), pyridine ethyl Huang Long (flazasulfuron), topiramate chlorine Huang Long (halosulfuron-methyl), pyridine Amy Huang Long (imazosulfuron) , A Huang Long (metsulfuron-methyl), nicosulfuron (nicosulfuron), Fluoxastrobin Huang Long (primisulfuron), -fluoropropoxy Huang Long (prosulfuron), pyrazosulfuron Huang Long (pyrazosulfuron-ethyl), rimsulfuron (rimsulfuron ), ethyl Huang Long (sulfometuron-methyl), oh Huang Long (thifensulfuron-methyl), chain stupid Huang Long (triasulfuron), benzene Huang Long (tribenuron-methyl), amine fluoride Huang Long (triflusulfuron-methyl), trifluoromethyl Yue metsulfuron (tritosulfuron);

    环己烯酮类作物保护剂,如枯杀达(alloxydim)、烯草酮(dethodim)、环己烯草酮(doproxydim)、噻草酮(cycloxydim)、稀禾定(sethoxydim)和肟草酮(tralkoxydim)。 Cyclohexanedione crop protection agents, such as dry kill up (alloxydim), clethodim (dethodim), cyclohexanone clethodim (doproxydim), thiophene grass ketone (cycloxydim), sethoxydim (sethoxydim) and tralkoxydim (tralkoxydim). 非常特别优选的环己烯酮类除草活性化合物是吡喃草酮(tepraloxydim)(参见AGROW,第243期,1995年11月3日,第21页,醌肟草(caloxydim))和2-(1-[2-{4-氯苯氧基}丙氧亚氨基】丁基)-3-羟基-5-(2H-四氢噻喃-3-基)-2-环己烯-l-酮,而非常特别优选的磺酰脲类除草活性化合物是N-(((4-甲氧基-6-l三氟甲基ll,3,5-三嗪-2-基)氨基)羰基)-2-(三氟甲基)苯磺酰胺。 Very particularly preferred herbicidal cyclohexenone active compound is tepraloxydim (tepraloxydim) (see AGROW, Section 243, November 3, 1995, p. 21, quinone oxime grass (caloxydim)) and 2- ( 1- [2- {4-chlorophenoxy} -propoxyimino} butyl) -3-hydroxy -5- (2H- tetrahydro-thiopyran-3-yl) -2-cyclohexen-one -l- , and very particularly preferred sulfonylurea herbicidal active compound is N - (((4- methoxy -6-l trifluoromethyl ll, 3,5- triazin-2-yl) amino) carbonyl) - 2- (trifluoromethyl) benzenesulfonamide. 可配制成本发明的含水活性化合物组合物的杀虫剂实例包括: Examples of the aqueous active compound may insecticides are formulated into a composition of the invention comprises:

    有机(硫代)磷酸酯类:高灭礴(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、 毒死蜱(chlorpyrifos)、 甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvi叩hos)、 二漆农(diazinon)、敌敌畏(dichlorphos)、 曱基毒虫畏(dimethylvinphos)、 杀抗松(dioxabenzofos)、 百治磷(dicrotophos)、 乐果(dimethoate)、 乙拌磷(disulfoton)、乙硫磷(ethion)、 ^5克磷(EPN)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异^悉唑磷(isoxathion)、马拉硫磷(malathion)、曱胺磷(methamidophos)、 杀朴磷(methidathion)、 曱基一六零五(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸裤(oxydematon-methyl)、对氧磷(paraoxon)、 一六零五(parathion)、 稻丰散(phenthoate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、 甲拌磷(phorate)、 辛硫磷(phoxim)、 虫螨磷(pirimiphos-methyl)、 丙淡磷(profenofos)、 丙石克磷(prothiofos)、 primiphos-ethyl、 p比峻石危磷(pyraclofos)、打杀磷(pyridaphenthion)、 乙丙石充磷(sulprophos)、三喳磷(triazophos)、敌百虫(trichlorfon)、杀虫畏(tetrachlorvinphos)、对灭多(vamidothion); Organic (thio) phosphates: High off Bo (acephate), azole pyridine phosphorus (azamethiphos), azinphos-methyl (azinphos-methyl), chlorpyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), chlorfenvinphos (chlorfenvi knock hos), two lacquer agriculture (diazinon), dichlorvos (dichlorphos), Yue group chlorfenvinphos (dimethylvinphos), to kill the anti-pine (dioxabenzofos), Dicrotophos (dicrotophos), dimethoate (dimethoate), Disulfoton (disulfoton) ethion (ethion), ^ 5 克 phosphorus (EPN), fenitrothion (fenitrothion), Fenthion (fenthion), iso ^ noted Triazophos (isoxathion), malathion (malathion), Yue amine phosphorus (methamidophos), kill Park phosphorus (methidathion), Yue group one thousand six hundred and five (methyl-parathion), mevinphos (mevinphos), monocrotophos (monocrotophos), sulfone suction pants (oxydematon-methyl), paraoxon ( paraoxon), one thousand six hundred and five (parathion), phenthoate (phenthoate), phosalone (phosalone), phosmet (phosmet), phosphamidon (phosphamidon), phorate (phorate), phoxim ( phoxim), pirimiphos (pirimiphos-methyl), prop light phosphorus (profenofos), prop-grams of phosphorus (prothiofos), primiphos-ethyl, p than the steep stone crisis phosphorus (pyraclofos), imputed phosphorus (pyridaphenthion), ethylene-propylene stone charge phosphorus (sulprophos), three twitter phosphorus (triazophos), trichlorfon (trichlorfon), tetrachlorvinphos (tetrachlorvinphos), for methomyl (vamidothion);

    '氨基甲酸酯类:棉铃威(alanycarb)、丙硫克百威(benfuracarb)、、噪虫威(bendiocarb)、 甲萘威(carbaryl)、 虫螨威(carbofuran) 、 丁硫克百威(carbosulfan)、双氣威(fenoxycarb)、吹线威(furathiocarb)、噍二峻虫(indoxacarb)、 灭虫威(methiocarb)、 灭多虫(methomyl)、 甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、 峻椅威(triazamate); 'Carbamates: alanycarb (alanycarb), benfuracarb (benfuracarb) ,, noise worm Granville (bendiocarb), carbaryl (carbaryl), carbofuran (carbofuran), carbosulfan (carbosulfan ), Double Air Granville (fenoxycarb), blowing line Granville (furathiocarb), Jun Jiao two insects (indoxacarb), methiocarb (methiocarb), methomyl (methomyl), carbamoyl fork K (oxamyl), pirimicarb ( pirimicarb), propoxur (propoxur), thiodicarb (thiodicarb), chair Wei Jun (triazamate);

    合成除虫菊酯类:丙烯菊酯(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、苯醚氛菊酯(cyphenothrin)、乙氰菊酯(cydoprothrin)、 氯氰菊酯(cypermethrin)、溴氰菊酯(ddtamethrin)、高氰戊菊酯(esfenvalerate),醚菊酯(ethofenprox)、 甲氰菊酯(fe叩ropathrin)、杀灭菊酯(fenvalerate) 、 (RS)氯氟氰菊酯(cyhalothrin)、氯氟氰菊酯(lambda-cyhalothrin)、咪炔菊酯(imoprothrin)、氯菊酯(permethrin)、 炔酮菊酯(prallethrin)、炔酮菊酯I、炔酮菊酯II、灭虫硅醚(silafluofen)、 氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、四溴菊酯(tralomethrin)、 四氟菊酯(transfluthrin)、 甲体氯氰菊酯(alpha-cypermethrm)、 己体氯氰菊酉旨(zeta-cypermethrin)、 氯菊酉旨(permethrin); Pyrethroid: allethrin (allethrin), bifenthrin (bifenthrin), cyfluthrin (cyfluthrin), benzene, ether atmosphere permethrin (cyphenothrin), B cyhalothrin (cydoprothrin), cypermethrin (cypermethrin), bromine cyanide permethrin (ddtamethrin), esfenvalerate (esfenvalerate), phenothrin (ethofenprox), fenpropathrin (fe knock ropathrin), fenvalerate (fenvalerate), (RS) cyhalothrin (cyhalothrin ), cyhalothrin (lambda-cyhalothrin), imiprothrin (imoprothrin), permethrin (permethrin), alkynone permethrin (prallethrin), alkynone permethrin I, alkynone permethrin II, pest control Silicon ether (silafluofen), fluvalinate (tau-fluvalinate), tefluthrin (tefluthrin), tralomethrin (tralomethrin), tetrafluoroethylene pyrethroid (transfluthrin), A-cypermethrin (alpha-cypermethrm), has unitary body cypermethrin purpose (zeta-cypermethrin), permethrin unitary purpose (permethrin);

    .节肢动物生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类,如定虫隆(chlorfluazuron)、灭竭胺(cyromacin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、 氟虫脲(flufenoxuron)、 氟铃脲(hexaflumuron)、 氟丙氧脲(lufemiron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(trifluniuron);嚷溱酮(b叩rofezhi)、、懲茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯^悉唑(etoxazole)、四螨唤(clofentazine); b)蜕皮激素拮抗剂,如特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、 双笨酰耕(tebufenozide); c)保幼激素类似物,如蚊蝇醚(pyriproxyfen)、 蒙五一五(methoprene)、双氧威(fenoxycarb); d)类脂生物合成抑制剂, 如螺螨酉旨(spirodidofen); . Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas as Chlorfluazuron (chlorfluazuron), off exhaust amine (cyromacin), fluorouracil kill (diflubenzuron), fluorine mites urea (flucycloxuron) , flufenoxuron (flufenoxuron), hexaflumuron (hexaflumuron), fluorine propoxyphene urea (lufemiron), novaluron (novaluron), teflubenzuron (teflubenzuron), insecticide-long (trifluniuron); Qin cried one (b knock rofezhi) ,, Correctional Mao ether (diofenolan), hexythiazox (hexythiazox), especially benzene ^ noted azole (etoxazole), four mites call (clofentazine); b) ecdysone antagonists, such as halofenozide (halofenozide ), methicillin hydrazide (methoxyfenozide), double stupid acid plow (tebufenozide); c) juvenoids, such as pyriproxyfen (pyriproxyfen), methoprene (methoprene), fenoxycarb (fenoxycarb); d) lipid biosynthesis inhibitors, such as spirodiclofen unitary purpose (spirodidofen);

    •新烟碱类(neonicotinoids), 如氟咬虫酰胺(flonicamid)、塞虫胺(dothianidin)、吹虫胺(dmotefuran)、吡虫啉(imidadoprid)、噢虫唤(thiamethoxam)、硝胺烯啶(nitenpyram)、硝虫嚷唤(nithiazine)、吡虫清(acetamiprid)、嚷虫啉(thiacloprid); • neonicotinoids (neonicotinoids), biting insects such as fluorine amide (flonicamid), plug insect amine (dothianidin), blowing insect amine (dmotefuran), imidacloprid (imidadoprid), oh insect call (thiamethoxam), nitenpyram (nitenpyram ), nitro worms cried call (nithiazine), acetamiprid (acetamiprid), cried insect morpholine (thiacloprid);

    不属于上述类别的其它杀虫剂,如齐墩螨素(abamecthi)、灭螨醌(acequinocyl) 、 ? Other pesticides do not belong to the above categories, such as abamectin (abamecthi), mites quinone (acequinocyl),? 比虫清(acetamiprid)、 虫螨脒(amitraz)、 艾丁(azadirachtin)、杀虫磺(bensultap)、联苯肼酯(bifenazate)、杀螟丹(cartap)、 氟峻虫清(chlorfenapyr)、 杀虫脒(chlordimeform)、 灭錄胺(cyromazine)、杀螨硫隆(diafenthiuron)、呋虫胺(dmetofuran)、,噪、茂醚(diofenolan)、 埃3马菌素(emamectin)、石克丹(endosulfan)、 乙虫清(ethiprole)、壹螨醃(fenazaquin)、锐劲特(fipronil)、伐虫脒(formetanate)、 伐虫脒盐酸盐(formetanate hydrochloride),林丹(gamma-HCH)、灭蚁腙(hydramethylnon)、 p比虫啉(imidacloprid)、 ? Clear than the worm (acetamiprid), amitraz (amitraz), Edin (azadirachtin), bensultap (bensultap), BIFENAZATE (bifenazate), cartap (cartap), fluorine Jun ACETAMIPRID (chlorfenapyr), chlordimeform (chlordimeform), off the record amine (cyromazine), acaricide sulfur Long (diafenthiuron), dinotefuran (dmetofuran) ,, noise, Mao ether (diofenolan), Egypt 3 Ma streptozotocin (emamectin), Danke Dan (endosulfan ), ethiprole (ethiprole), One mite pickled (fenazaquin), fipronil (fipronil), cutting acetamiprid (formetanate), cutting worm hydrochloride (formetanate hydrochloride), lindane (gamma-HCH), mirex hydrazone (hydramethylnon), p ratio insect morpholine (imidacloprid),? 悉二哇虫(indoxacarb)、 异丙威(isoprocarb)、速灭威(metolcarb)、化螨酮(pyridaben)、才巨噪酮(pymetrozine)、艾克敌105(spinosad)、他螨胺(tebufe叩yrad)、噢虫* (thiamethoxam)、硫环杀(thiocyclam)、啶虫丙醚(pyridalyl)、氟咬虫酰胺(flonicamid) 、 fluacypyrim 、米尔螨素(milbemectin)、螺甲螨酯(spiromesifen) 、 flupyrazofos 、 NC 512 、 峻虫酰胺(tolfe叩yrad)、 flubendiamide、双三氟虫脲(bistrifluron)、 bendothiaz、 pyrafluprole、 pyriprole、 amidoflumet、 flufenerim、 cyflumetofen、灭竭職(acequinocyl)、 lepknectin、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin)、 腙(amidrazone)、 metaflumizone、 NR,-2,2-二面代-lR"-环丙烷甲酰胺-2-(2,6-二氧-a,a,a-三氟对曱苯基)腙、NR,-2,2-二(R',,)丙酰胺-2-(2,6画二氧《,a,a-三氟甲苯基)腙,其中卤素为氯或溴,R,为甲基或乙基,R"为氢或甲基且R,"为甲基或乙基,二甲威(XMC)和灭杀威(xylylcarb)以及下式化合物: Noted the two wow insects (indoxacarb), isoprocarb (isoprocarb), metolcarb (metolcarb), one of the mite (pyridaben), only one giant noise (pymetrozine), spinosad 105 (spinosad), he mite amine (tebufe knock yrad), oh insect * (thiamethoxam), sulfur ring kill (thiocyclam), Acetamiprid propyl ether (pyridalyl), fluorine insect bite amide (flonicamid), fluacypyrim, Mill mites hormone (milbemectin), spiromesifen (spiromesifen) , flupyrazofos, NC 512, Jun insect amide (tolfe knock yrad), flubendiamide, bistrifluoromethyl worm urea (bistrifluron), bendothiaz, pyrafluprole, pyriprole, amidoflumet, flufenerim, cyflumetofen, dried off grade (acequinocyl), lepknectin, propionic fluorine-ju ester (profluthrin), tetrafluoroethylene pyrethroid ether (dimefluthrin), hydrazone (amidrazone), metaflumizone, NR, -2,2- two side substituting -lR "- cyclopropanecarboxamide -2- (2,6-dioxo -a, a, a- trifluoro Yue phenyl) hydrazone, NR, -2,2- two (R ',,) propanamide -2- (2,6-dioxo-Videos ", a, a- trifluoro- tolyl) hydrazone, wherein the halogen is chlorine or bromine, R, is methyl or ethyl, R "is hydrogen or methyl and R," is methyl or ethyl, Macbanseok (XMC) and kill Wei ( xylylcarb) and a compound of the formula:

    33下式的氨基异噻唑: 33 formula aminoisothiazole:

    其中 Among them

    11=-(:1120-<:113或11,和 11 = - (: 1120-- <: 113 or 11, and

    R,=-CF2CF2CF3; 下式的邻氨基苯甲酰胺:<formula>formula see original document page 34</formula> R, = - CF2CF2CF3; formula anthranilamide: <formula> formula see original document page 34 </ formula>

    其中R为d-C4烷基如甲基、乙基、异丙基或正丁基, 以及下式化合物: Wherein R is d-C4 alkyl such as methyl, ethyl, isopropyl or n-butyl, and the compound of the formula:

    o o

    .在EP-A 462 456中以式I描述的N-苯基缩氨基脲,尤其是式IV化合物: . N- phenyl in EP-A 462 456 are described by formula I semicarbazone, especially the compound of formula IV:

    其中R"和RU相互独立地为氢、卤素、CN、 CrQ烷基、dQ烷氧基、 d-C4卤代烷基或C「C4卤代烷氧基且1113为d-C4烷氧基、d-Cj卣代烷基或CrC4囟代烷氧基,例如其中R11为3-CF3、 R12为4-CN且R13 为4-OCF3的化合物IV(-metaflumizone)。 有用的生长调节剂例如为矮壮素(chlormequat-chloride)、助壮素(mepiquat腸chloride)、环己酉同酸4丐(prohexadione-calcium)或赤霉素类。这些例如包括赤霉素GAp GA3、 GA4、 GAs和GA7等,对应的外-16,17-二氢赤霉素,及其衍生物,例如与d-C4羧酸的酯。本发明优选外-16,17-二氢-GAsl3-乙酸酯,此外还有l-萘基乙酰胺、l-萘基乙酸、2-萘氧基乙酸、 调果酸(3-CPA)、促生灵(4-CPA)、嘧啶醇(ancymidol)、蒽醌、苄胺基嘌呤(BAP)、脱叶亚磷(butifos)、 丁硫亚磷(tribufos)、地乐胺(butralin)、氯曱丹(chlorflurenol)、苯哒酮酸(clofencet)、环丙酸酰胺(cyclanilide)、 丁酰肼(daminozide)、 麦草畏(dicamba)、 双古钠(dikegulac sodium)、 噢节因(dimethipin)、杀螨醇(chlorfenethol)、娃长素(etacelasil)、乙烯利(ethephon)、 果宝素(ethychlozate) 、 2,4,5-弟丙酸(fenoprop) 、 2,4,5-TP 、氟磺胺素(fluoridamid)、调嘧醇(flurprimidol)、粉唑醇(flutriafol)、双胍盐(guazatin)、 烯菌灵(imazalil)、吲咮丁酸(indolylbutyric acid)、吲哚乙酸(indolylacetic acid)、 karetazan、 动力精(kinetin)、 lactidichlor-ethyl、 抑芽丹(maleic hydrazide)、 氟草磺(mefluidide)、 抑草生(naptalam)、 多效唑(paclobutrazole)、 壹草酸(quinmerac)、 杀雄淋(sintofen)、 调环烯(tetcyclacis)、赛二唑素(thidiazuron)、三碘笨甲酸、抑芽唑(triapenthenol)、 triazethan 、 丁硫亚磷(tribufos)、抗倒酉旨(trinexapac-ethyl)和烯效唑(uniconazole)。 Wherein R "and RU are independently hydrogen, halogen, CN, CrQ alkyl, dQ alkoxy, d-C4 haloalkyl or C" C4 haloalkoxy and 1113 is d-C4-alkoxy, d-Cj wine container substituted alkyl or CrC4 haloalkoxy, e.g., wherein R11 is 3-CF3, R12 and R13 is 4-CN Compound IV 4-OCF3 of (-metaflumizone). Useful growth regulators, for example, chlormequat (chlormequat -chloride), mepiquat (mepiquat intestinal chloride), loop Ji you with acid 4 beggar (prohexadione-calcium) or gibberellins. These, for example GA GAp GA3, GA4, GAs and GA7 etc., corresponding alia 16,17-dihydro gibberellin, and derivatives thereof, for example, d-C4 carboxylic acids. Preferably the present invention is 16,17-dihydro outer -GAsl3- acetate, in addition to l- naphthyl acetamide, l- naphthyl acetic acid, 2-naphthoxy acetic acid, adjusting the acid (3-CPA), promoting creatures (4-CPA), pyrimidine-ol (ancymidol), anthraquinone, benzylamino purine (BAP) , defoliation phosphorous (butifos), Ding sulfur phosphorous (tribufos), Butralin (butralin), chlorine Yue Dan (chlorflurenol), benzene da acid (clofencet), cyclic acid amide (cyclanilide), daminozide (daminozide ), dicamba (dicamba), double the ancient sodium (dikegulac sodium), oh section because (dimethipin), mites alcohol (chlorfenethol), baby long element (etacelasil), ethephon (ethephon), fruit Po plain (ethychlozate), 2,4,5 brother acid (fenoprop), 2,4,5-TP, fomesafen hormone (fluoridamid), adjust ethyl alcohol (flurprimidol), Flutriafol (flutriafol), guazatine (guazatin), ene bacteria Ling (imazalil), indole NEB butyric acid (indolylbutyric acid), indole acetic acid (indolylacetic acid), karetazan, dynamic fine (kinetin), lactidichlor-ethyl, maleic hydrazide (maleic hydrazide), fluoride grass sulfonamide (mefluidide), suppression Sod (naptalam), MET (paclobutrazole), One oxalic acid (quinmerac), CHA leaching (sintofen), adjust the cycloolefin (tetcyclacis), race oxadiazole hormone (thidiazuron), triiodobenzoic stupid acid, suckering azole (triapenthenol), triazethan, Ding sulfur phosphorous (tribufos), lodging unitary purpose (trinexapac-ethyl) and uniconazole (uniconazole).

    本发明的优选实施方案涉及本发明两亲性聚合物组合物在制备杀真菌剂,尤其是例如在每种情况下在WO 98/46608、 WO 99/41255或WO 03/004465中以式I描述的嗜球果伞素类、唑类和6-芳基三唑并[l,5a】嘧啶, 特别是式V的活性化合物的含水活性化合物组合物中的用途: A preferred embodiment of the present invention relates to an amphiphilic polymer composition of the present invention in the preparation of fungicides, particularly for example in each case in WO 98/46608, WO 99/41255 or WO 03/004465 to formula I described The strobilurin class azole and 6-aryl-triazolo [l, 5a] pyrimidine, especially aqueous active compound compositions containing the active compounds of Formula V uses:

    Rx为基团NR"R"或任选被卤素、OH、 d-C4烷氧基、苯基或(:3-(:6环烷基取代的线性或支化d-Cs烷基,为CVC6链烯基、CVC6环烷基、CrC6 环烯基、苯基或萘基,其中后提到的4个基团可以具有1、 2、 3或4个 Rx is a group NR "R" or optionally substituted with halogen, OH, d-C4 alkoxy, phenyl or (: 3 - (: 6 cycloalkyl substituted linear or branched d-Cs alkyl group, as CVC6 alkenyl, CVC6 cycloalkyl, CrC6 cycloalkenyl, phenyl or naphthyl, which last mentioned four groups may have 1, 2, 3 or 4

    其中选自卣素、OH、 dQ烷基、dQ鹵代烷秘、C广C4烷氣基和CrC4 面代烷基的取代基; Wherein the selected wine container elements, OH, dQ alkyl, dQ Halon secret, C wide C4 alkyl group and CrC4 surface gas substituted alkyl substituent;

    R14、 R"相互独立地为氢、CrQ烷基、dQ卣代烷基、CrQo环烷基、 C3-C6卣代环烷基、C2-Cs链烯基、Odo链二烯基、CrC8卣代链烯基、C3-C6环烯基、CVC8卣代环烯基、CVC8炔基、CrCs面代炔基或CrC6环炔基, R14, R "are independently hydrogen, CrQ alkyl, dQ wine container alkyl group, CrQo cycloalkyl, C3-C6 cycloalkyl-generation wine container, C2-Cs alkenyl, Odo alkadienyl group, CrC8 wine container generations alkenyl, C3-C6 cycloalkenyl, CVC8 wine container behalf cycloalkenyl, CVC8 alkynyl, CrCs surface behalf alkynyl or CrC6 cycloalkynyl,

    R"和R"与它们所连接的氮原子一起为5-8员杂环基,该杂环基经由N连接且可以另外含有1、 2或3个选自O、 N和S的杂原子作为环成员和/或可以带有一个或多个选自卤素、dQ烷基、d-C6囟代 R "and R" together with the nitrogen atom to which they are attached 5-8 membered heterocyclic group, the heterocyclic group is connected via N and may additionally contain 1, 2 or 3 heteroatoms selected from O, N and S as heteroatoms ring members and / or one or more substituents selected from halo, dQ alkyl, d-C6 haloalkyl which may have

    烷基、CVC6链烯基、CrC6卣代链烯基、d-C6烷氧基、CrC6卤代 Alkyl, CVC6 alkenyl, CrC6 wine container behalf alkenyl, d-C6 alkoxy, CrC6 haloalkyl

    烷氧基、CVC6链烯氧基、CVC6卣代链烯氧基、(外)-CrC6亚烷基和氧基-Q-C3亚烷氧基的取代基; L选自卤素、氰基、d-C6烷基、CrC4卤代烷基、C广Q烷氧基、d-C4 Alkoxy, CVC6 alkenyloxy, CVC6 wine container behalf alkenyloxy, (outer) -CrC6 alkylene and alkylene group -Q-C3 alkoxy substituent; L is selected from halo, cyano, d -C6 alkyl, CrC4 haloalkyl, C alkoxy wide Q, d-C4

    卤代烷氧基和CrC6烷氧羰基; U为卣素、d-C6烷基或d-C6卣代烷基,尤其是氟或氯; Haloalkoxy and CrC6 alkoxycarbonyl group; U is prime wine container, d-C6-alkyl or d-C6 alkyl group wine container, especially fluorine or chlorine;

    X为卣素、d-C4烷基、M、 d-C4烷氣基或C广C4卣代烷基,优选卣素 X is a wine container elements, d-C4 alkyl, M, d-C4 alkyl group or a C gas wide wine container C4 alkyl group, preferably vegetarian wine container

    或甲基,尤其是氯。 Or methyl, in particular chlorine. 式V化合物的实例是5-氯-7-(4-甲基哌啶-l-基)-6-(2,4,6-三氟苯基)-[l,2,4j三唑并[l,5-al嘧啶,5-氯-7-(4-甲基哌嗪-l-基)-6-(2,4,6-三氟苯基)-[l,2,4】三唑并[l,5-al嘧啶,5-氯-7-(吗啉小基)-6-(2,4,6-三氟苯基Hl,2,4j 三唑并【l,5-a】嘧啶,5-氯-7-(哌啶-l-基)-6-(2,4,6-三氟苯基)-[l,2,4j三唑并【1,5-a】嘧啶,5-氯-7-(吗啉-l-基)-6-(2,4,6-三氟苯基)-【l,2,4j三唑并[l,5-al嘧啶,5-氯-7-(异丙基氨基)-6-(2,4,6-三氟苯基Hl,2,4j三唑并[l,5-a】嘧啶,5-氯_7-(环戊基氨基)-6-(2,4,6-三氟苯基)-[1,2,41三唑并【1,5-aj嘧啶,5-氯-7-(2,2,2-三氟乙基氨基)-6-(2,4,6-三氟苯基)-【1,2,4]三唑并【1,5-31嘧啶,5-氯-7-(1,1,1-三氟丙-2-基氨基)-6-(2,4,6-三氟苯基)-【1,2,4】三唑并【1,5-31嘧啶,5-氯-7-(3,3-二甲基丁-2-基絲)-6-(2,4,6-三氟苯基Hl,2,4】三唑并ri,5-al嘧啶, 5-氯-7-(环己基甲基)-6-(2,4,6-三氟苯基Hl,2,4〗三唑并[l,5-al嘧啶,5-氯-7-(环己基)-6-(2,4,6-三氟苯基)-【1,2,4】三唑并[1,5-3】嘧啶,5-氯-7-(2-甲基丁-3-基)-6-(2,4,6-三氟苯基)-[l,2,4j三唑并【1,5-a】嘧啶,5-氯-7-(3-甲基丙-1-基)-6-(2,4,6-三氟苯基)-【l,2,4j三唑并【1,5-aj嘧啶,5-氯-7-(4-甲基环己-1-基)-6-(2,4,6-三氟苯基Hl,2,4j三唑并[l,5-a]嘧啶,5-氯-7-(己-3-基)-6-(2,4,6-三氟苯基Hlv2,司三唑并[l,S-aj嘧啶,5-氯-7-(2-甲基丁-l-基)-6-(2,4,6-三氟苯基)-【1,2,41三唑并【1,5-aj嘧啶,5-氯-7-(3-甲基丁-1-基)-6-(2,4,6-三氟苯基)-【1,2,4】三唑并[1,5-a】嘧啶,5-氯-7-(1-甲基丙-l-基)-6-(2,4,6-三氟苯基)-【l,2,司三唑并[l,5-a】嘧啶,5-甲基-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-【l,2,41三唑并【l,5-al嘧啶,5-甲基-7-(4-甲基哌嗪-l-基)-6-(2,4,6-三氟苯基)-[l,2,4】三唑并【1,5-aj嘧啶,5-甲基-7-(吗啉-1-基)-6-(2,4,6-三氟苯基)-[1,2,4】三唑并[l,5-a】嘧啶,5-甲基-7-(哌啶-1-基)-6-(2,4,6-三氟苯基)-【1,2,4】三唑并[1,5-a】嘧啶,5-甲基-7-(吗啉-1-基)-6-(2,4,6-三氟苯基Hl,2,司三唑并【l,5-a】嘧啶,5-甲基-7-(异丙基氨基)-6-(2,4,6-三氟苯基)-【l,2,4j三唑并[1,5-a】嘧啶,5-甲基-7-(环戊基氨基)-6-(2,4,6-三氟苯基)-【1,2,4】三唑并[1,5-31嘧啶,5-甲基-7-(2,2,2-三氟乙基氨基)-6-(2,4,6-三氟苯基)-[l,2,41三唑并[l,5-a】嘧啶,5-甲基-7-(l,l,l-三氟丙-2-基tt)-6-(2,4,6-三氟苯基)-【1,2,4】三唑并【1,5-al嘧啶,5-甲基-7-(3,3-二甲基丁-2-基氨基)-6-(2,4,6_三氟笨基)-【1,2,41三唑并【1,5-a】嘧啶,5-甲基-7-(环己基甲基)-6-(2,4,6-三氟苯基)-【1,2,4]三唑并[1,5-a】嘧啶,5-甲基-7-(环己基)-6-(2,4,6-三氟苯基)-[l,2,4j三唑并[1,5-a】嘧啶,5-曱基-7-(2-甲基丁-3-基)-6-(2,4,6-三氟苯基Hl,;4j三唑并【1,5-al嘧啶,5-甲基-7-(3-甲基丙-1-基)-6-(K6-三氟苯基)-【l,2,4】三唑并【l,5-al嘧啶,5-甲基-7"4-甲基环己-l-基)-6-(2,4,6-三氟苯基)-[l,2,4j三唑并【1,5-a】嘧啶,5-甲基-7-(己-3-基)-6-(2,4,6-三氟苯基H1,2,4】三唑并U,5-a】嘧啶,5-甲基-7-(2-甲基丁-1-基)-6-(2,4,6-三氟苯基Hl,2,41三唑并【l,5-a】嘧啶,5-曱基-7-(3-甲基丁-l-基)-6-(2,4,6-三氟苯基)-[l,:2,4j三唑并[l,5-aj嘧啶和5-甲基-7-(1-曱基丙-1-基)-6-(2,4,6-三氟苯基Hl,2,41三唑并[l,5-a】嘧啶。 Examples of compounds of formula V is 5-chloro-7- (4-methyl-piperidin -l- yl) -6- (2,4,6-trifluoro-phenyl) - [l, 2,4j triazolo [ l, 5-al pyrimidine, 5-chloro-7- (4-methyl-piperazin--l- yl) -6- (2,4,6-trifluoro-phenyl) - [l, 2,4] triazole and [l, 5-al pyrimidine, 5-chloro-7- (morpholin-small-yl) -6- (2,4,6-trifluorophenyl Hl, 2,4j triazolo [l, 5-a] pyrimidine, 5-chloro-7- (piperidin -l- yl) -6- (2,4,6-trifluoro-phenyl) - [l, 2,4j triazolo [1,5-a] pyrimidine, 5-chloro-7- (morpholin -l- yl) -6- (2,4,6-trifluoro-phenyl) - [l, 2,4j triazolo [l, 5-al pyrimidine, 5-chloro- 7- (isopropylamino) -6- (2,4,6-trifluorophenyl Hl, 2,4j triazolo [l, 5-a] pyrimidine, 5-chloro-_7- (cyclopentyl amino) -6- (2,4,6-trifluoro-phenyl) - [1,2,41 triazolo [1,5-aj pyrimidine, 5-chloro-7- (2,2,2-trifluoro- ethylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-31 pyrimidine, 5-chloro-7- (1,1,1 - trifluoro-propan-2-ylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-31 pyrimidine, 5-chloro-7- (3,3-dimethoxy-2-Jisi) -6- (2,4,6-trifluorophenyl Hl, 2,4] triazolo ri, 5-al pyrimidine, 5-chloro-7 - (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl Hl, 2,4〗 triazolo [l, 5-al pyrimidine, 5-chloro-7- (cyclohexyl) -6 - (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-3] pyrimidine, 5-chloro-7- (2-methylbut-3-yl) -6- (2,4,6-trifluoro-phenyl) - [l, 2,4j triazolo [1,5-a] pyrimidine, 5-chloro-7- (3-methyl-propan-1-yl ) -6- (2,4,6-trifluoro-phenyl) - [l, 2,4j triazolo [1,5-aj pyrimidine, 5-chloro-7- (4-methyl-cyclohex-l- yl) -6- (2,4,6-trifluorophenyl Hl, 2,4j triazolo [l, 5-a] pyrimidine, 5-chloro-7- (hex-3-yl) -6- ( 2,4,6-trifluoro-phenyl Hlv2, Division triazolo [l, S-aj pyrimidine, 5-chloro-7- (2-methylbut--l- yl) -6- (2,4,6 - trifluoromethyl phenyl) - [1,2,41 triazolo [1,5-aj pyrimidine, 5-chloro-7- (3-methylbut-1-yl) -6- (2,4,6 - trifluoromethyl phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (1-methyl-propyl -l- yl) -6- (2,4 , 6-trifluoromethyl-phenyl) - [l, 2, Division triazolo [l, 5-a] pyrimidine, 5-methyl-7- (4-methylpiperazin-1-yl) -6- ( 2,4,6-trifluoro-phenyl) - [l, 2,41 triazolo [l, 5-al pyrimidine, 5-methyl-7- (4-methylpiperazin--l- yl) -6 - (2,4,6-trifluoro-phenyl) - [l, 2,4] triazolo [1,5-aj pyrimidine, 5-methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [l, 5-a] pyrimidine, 5-methyl-7- (piperidin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluoro-phenyl Hl, 2, Division triazolo [l, 5-a] pyrimidine, 5-methyl-7- (isopropylamino) -6- (2,4,6 - trifluoromethyl phenyl) - [l, 2,4j triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclopentylamino) -6- (2,4,6-trifluoro- phenyl) - [1,2,4] triazolo [1,5-31 pyrimidine, 5-methyl-7- (2,2,2-trifluoroethyl) -6- (2,4, 6-trifluoromethyl-phenyl) - [l, 2,41 triazolo [l, 5-a] pyrimidine, 5-methyl -7- (l, l, l- trifluoro-2-yl tt) - 6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-al pyrimidine, 5-methyl-7- (3,3-dimethylbut-- 2- ylamino) -6- (trifluoromethyl 2,4,6_ stupid yl) - [1,2,41 triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclohexyl methyl yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclohexyl) -6 - (2,4,6-trifluoro-phenyl) - [l, 2,4j triazolo [1,5-a] pyrimidine, 5-Yue-7- (2-methylbut-3-yl) -6- (2,4,6-trifluorophenyl Hl,; 4j triazolo [1,5-al pyrimidine, 5-methyl-7- (3-methyl-propan-1-yl) -6- (K6- trifluoro-phenyl) - [l, 2,4] triazolo [l, 5-al pyrimidine, 5-methyl-7 "-l- yl 4-methyl-cyclohexyl) -6- (2 , 4,6-trifluoro-phenyl) - [l, 2,4j triazolo [1,5-a] pyrimidine, 5-methyl-7- (hex-3-yl) -6- (2,4 , 6-trifluoromethyl-phenyl] triazolo H1,2,4 U, 5-a] pyrimidine, 5-methyl-7- (2-methyl-1-yl) -6- (2,4, 6-trifluoromethyl-phenyl Hl, 2,41 triazolo [l, 5-a] pyrimidine, 5-Yue-7- (3-methylbut--l- yl) -6- (2,4,6 - trifluoromethyl phenyl) - [l,: 2,4j triazolo [l, 5-aj pyrimidine and 5-methyl-7- (prop-1-yl Yue 1- yl) -6- (2,4 , 6-trifluoromethyl-phenyl Hl, 2,41 triazolo [l, 5-a] pyrimidine.

    本发明的另一优选实施方案涉及本发明的两亲性聚合物组合物在制备杀虫剂,尤其是芳基吡咯类如氟唑虫清(chiorfenapyr),合成除虫菊酯类如氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、乙氰菊酯(cycloprothrin)、 In another preferred embodiment of the present invention it relates to the present invention, the amphiphilic polymer composition in the preparation of pesticides, especially arylpyrroles as chlorfenapyr (chiorfenapyr), synthetic pyrethroid such as bifenthrin ( bifenthrin), cyfluthrin (cyfluthrin), B cyhalothrin (cycloprothrin),

    37氯氰菊酯(cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊6旨(ethofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate) 、 (RS)氯氟氰菊酯(cyhalothrin)、 氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、灭虫硅醚(silafluofen)、 氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、四溴菊酯(tralomethrin)、 甲体氯氰菊酯(alpha-cypermethrin)、 己体氯氰菊酯(zeta-cypermethrin)和氯菊酯(permethrin),新烟碱类以及式IV的缩氩基脲的活性化合物組合物, 尤其是含水活性化合物组合物中的用途。 37 cypermethrin (cypermethrin), deltamethrin (deltamethrin), esfenvalerate (esfenvalerate), ether chrysanthemum 6 purpose (ethofenprox), fenpropathrin (fenpropathrin), fenvalerate (fenvalerate), (RS) cyhalothrin (cyhalothrin), cyhalothrin (lambda-cyhalothrin), permethrin (permethrin), pest silicon ether (silafluofen), fluvalinate (tau-fluvalinate), tefluthrin (tefluthrin), tralomethrin (tralomethrin), A-cypermethrin (alpha-cypermethrin), has cypermethrin (zeta-cypermethrin) and permethrin (permethrin), neonicotinoids and type IV condensing argon ylurea active compound composition, in particular an aqueous active compound composition in use.

    本发明的两亲性聚合物组合物此外还适于制备药物活性化合物和前药的活性化合物组合物。 Amphiphilic polymer composition of the present invention are also suitable for preparing pharmaceutically active compounds and prodrugs of the active compound composition. 这些包括苯并二氮杂革、抗高血压药、维生素、细胞抑制剂一尤其是紫杉醇、麻醉药、神经安定药、抗抑郁药、抗生素、抗真菌剂、杀真菌剂、化疗药物、泌尿系统用药、血小板凝集抑制剂、磺酰胺类、解痉药、激素、免疫球蛋白、血清、甲状腺治疗药、精神药物、抗 These include benzodiazepine leather, antihypertensives, vitamins, cytostatics an especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antimycotics, fungicides, chemotherapeutics, urinary system drugs, platelet aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroid therapeutic agents, psychotropic drugs, anti-

    帕金森药和其他抗运动机能亢进药、眼科用药、神经病用产品、钙代谢调节剂、肌肉松弛药、麻醉药、类脂降低药、肝治疗药、冠状动脉药、心脏药、免疫治疗药、调节性肽及其抑制剂、催眠药、镇静药、妇科用药、抗痛风药、纤维蛋白溶解药、酶产品和运输蛋白、酶抑制剂、催吐药、血流刺激药、利尿药、诊断助剂、皮质激素类、胆减药、胆用治疗药、平喘药、 支气管解痉药(bronchospasmolytics)、 /3受体阻断剂、钙拮抗剂、ACE抑制剂、抗动脉;更化药、抗炎药、抗凝血药、抗〗McL压药、抗低血糖药、抗高血压药、抗纤维蛋白溶解药、抗癫痫药、抗呕吐药、解毒药、抗糖尿病药、抗心律不齐药、抗贫血药、抗过敏药、驱肠虫药、止痛药、兴奋剂、 醛固酮拮抗药和减肥产品。 Parkinson drugs and other anti-hyperkinetic drug, ophthalmic, neurological use products, calcium metabolism regulators, muscle relaxants, anesthetics, lipid lowering drugs, liver therapeutic drugs, coronary agents, cardiac drugs, immunotherapeutic agents, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecological medicine, anti-gout drug, fibrinolytic agents, enzyme products and transport proteins, enzyme inhibitors, emetics, blood flow stimulation, diuretics, diagnostic aids , corticosteroids, reduce the dosage of bile, gall therapeutic drugs, asthma drugs, bronchial antispasmodic drugs (bronchospasmolytics), / 3-blockers, calcium channel blockers, ACE inhibitors, anti-artery; more of the drugs, anti- inflammatory drugs, anticoagulants, anti〗 McL pressure medicine, anti-low blood sugar, anti-hypertensive, anti-fibrinolytic drugs, antiepileptics, anti-emetic drugs, antidotes, anti-diabetic drugs, anti-arrhythmic drugs , anti-anemia drug, antiallergic agents, anthelmintics, analgesics, stimulants, aldosterone antagonists and slimming products. 合适药物活性化合物的实例尤其是在US 2003/0157170第0105-0131段提到的活性化合物。 Examples of suitable pharmaceutically active compounds are particularly active compounds mentioned in US 2003/0157170 paragraph 0105-0131.

    此外,本发明的两亲性聚合物组合物适于制备化妆品活性化合物,尤其是化妆油和脂肪如花生油、霍霍巴油、椰子油、杏仁油、橄榄油、棕榈油、蓖麻油、大豆油或小麦胚芽油,精油如中欧山松油、薰衣草油、迷迭香油、杉油、松针油、桉树油、薄荷油、鼠尾草油、香柠檬油、松脂油、 蜂花油、刺柏油、柠檬油、茴香油、小豆蔻油、樟脑油等或这些油的混合物的含水制剂。 Furthermore, amphiphilic polymer composition of the present invention are suitable for the preparation of cosmetic active compounds, in particular cosmetic oils and fats such as peanut oil, jojoba oil, coconut oil, almond oil, olive oil, palm oil, castor oil, soybean oil, or wheat germ oil, essential oils such as Central Europe mountain pine oil, lavender oil, rosemary oil, cedar oil, pine needle oil, eucalyptus oil, peppermint oil, sage oil, bergamot oil, turpentine oil, bee flower oil, juniper, lemon mixture of aqueous formulation oil, anise oil, cardamom oil, camphor oil or these oils.

    此外,根据本发明的两亲性聚合物组合物适于制备食品添加剂如水不 In addition, according to an amphiphilic polymer composition of the present invention are suitable for the preparation of food additives such as water is not

    溶性维生素和维生素原,如维生素A、维生素A乙酸酯、维生素D、维生素E,生育酚衍生物如生育酚乙酸酯以及维生素K的制剂,尤其是含水制剂。 Soluble vitamins and provitamins, such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopheryl acetate and vitamin K preparations, particularly aqueous preparations.

    可以配制成本发明活性化合物组合物的有效物质的实例是: 染料:例如DE-A 10245209中所述的染料以及根据Color Index称为M 染料和溶剂染料和也称为M体染料的化合物。 Examples of the invention may be formulated into an effective substance of the active compound composition is: dye: such as dyes described in DE-A 10245209 and the compounds called M Color Index dyes and solvent dyes and dye, also known as M based. 合适的^Ht体染料的汇总 Summary ^ Ht suitable dye of

    例如可以在Ulhnanns EnzyklopSdie der technischen Chemie[Ullmann工业化学百科全书j,第4版,第10巻,第155-165页(还参见第7巻,第585 页及随后各页-蒽醌染料;第8巻,第244页及随后各页-偶氮染料;第9 巻,第313页及随后各页-喹酞酮染料)中找到。 For example, in Ulhnanns EnzyklopSdie der technischen Chemie [Encyclopedia of Industrial Chemistry Ullmann j, 4th edition, Volume 10, pages 155-165 section (see also Volume 7, page 585 ff - anthraquinone dye; Article 8 Volume, page 244 ff - dyes; Volume 9, page 313 ff - quinophthalone dye) found. 该文献及其中所提到的化合物作为参考引入本文中。 The compounds mentioned in the document and incorporated by reference herein. 根据本发明合适的分散体染料和溶剂染料包括类别大为不同的具有不同发色团的染料,例如蒽醌染料、单偶氮和重氮染料、喹酞酮染料、次曱基和偶氮次甲基染料、萘二曱酰亚胺染料、萘醌染料和硝基染料。 According to a suitable dispersion dyes and solvent dyes according to the invention comprises a very different category of dyes with different chromophores, for example anthraquinone dyes, monoazo and diazo dyes, quinophthalone dyes, and azo times base times 曱methyl dyes, naphthalenedicarboxylic Yue imide dyes, naphthoquinone dyes and nitro dyes. 根据本发明合适的M体染料的实例是下列Color Index 的分散体染料:CI分散黄l-228, CI錄橙1-148, C丄分散红1-349, C. 1.絲紫1-97, CI綠蓝1-349, C. 1.絲绿1-9, C. L絲棕1-21, CIM黑1-36。 According to embodiments of the present invention suitable M dye are the following dispersion dye Color Index: CI Disperse Yellow l-228, CI recorded orange 1-148, C Shang Disperse Red 1-349, C. 1. silk purple 1-97 , CI green blue 1-349, C. 1. silk green 1-9, C. L wire Brown 1-21, CIM black 1-36. 根据本发明合适的溶剂染料的实例是下列Color Index 的化合物:CI溶剂黄2-191, CI溶剂橙1-113, CI溶剂红1-248, CI 溶剂紫2-61, CI溶剂蓝2-143, CI溶剂绿l-35, C丄溶剂棕1-63, C. 1. 溶剂黑3-50。 According to embodiments of the present invention suitable solvent dyes are compounds of the following Color Index: CI Solvent Yellow 2-191, CI Solvent Orange 1-113, CI Solvent Red 1-248, CI Solvent Violet 2-61, CI Solvent Blue 2-143 , CI Solvent Green l-35, C Shang Solvent Brown 1-63, C. 1. Solvent Black 3-50. 根据本发明合适的其他染料是萘、蒽、芘、三并苯(terylene)、 四并苯(quarterylene)的衍生物,还有二酮基吡咯并吡咯染料、紫环酮染料、 香豆素染料、异二氢吲哚和异二氢吲哚酮染料,卟啉染料,酞菁和萘肽胥 According to the present invention, other suitable dyes are naphthalene, anthracene, pyrene, and benzene (terylene), four and benzene (quarterylene) derivatives, as well as diketone pyrrole dyes, perinone dyes, coumarin dyes , isoindoline and isoindolinone ketone dyes, porphyrin dyes, phthalocyanine and naphthalene peptide Xu

    染料;和 Dye; and

    UV吸收剂:尤其是选自如下a)-g)组的化合物。 UV absorbers: in particular compounds selected from the group a) -g).

    a) 4,4-二芳基丁二烯, a) 4,4- diaryl-butadiene,

    b) 肉桂酸酯类, b) cinnamic acid esters,

    c) 苯并三峻类,d) 羟基二苯甲酮类, c) Jun benzotriazole class, d) hydroxy benzophenones,

    e) 二苯基氰基丙烯酸酯类, e) diphenyl cyanoacrylate,

    f) 草酰胺类, f) grass amides,

    g) 2-苯基-l,3,5-三嗪类; g) 2- phenyl -l, 3,5- triazine;

    a)组的4,4-二芳基丁二烯例如包括式A化合物: a) the group of 4,4-diaryl-butadiene e.g. compounds of formula A:

    这些化合物由EP-A-916 335已知。 These compounds are known from the EP-A-916 335. 取代基111()和/或Ru优选为CrC8 111 substituents () and / or Ru is preferably CrC8

    烷基和Cs-C8环烷基。 Cs-C8 alkyl and cycloalkyl.

    b) 组的肉桂酸酯类例如包括4-曱氧基肉桂酸2-异戊基酯、4-甲氧基肉桂酸2-乙基己基酯、a-甲氧羰基肉桂酸甲酯、aMP-甲基-对甲氣基肉桂酸甲酯、a-氛基-P-甲基-对甲氧基肉桂酸丁酯和a-甲氧羰基对甲氧基肉桂酸甲酯。 b) group of cinnamic acid esters, for example include 4 曱 group cinnamic acid 2-iso-amyl, 4-methoxy cinnamic acid 2-ethylhexyl ester, a- cinnamate methoxycarbonyl, aMP- methyl - Toluene gas-cinnamic acid methyl ester, a- atmosphere group -P- methyl - methoxy cinnamic acid ester and a- methoxycarbonyl-methoxy cinnamic acid methyl ester.

    c) 组的苯并三唑类例如包括2-(2'-羟基苯基)苯并三唑类,如2-(2'-羟基-5'-甲基苯基)苯并三唑,2-(3,,5'-二叔丁基-2,-羟基苯基)苯并三唑,2-(5'-叔丁基-2'-羟基苯基)苯并三唑,2-(2'-羟基-5'-(l,l,3,3-四甲基丁基)苯基)苯并三唑,2-(3',5'-二叔丁基-2,-羟基苯基)-5-氯苯并三唑,2-(3'-叔丁基-2,-羟基-5'-甲基苯基)-5-氯苯并三峻,2-(3'-仲丁基-5'-叔丁基-2'-羟基苯基)苯并三唑, 2-(2'-羟基-4'-辛氧基苯基)苯并三唑,2-(3,,5'-二叔戊基-2,-羟基苯基)苯并三唑,2-(3,,5'-二(a,a-二曱基苄基)-2'-羟基苯基)苯并三唑,2-(3,-叔丁基-2'-羟基-5'-(2-辛氧羰基乙基)苯基)-5-氯苯并三唑,2-(3'-叔丁基-5'-12-(2-乙基己氧基)羰基乙基l-2'-羟基苯基)-5-氯苯并三峻,2-(3,-叔丁基-2'-羟基-5'-(2-甲氧羰基乙基)笨基)-5-氯苯并三哇,2-(3'-叔丁基-2'-羟基-5,-(2-甲氧羰基乙基) 苯基)苯并三唑,2-(3'-叔丁基-2'-羟基-5'-(2-辛氧羰基乙基)苯基沐并三喳, 2-(3,-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基】-2'-羟基苯基)苯并三唑, 2-(3'-十二烷基-2'-羟基-5'-甲基苯基)苯并三唑和2-(3'-叔丁基-2,-羟基-5,-(2-异辛氧羰基乙基)苯基苯并三唑,2,2'-亚甲基二14-(1,1,3,3-四甲基丁 c) groups such as benzotriazoles include 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 - (3,, 5'-di-t-butyl-2 - hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- ( 2'-hydroxy -5 '- (l, l, 3,3- tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-t-butyl-2 - hydroxyphenyl yl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 - hydroxy-5'-methylphenyl) -5 three Jun, 2- (3'-sec- butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ,, 5'-di-t-pentyl-2, - hydroxyphenyl) benzotriazole, 2- (3, 5'-di (a, a- two Yue benzyl) -2'-hydroxyphenyl) benzene benzotriazole, 2- (3, - tert-butyl-2'-hydroxy-5 '- (2-octyloxy-carbonyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert- butyl-5'-12- (2-ethyl-hexyloxy) carbonyl-ethyl l-2'- hydroxyphenyl) -5 three Jun, 2- (3, - tert-butyl-2 ' - hydroxy-5 '- (2-methoxycarbonyl-ethyl) stupid yl) -5 three wow, 2- (3'-tert-butyl-2'-hydroxy-5 - (2-methoxy carbonyl ethyl) phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '- (2-octyloxy-carbonyl) phenyl Mu and three chirp, 2- (3 , - tert-butyl-5 '- [2- (2-ethyl-hexyloxy) carbonyl] ethyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl -2 '- hydroxy-5'-methyl phenyl) benzotriazole and 2- (3'-tert-butyl-2 - hydroxy-5 - (2-ethylhexyl oxy-carbonyl) phenyl benzotriazole oxazole, 2,2'-methylenebis 14- (1,1,3,3-tetramethylbutyl butyric

    40基)-6-苯并三唑-2-基苯酚j; 2-[3,-叔丁基-5'-(2-甲氧羰基乙基)-2'-羟基苯基j-2H-苯并三唑与聚乙二醇300的酯化产物;【R-CH2CH2-COO(CH2)3h, 其中R-3'-叔丁基-4'-羟基-5'-2H-苯并三唑-2-基苯基,及其混合物。 40-yl) -6-benzotriazol-2-yl phenol j; 2- [3, - tert-butyl-5 '- (2-methoxycarbonyl-ethyl) -2'-hydroxyphenyl j-2H- benzotriazole with polyethylene glycol esterification product 300; [R-CH2CH2-COO (CH2) 3h, wherein R-3'- tert-butyl-4'-hydroxy -5'-2H- benzotriazole 2-phenyl, and mixtures thereof.

    d) 组的羟基二苯甲酮类例如包括2-羟基二苯甲酮类,如2-羟基-4-甲氧基二苯甲酮,2,2'-二羟基-4-甲氧基二苯甲酮,2,4-二羟基二苯甲酮,2,2,,4,4'-四羟基二苯甲酮,2,2,-二羟基-4,4'-二甲氧基二苯甲酮,2,2'-二羟基-4,4'-二甲氧基二苯曱酮,2-羟基-4-(2-乙基己氧基)二笨曱酮,2-羟基-4-(正辛氧基) 二苯曱酮,2-羟基-4-甲氧基-4'-甲基二苯甲酮,2-羟基-3-^二苯甲酮,2-羟基-4-甲氧基二苯甲酮-5-磺酸及其钠盐,2,2'-二羟基-4,4'-二甲氧基二苯甲酮-5,5'-二磺酸及其钠盐。 d) hydroxy group e.g. benzophenones include 2-hydroxy benzophenones, such as 2-hydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone benzophenone, 2,4-dihydroxy benzophenone, 2,2,, 4,4'-tetrahydroxy-benzophenone, 2,2 - dihydroxy-4,4'-dimethoxy two benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy diphenyl Yue ketone, 2-hydroxy-4- (2-ethyl-hexyloxy) two stupid Yue ketone, 2-hydroxy - 4- (n-octyloxy) Yue diphenyl ketone, 2-hydroxy-4-methoxy-4'-methyl benzophenone, 2-hydroxy-3 ^ benzophenone, 2-hydroxy-4 - methoxy benzophenone-5-sulfonic acid and its sodium salt, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone-5,5'-disulfonate and sodium.

    e) 組的二苯基氛基丙烯酸酯类例如包括2-氰基-3,3-二苯基丙烯酸乙酯,其可以例如以名称Uvinul®3035由BASF AG, Ludwigshafen市购, 2-g-3,3-二苯基丙烯酸2-乙基己基酯,其可以例如以名称Uvinul®3039 由BASF AG, Ludwigshafen市购,以及1,3-二1(2,-^-3',3'-二苯基丙烯酰基)氧基1-2,2-二{[2'-^-3',3'-二苯基丙烯酰基】氧基}甲基}丙烷,其可以例如以名称Uvinul® 3030由BASF AG, Ludwigshafen市购。 e) the group atmosphere diphenyl acrylate group include, for example 2-cyano-3,3-diphenyl acrylate, which may for example by a name Uvinul®3035 BASF AG, Ludwigshafen commercially available, 2-g- 3,3-diphenyl acrylate, 2-ethylhexyl acrylate, which may for example by a name Uvinul®3039 BASF AG, Ludwigshafen commercially available, and a 1,3-bis (2, - ^ --3 ', 3'- diphenylacryloyl) oxy 1-2,2- bis {[2 '- ^ --3', 3'-phenyl-acryloyl] oxy} methyl} propane, which may, for example under the name Uvinul® 3030 by the BASF AG, Ludwigshafen commercially available.

    f) 组的草酰胺类例如包括4,4,-二辛氧基草酰二苯胺,2,2'-二乙氧基草酰二苯胺,2,2'-二辛氧基-5,5'-二叔丁草酰二苯胺,2,2'-二-十二烷氧基-5,5'-二叔丁草酰二苯胺,2-乙氧基-2,-乙基草酰二苯胺,N,N,-二(3-二甲氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2'-乙草酰二苯胺及其与2-乙氧基-2,-乙基-5,4'-二叔丁草酰二笨胺的混合物,还有邻-、对-曱氧基二取代草酰二笨胺的混合物以及邻-和对-乙氧基二取代草酰二苯胺的混合物。 f) group of grass amides include, for example 4,4 - dioctyloxy oxanilide, 2,2'-diethoxy oxanilide, 2,2'-octyloxy-5,5 '- di-tert-oxanilide, 2,2 - 5,5-di-tert-butyl-dodecyloxy-oxanilide, 2-ethoxy -2 - ethyl oxalyl two aniline, N, N, - bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and with 2-ethoxy -2 - a mixture of ethyl-5,4-di-tert-butyl oxalyl two stupid amine, as well as o - on - 曱 oxalyl group disubstituted amine mixtures of two stupid neighbor - and on - ethoxydiethylene replace oxanilide mixture.

    g) 组的2-苯基-l,3,5-三溱类例如包括2-(2-羟基苯基)-l,3,5-三溱,如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-二(2,4-二甲基苯基)-l,3,5-三嗪、2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基笨基)-l,3,5-三嗪、2,4-二(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-l,3,5-三嗪、2-(2-羟基-4-辛氣基苯基)-4,6-二(4-甲基苯基)-l,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-二(2,4-二甲基苯基)-l,3,5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4,6-二(2,4-二甲基苯基H,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基】-4,6-二(2,4-二曱基)-l,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基H,6-二(2,4-二甲基)-l,3,5-三嗪、2-[4-(十二烷氣基/十三烷氧基-2-羟基丙氧基)-2-羟基苯基1-4,6-二(2,4-二甲基苯基)-1,3,5-三溱、2-【2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基1-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、 2-(2-羟基-4-己氧基苯基)-4,6-二苯基-l,3,5-三溱、2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-l,3,5-三嗪、2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基卜l,3,5-三嗪和2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-l,3,5-三嗪。 g) the group of 2-phenyl -l, 3,5- Qin three classes include, for example 2- (2-hydroxyphenyl) -l, 3,5- three Qin, such as 2,4,6-tris (2- hydroxy-4-octyloxy-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl yl) -l, 3,5- triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethyl stupid yl) -l, 3,5- triazine , 2,4-bis (2-hydroxy-4-propoxy-phenyl) -6- (2,4-dimethylphenyl) -l, 3,5- triazine, 2- (2-hydroxy - 4- oct gas-yl) -4,6-bis (4-methylphenyl) -l, 3,5- triazine, 2- (2-hydroxy-4-dodecyloxy-phenyl) - 4,6-bis (2,4-dimethylphenyl) -l, 3,5- triazine, 2- (2-hydroxy-4-tridecyl-phenyl) -4,6-bis ( 2,4-dimethylphenyl H, 3,5- triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butoxy-propoxy) phenyl] -4,6-bis (2,4-Yue-yl) -l, 3,5- triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propoxy) phenyl H, 6- bis ( 2,4-dimethylphenyl) -l, 3,5- triazine, 2- [4- (dodecyloxy group gas / thirteen-alkoxy-2-hydroxypropoxy) -2-hydroxyphenyl 1 4,6-bis (2,4-dimethylphenyl) -1,3,5-Qin, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy yl) phenyl 1-4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy-phenyl) -4, 6- diphenyl -l, 3,5- three Qin, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl -l, 3,5- triazine, 2, 4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl Jibu l, 3,5- triazine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl -l, 3,5- triazine.

    除了上述组分外,本发明的含水活性化合物组合物还可以包含常^L4 面活性物质及其他添加剂。 In addition to the above components, the aqueous composition of the active compounds of the present invention may further contain ordinary ^ L4 surface active substances and other additives. 表面活性物质包括表面活性剂、分歉剂和润湿剂。 Surface-active substances include surfactants, sub apology and wetting agents. 其他添加剂尤其包括增稠剂、消泡剂、防腐剂、防冻剂、稳定剂等。 Other additives include, inter alia thickeners, defoamers, preservatives, antifreeze agents, stabilizers and the like.

    原则上合适的是阴离子、阳离子、非离子和两性表面活性剂,其包括聚合物表面活性剂和在疏水基团中具有杂原子的表面活性剂。 In principle, suitable anionic, cationic, nonionic and amphoteric surfactants, including polymer surfactants and have a hetero atom in a hydrophobic surfactant groups.

    阴离子表面活性剂例如包括羧酸盐,尤其是脂肪酸的碱金属、碱土金属和铵盐,例如硬脂酸钾,其通常也称为皂;酰基谷氨酸盐;肌氨酸盐, 例如月桂酰肌氨酸钠;牛磺酸盐;甲基纤维素;磷酸烷基酯,尤其是单-和二磷酸的烷基酯;硫酸盐,尤其是烷1^琉酸盐和烷基醚硫酸盐;磺酸盐, 此外还有烷基磺酸盐和烷基芳基磺酸盐,尤其是芳基磺酸和烷基取代的芳基磺酸、烷基M酸如木素-和苯酚磺酸、萘-和二丁基萘磺酸的碱金属、 碱土金属和铵盐,或十二烷基M酸盐,烷基M酸盐,烷基曱基酯磺酸盐,磺化萘及其衍生物与曱醛的缩合物,萘磺酸、苯酚-和/或苯酚磺酸与甲醛或与甲醛和脲的缩合物,单-或二烷基磺基琥珀酸酯;还有蛋白水解物和木素亚硫酸盐废液。 Anionic surfactants include carboxylates such as, in particular, a fatty acid alkali metal, alkaline earth metal and ammonium salts, for example potassium stearate, which are usually referred to as soaps; acyl glutamates; sarcosinates such as lauroyl sarcosinate; taurates; methyl cellulose; alkyl phosphates, especially single - and di-alkyl phosphate esters; sulfates, especially 1 ^ alkoxy sulfur salts and alkyl ether sulfates; sulfonates, alkyl sulfonates and in addition to alkyl aryl sulfonates, aryl sulfonates and especially alkyl-substituted aryl sulfonic acid, alkyl acids such as lignin M - and phenolsulfonic acid, naphthalene - and dibutyl naphthalene sulfonic acid alkali metal, alkaline earth metal and ammonium salts, or salts dodecyl M, M alkyl formate, Yue alkyl ester sulfonates, sulfonated naphthalene and its derivatives and Yue aldehyde condensates, naphthalenesulfonic acid, phenol - and / or phenolsulfonic acid with formaldehyde or with formaldehyde and urea condensates, single - or dialkyl sulfosuccinates; and protein hydrolysates and lignin sulfite liquor. 上述磺酸有利的是以其中性或合适的话碱性盐的形式使用。 Wherein said acid is advantageous or, if appropriate, in the form of an alkaline salt.

    阳离子表面活性剂例如包括季铵化铵化合物,尤其是烷基三甲基卣化铵,二烷基二甲基卣化铵,烷基三甲基铵烷基硫酸盐,二烷基二甲基铵烷基硫酸盐,还有吡啶和咪唑啉衍生物,尤其是烷基吡啶错卣化物。 Cationic surfactants include, for example quaternized ammonium compounds, in particular alkyltrimethylammonium wine container ammonium, dialkyl dimethyl ammonium wine container, alkyl trimethyl ammonium alkyl sulfates, dialkyldimethylammonium ammonium alkyl sulfates, and pyridine and imidazoline derivatives, in particular alkylpyridinium wrong wine container thereof.

    非离子表面活性剂例如包括: -脂肪醇聚氧乙烯酯,例如月桂醇聚氧乙烯醚乙酸酯, -例如异十三烷醇的烷基聚氧乙烯醚和烷基聚氧丙烯醚,以及脂肪醇聚氧乙烯醚, Non-ionic surfactants include, for example: - alcohol polyoxyethylene esters, for example lauryl alcohol polyoxyethylene ether acetate, - for example isotridecyl polyoxyethylene alkyl ether and polyoxypropylene alkyl ether, and Fatty alcohol ethoxylates,

    -烷基芳基醇聚氧乙烯醚,例如辛基苯酚聚氣乙烯醚, - Alkyl aryl alcohol ethoxylates, such as octyl phenol poly vinyl ether gas,

    -烷氧基化动物和/或植物脂肪和/或油,例如玉米油乙氧基化物、蓖麻油 - Alkoxylated animal and / or vegetable fats and / or oils, such as corn oil ethoxylates, castor oil

    乙氧基化物、牛油脂肪乙氧基化物, -甘油酯,如甘油单硬脂酸酯, Ethoxylates, tallow fat ethoxylates, - glycerides, such as glyceryl monostearate,

    -脂肪醇烷氧基化物和羰基合成醇烷氧基化物,尤其是 - Fatty alcohol alkoxylates and oxo-alcohol alkoxylates, especially

    RO-(RwO)r(RwO)sR2o类型的烷l^化物,其中1118和1119相互独立地为C2H4、 C3H6、 C4H8且R20为H或d-Cu烷基,R为C3-C30烷基或C6-C30 链烯基,r和s相互独立地为0-50,其中这些数中的一个必须不为0, 如异十三烷醇和油醇聚氧乙烯醚, -烷基酚烷氣基化物,如乙氧基化异辛基酚、辛基酚或壬基酚,三丁基酚聚氧乙烯醚, RO- (RwO) r (RwO) sR2o type l ^ alkoxy compounds, wherein 1118 and 1119 are independently C2H4, C3H6, C4H8 and R20 is H or d-Cu alkyl group, R is C3-C30 alkyl or C6 -C30 alkenyl, r and s are independently from 0 to 50, where the number one must not be zero, such as isotridecyl alcohol and oleyl alcohol ethoxylates, - alkylphenol alkyl gas-based compounds, such as ethoxylated isooctylphenol, octylphenol or nonylphenol, tributyltin phenol ethoxylates,

    -脂肪胺烷氧基化物,脂肪酸酰胺烷氧基化物和脂肪酸二乙醇酰胺烷氧基 - Fatty amine alkoxylates, fatty acid amide alkoxylates and fatty acid diethanolamide alkoxy

    化物,尤其是其乙氧基化物, -糖类表面活性剂,山梨醇酯,如脱水山梨糖醇脂肪酸酯(脱水山梨糖醇单 Compounds, in particular its ethoxylates, - a saccharide surfactants, sorbitol esters such as sorbitan fatty acid esters (sorbitan glycol monomethyl

    油酸酯,脱水山梨糖醇三硬脂酸酯),聚氧乙烯脱水山梨糖醇脂肪酸酯, Oleate, dehydrated sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters,

    烷基聚糖苷,N-烷基葡糖酰胺, -烷基甲基亚砜, Alkyl polyglycosides, N- alkyl glucamides, - alkyl methyl sulfoxide,

    -烷基二甲基氧化膦,如十四烷基二甲基氧化膦。 - Alkyl dimethyl phosphine oxide, e.g. tetradecyl dimethyl phosphine oxide.

    两性表面活性剂例如包括磺基甜菜碱、g甜菜碱和烷基二甲基胺氧化物,例如十四烷基二甲基胺氧化物。 Amphoteric surfactants include, for example sulfobetaines, g betaines and alkyl dimethyl amine oxides, e.g., myristyl dimethyl amine oxide.

    在这里可以作为举例提到的其他表面活性剂是全氟化表面活性剂,聚硅氧烷表面活性剂,磷脂如卵磷脂或化学改性的卵磷脂,氨基酸表面活性剂,例如N-月桂酰基谷氨酸盐。 Here as examples of other surfactants mentioned are perfluorinated surfactants, silicone surfactants, phospholipids such as lecithin or chemically modified lecithins, amino acid surfactants, e.g., N- lauroyl glutamate.

    除非另有指明,上面所列表面活性剂的烷基链是通常具有8-20个碳原子的线性或支化基团。 Unless otherwise indicated, alkyl chain surfactants listed above are generally having 8-20 carbon atoms, a linear or branched group.

    在一个实施方案中,本发明的含水活性化合物组合物包含不超过10 重量%,优选不超过5重量%,尤其不超过3重量%,例如0.01-5重量% 或0.1-3重量%的常规表面活性物质,在每种情况下基于活性化合物和聚合 In one embodiment, the aqueous composition of the active compounds of the present invention comprise not more than 10 wt%, preferably not more than 5 wt%, in particular not more than 3% by weight, e.g., from 0.01 to 5% by weight of a conventional surface or 0.1-3% by weight active substance, in each case based on the active compound and the polymerization

    43物组合物的总量。 43 of the total composition. 在该情况下,常M面活性物质优选基于组合物的总重 In this case, the surface active material M is preferably constant based on the total composition weight

    量不超过5重量%,尤其不超过3重量%,例如为0.01-5重量%或0.1-3 重量%。 Amount of not more than 5% by weight, in particular not more than 3% by weight, e.g., 0.01 to 5% by weight or 0.1 to 3 wt%.

    然而,取决于应用,可能有利的是用表面活性物质配制本发明的活性化合物组合物。 However, depending on the application, it may be advantageous to use the active compounds are formulated surfactant composition of the present invention. 此时常规表面活性物质的比例基于活性化合物和聚合物组合物的总量通常为0.5-30重量%,尤其是1-20重量%,或基于配制的组合物总重量为0.2-20重量%,尤其是0.5-15重量%。 In this case the ratio of conventional surface active material based on the total amount of the active compound and the polymer composition is generally 0.5 to 30% by weight, in particular 1-20% by weight, or based on the total weight of the formulated composition 0.2 to 20% by weight, in particular 0.5 to 15% by weight.

    尽管本发明组合物的优点之一是它们的挥发性有机化合物含量j氐这一事实,但例如对某些应用而言可能需要将本发明组合物与有机溶剂、油和脂肪混合,优选环境友好或生物相容的溶剂或油和脂肪,例如上述水溶混性溶剂或其与水的溶混性仅非常有限或不与水溶混的溶剂、油或脂肪,例如: Although one advantage of the compositions of the present invention is that they are VOC j Di fact that, but for example, may require the compositions of the present invention and organic solvents, oils and fats mix for some applications, preferably environmentally friendly or biocompatible solvents or oils and fats, such as the aforementioned water-miscible solvent or water-miscible solvent or only a very limited solvent immiscible with water, oil or fat, for example:

    -石蜡油,芳族烃及芳族烃的混合物,例如二甲苯混合物,Solvesso100、 - Paraffin oil, aromatic hydrocarbons and mixtures of aromatic hydrocarbons, such as xylene mixtures, Solvesso100,

    150或200等, -酴类和烷基盼,例如苯酴、氢醌、壬基酚等, 150 or 200, etc., - yeast class and alkyl hope, yeast such as benzene, hydroquinone, nonylphenol,

    -具有4个以上碳原子的酮类,如环己酮、异佛尔酮、is叩herone、苯乙酮、茶乙酮, - Ketones having 4 or more carbon atoms, such as cyclohexanone, isophorone, is knocking herone, acetophenone, tea ethyl ketone,

    -具有4个以上碳原子的醇类,如乙酰化羊毛脂醇、鲸蜡醇、l-癸醇、1-庚醇、l-己醇、异十八烷醇、异丙醇、油醇、千醇, - Alcohols having 4 or more carbon atoms, such as acetylated lanolin alcohol, cetyl alcohol, l- decanol, 1-heptanol, l- hexyl alcohol, isostearyl alcohol, isopropyl alcohol, oleyl alcohol, one thousand alcohol,

    -羧酸酯,如己二酸二烷基酯如己二酸二(2-乙基己基)酯,邻苯二甲酸二烷基酯,如邻苯二甲酸二(2-乙基己基)酯,乙酸烷基斷还有支化的烷基), 如乙酸乙酯和乙酰乙酸乙酯,硬脂酸酯,如硬脂酸丁酯、甘油单石更脂酸酉旨,柠檬酸酯,如乙酰柠檬酸三丁酯,此外还有辛酸鲸蜡基酯、油酸甲酉旨、对羟基苯甲酸甲酯、十四烷酸甲酯、对羟基苯曱酸丙酯、苯甲酸甲酯,乳酸酯如乳酸异丙酯、乳酸丁酯和乳酸2-乙基己基酯, - Carboxylic acid esters, such as adipic acid dialkyl esters such as adipic acid di (2-ethylhexyl) phthalate, dialkyl esters, such as phthalic acid di (2-ethylhexyl) phthalate acetate, as well as branched alkyl off-alkyl), such as ethyl acetate and ethyl acetoacetate, stearates, such as butyl stearate, fatty acid monoglyceride stone more unitary purpose, citric acid esters, e.g. ATBC, in addition to the bitterness of cetyl ester, oleic acid methyl unitary purpose, methylparaben, tetradecane, methyl paraben, propyl Yue acid, methyl benzoate, milk esters such as lactic acid, isopropyl, butyl lactate and lactic acid, 2-ethylhexyl acrylate,

    -植物油,如棕榈油,菜籽油,蓖麻油及其衍生物,如氧化蓖麻油,椰子油,鳕鱼肝油,玉米油,大豆油,亚麻子油,,油,花生油,红花油, 芝眛油,圆柚油,罗勒油,杏仁油,姜油,香叶油,橙油,迷迭香油, 澳洲胡桃油,洋葱油,橘子油,松油,向日葵油, - Vegetable oils, such as palm oil, rapeseed oil, castor oil and derivatives thereof, such as castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil ,, oil, peanut oil, safflower oil, Chi Mei oil, grapefruit oil, basil oil, almond oil, ginger oil, geranium oil, orange oil, rosemary oil, macadamia nut oil, onion oil, orange oil, pine oil, sunflower oil,

    44-氢化植物油,如氢化棕榈油、氢化菜籽油、氢化大豆油, - 动物油,々P猪油、鱼油, 44- hydrogenated vegetable oils, such as hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated soybean oil, - animal oil, 々P lard, fish oil,

    -中链至长链脂肪酸的二烷基酰胺,例如Hallcomides,以及-植物油酯,如菜籽油甲基酯。 - Medium-chain to long chain fatty acid dialkyl amides, e.g. Hallcomides, and - esters of vegetable oils, such as rapeseed oil methyl ester.

    合适的增稠剂是赋予配制剂以假塑性流动行为,即在静止时粘度高且在搅拌状态下粘度低的化合物。 Suitable thickeners are impart to the formulation pseudoplastic flow behavior, ie high viscosity at rest and low viscosity in stirring state compounds. 就此而言例如可以提到多糖或有机片状矿物,如Xanthan Gum⑧(购自Kelco的Kdzan®), Rliodopo!® 23(Rhone Poulenc)或Veegum⑧(购自RT Vanderbilt)或Attada》,(购自Engelhardt), 优选Xanthan Gum®。 In this regard, for example may be mentioned polysaccharides or organic flake minerals, such as Xanthan Gum⑧ (available from Kelco's Kdzan®), Rliodopo! ® 23 (Rhone Poulenc) or Veegum⑧ (available from RT Vanderbilt) or Attada ", (available from Engelhardt ), preferably Xanthan Gum®.

    适于本发明*体的消泡剂例如为聚硅氧烷乳液(例如购自Wacker的Silikon® SRE或购自Rhodia的Rhodorsif),长链醇,脂肪酸,有机氟化合物及其混合物。 * Suitable defoamer of the present invention, for example, silicone emulsions (e.g. of Silikon® SRE, available from Wacker or available from Rhodia Rhodorsif), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.

    可以加入杀菌剂以稳定本发明组合物而防止械/微生物侵袭。 Fungicides can be added to stabilize the composition of the present invention to prevent mechanical / microbial attack. 合适的杀菌剂例如为购自ICI的Proxel⑧或购自Thor Chemie的Acticide® RS和购自Rohm & Haas的Kathon® MK。 Suitable fungicides, for example, available from ICI's Proxel⑧ or purchased from Acticide® RS from Thor Chemie and available from Rohm & Haas in Kathon® MK.

    合适的防冻剂是有机多元醇,例如乙二醇、丙二醇或甘油。 Suitable antifreeze are organic polyols, such as ethylene glycol, propylene glycol or glycerol. 这些防冻剂的用量基于活性化合物组合物的总重量通常不超过10重量%,从而不超过所需挥发性化合物的含量。 These antifreeze in an amount of active compound based on the total weight of the composition is typically no more than 10% by weight, whereby the content of volatile compounds is not more than required. 在本发明的一个实施方案中,不同于防冻剂的挥发性有机化合物的比例优选不超过1重量%,尤其不超过1000ppm。 In one embodiment of the present invention, the proportion of volatile organic compound is different from the antifreeze is preferably not more than 1% by weight, in particular not more than 1000ppm.

    合适的话,本发明的活性化合物组合物可以基于所制备的配制剂的总量包含1-5重量%的緩冲剂,以调节pH,其中所用緩沖剂的量和类型取决于活性化合物的化学性能。 If appropriate, the active compound compositions of the invention may comprise based on the total formulation prepared 1-5% by weight of a buffering agent to adjust the pH, wherein the amount and type of the buffer used depending on the chemical properties of the active compound. 緩冲剂的实例是弱无机或有机酸如磷酸、硼酸、 乙酸、丙酸、柠檬酸、富马酸、酒石酸、草酸和琥珀酸的碱金属盐。 Examples of buffers is weak inorganic or organic acids such as phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid alkali metal salt.

    取决于其中所含活性化合物或有效物质的性质,本发明的活性化合物 Depending on the nature of which contains the active compound or the active substance, the active compounds of the invention

    配制剂相当的方式使用。 Formulation equivalent manner. 例如,包含至少一种杀虫、杀螨或杀线虫活性化合物的活性化合物组合物可以用于防治有害昆虫、螨虫或线虫。 For example, the active compound composition comprising at least one insecticidal, acaricidal or nematicidal active compound may be used for controlling harmful insects, mites or nematodes. 若本发明的活性化合物组合物包含至少一种杀真菌活性化合物,则它们可以用于防治有害真菌。 If the active compound compositions of the invention comprise at least one fungicidally active compound to kill, they can be used for controlling harmful fungi. 若本发明的活性化合物组合物包含除草活性化合物,则它们可以用于防治杂草等。 If the active compound compositions of the invention comprise herbicidally active compounds, they may be used to control weeds.

    取决于活性化合物的性质,本发明的组合物尤其用于保护植物以防被有害生物体如昆虫、螨虫、线虫侵袭,或用于防止被植物病原性真菌等侵袭,或用于处理种子或用于保护材料,例如用于保护木质纤维素材料如木材以防有害昆虫如木材破坏性甲虫、白蚁、蚂蚁等的侵袭,或防止被木材变色或木材破坏性真菌侵袭。 Depending on the nature of the active compound, the compositions of the present invention are particularly useful for protecting plants against harmful organisms such as insects, mites, nematodes attack, or to prevent the plant pathogenic fungi and other attacks, or for the treatment of seeds or in protective material, such as for the protection of lignocellulosic materials such as wood to prevent the invasion of harmful insects such as wood damaging beetles, termites, ants, etc., or to prevent the invasion of wood or wood-destructive fungus discoloration.

    本发明组合物当然还可以用于化妆品或药物或工业应用中。 The compositions of the invention may of course also be used for cosmetic or pharmaceutical or industrial applications.

    现在使用下列实施例更详细说明本发明。 Now use the following examples of the present invention is described in more detail.

    I.制备两亲性聚合物组合物: 1.1制备实施例1: I. amphiphilic polymer composition: 1.1 Preparation Example 1:

    • 将1444g四氢呋喃在回流下加热。 • The 1444g of tetrahydrofuran was heated at reflux. 在2小时内同时加入由2109g曱基丙烯酸曱酯和703g苯乙烯组成的进料la以及由1444g四氢呋喃(THF)、 18.6g偶氮二异丁腈(AIBN)和58.4g巯基乙醇组成的进料lb,并将混合物在回流下保持24小时。 Within two hours while adding the 2109g 曱 曱 based acrylic ester and 703g styrene feed la and the 1444g of tetrahydrofuran (THF), 18.6g of azobisisobutyronitrile (AIBN) and 58.4g mercaptoethanol feed lb, and the mixture was kept at reflux for 24 hours. 然后加入430g市售六亚甲基二异氰酸酯的缩二脲(NCO含量为22。/。,在23。C下的粘度为4.0Pa.s)和O.lg 二月桂酸二丁基锡, 并将反应混合物在相同温度下搅拌,直到混合物的NCO含量降至1.02%。 Then add 430g of commercially available hexamethylene diisocyanate biuret (NCO content of 22. /., The viscosity at 23.C for 4.0Pa.s) and O.lg dibutyl tin, and the reaction The mixture was stirred at the same temperature until the NCO content of the mixture is reduced to 1.02%. 然后向该混合物中加入3000g甲基封端的聚氧乙烯(数均分子量为2000道尔顿,KOH数为33mg/g固体物质)并将反应混合物在相同温度下搅拌,直到NCO含量为0。 To this mixture was then added 3000g methyl-capped polyoxyethylene (number average molecular weight of 2000 daltons, KOH number of 33mg / g solids) was added and the reaction mixture was stirred at the same temperature until the NCO content was 0. 然后在30分钟内加入14.7kg水并在减压下蒸除四氩呋咱。 14.7kg of water was then added over 30 minutes and evaporated under reduced pressure argon furazan four. 得到浓度为30重量%的两亲性聚合物组合物水^:体,其平均粒度为50nm(由动态光散射测定)。 To give a concentration of 30% by weight of amphiphilic polymer composition Water ^: body, having an average particle size of 50nm (as measured by dynamic light scattering). 1.2制备实施例2: 1.2 Preparation Example 2:

    将1444g THF在回流下加热。 The 1444g THF was heated at reflux. 在2小时内同时加入由2109g甲基丙烯酸甲酯和703g苯乙烯组成的进料la和由1444g四氢呋喃、18.6gAIBN和58.4g巯基乙醇组成的进料lb,并将混合物在回流下保持24小时。 It was added over 2 hours while the feed la 2109g 703g of methyl methacrylate and styrene and the 1444g of tetrahydrofuran, 18.6gAIBN mercaptoethanol and 58.4g feed lb, and the mixture was kept at reflux for 24 hours. 然后加入167g异佛尔酮二异氛酸酯和0.7g 二月桂酸二丁基锡,并将反应混合物在相同温度下搅拌,直到混合物的NCO含量降至0.53%。 Then add 167g of isophorone diisocyanate atmosphere ester and 0.7g of dibutyl tin, and the reaction mixture was stirred at the same temperature until the NCO content of the mixture is reduced to 0.53%. 然后向该混合物中加入1500g甲基封端的聚氧乙烯(数均分子量为2000道尔顿,KOH数为33mg/g固体物质)并将反应混合物在相同温度下搅拌,直到NCO含量为0。 To this mixture was then added 1500g methyl-capped polyoxyethylene (number average molecular weight of 2000 daltons, KOH number of 33mg / g solids) was added and the reaction mixture was stirred at the same temperature until the NCO content was 0. 然后在30分钟内加入10.6kg水并在减压下蒸除四氢呋喃。 10.6kg of water was then added over 30 minutes and the tetrahydrofuran was distilled off under reduced pressure. 得到浓度为30重量V。 To give a concentration of 30 wt V. 的两亲性聚合物组合物水分歉体,其平均粒度为52nm(由动态光散射测定)。 The amphiphilic polymer composition apology water body, having an average particle size of 52nm (as measured by dynamic light scattering). 1.3制备实施例3: 1.3 Preparation Example 3:

    将1444gTHF在回流下加热。 The 1444gTHF heated under reflux. 在2小时内同时加入由2109g甲基丙烯酸甲酯和703g苯乙烯组成的进料la和由1444g四氢呋喃、18.6g AIBN和58.4g巯基乙醇组成的进料lb,并将混合物在回流下保持24小时。 It was added over 2 hours while the feed la 2109g 703g of methyl methacrylate and styrene and the feed lb 1444g of tetrahydrofuran, 18.6g AIBN and 58.4g consisting of mercaptoethanol, and the mixture was kept at reflux for 24 hours . 然后加入430g市售六亚曱基二异氛酸酯的缩二脲(NCO含量为22%,在23。C下的粘度为4.0Pa.s)、3000g甲基封端的聚氧乙烯(数均分子量为2000道尔顿, KOH数为33mg/kg固体物质)和0.87g 二月桂酸二丁基锡,并将反应混合物在相同温度下搅拌,直到NCO含量降至0%。 Then add 430g of commercially available 曱 group hexamethylene diisocyanate biuret atmosphere ester (NCO content of 22% and a viscosity of at 23.C under 4.0Pa.s), 3000g methyl-terminated poly (ethylene oxide) (number average molecular weight of 2000 daltons, KOH number of 33mg / kg solids) and 0.87g dibutyltin dilaurate, and the reaction mixture was stirred at the same temperature until the NCO content is reduced to 0%. 然后在30分钟内加入14.7kg水并在减压下蒸除四氢呋喃。 14.7kg of water was then added over 30 minutes and the tetrahydrofuran was distilled off under reduced pressure. 得到浓度为30重量%的两亲性聚合物组合物水分散体,其平均粒度为52nm(由动态光散射测定)。 To give a concentration of 30% by weight of amphiphilic polymer composition an aqueous dispersion having an average particle size of 52nm (as measured by dynamic light scattering).

    I. 4制备实施例4: I. 4 Preparation Example 4:

    将430g制备实施例1中所用的市售六亚甲基二异氰酸酯的缩二脲、 3000g甲基封端的聚氧乙烯(OH数为33mg KOH/g固体物质)和117mg 二月桂酸二丁基锡溶于3430g四氢呋喃中。 The 430g Preparation Example 1 was used in a commercial embodiment of hexamethylene diisocyanate biuret, polyoxyethylene 3000g methyl-terminated (OH number of 33mg KOH / g solids) and 117mg of dibutyl tin dissolved 3430g of tetrahydrofuran. 将该溶液在回流温度下搅拌,直到NCO含量为0.46%。 The solution was stirred at reflux temperature until an NCO content of 0.46%.

    将1444gTHF在回流下加热。 The 1444gTHF heated under reflux. 在2小时内同时加入由2109g甲基丙烯酸甲酯和703g苯乙烯组成的进料la和由1444g四氢呋喃、18.6gAIBN和58.4g巯基乙醇组成的进料lb,并将混合物在回流下保持24小时。 It was added over 2 hours while the feed la 2109g 703g of methyl methacrylate and styrene and the 1444g of tetrahydrofuran, 18.6gAIBN mercaptoethanol and 58.4g feed lb, and the mixture was kept at reflux for 24 hours. 然后加入已经同时制备的六亚甲基二异氰酸酯的缩二脲与甲基封端的聚氣乙烯的反应产物,并将反应混合物在相同温度下搅拌,直到混合物的NCO含量为0%。 Biuret reaction product of methyl-terminated poly ethylene gas was then added at the same time have been prepared hexamethylene diisocyanate and the reaction mixture was stirred at the same temperature until the NCO content of the mixture was 0%. 然后在30分钟内加入14.7kg水并在减压下蒸除四氢呋喃。 14.7kg of water was then added over 30 minutes and the tetrahydrofuran was distilled off under reduced pressure. 得到浓度为30重量%的两亲性聚合物组合物水^体(粒度为129nm,由动态光散射测定)。 Amphiphilic polymer composition of water bodies ^ (particle size of 129nm, as determined by dynamic light scattering) to give a concentration of 30% by weight.

    II. 制备本发明的含水活性化合物制剂II.l分析: . II aqueous active compound formulation II.l invention are prepared analysis:

    这里所迷的粘度在旋转粘度计中根据DIN 53019-2测定。 The viscosity of the fans here in a rotational viscometer measured in accordance with DIN 53019-2. 平均粒径使用含水活性化合物配制剂的稀样品在20°C下由静态光散射方法测定。 The average particle size of the active compound with an aqueous formulation of dilute samples at 20 ° C as measured by static light scattering method.

    为了测试储存稳定性,将含水活性化合物组合物在54'C下储存2周并在5C下储存2周。 In order to test the storage stability, the aqueous active compound composition stored two weeks at 54'C and stored at 5C 2 weeks. 此外,冷冻和融化活性化合物组合物。 Furthermore, freezing and thawing of the active compound composition. 若在这些条件下既没有)i见察到沉降也没有观察到分层,则样品是储存稳定的。 If neither under these conditions) i see observed sedimentation stratification was not observed, the sample is storage stable. II.2通用制备程序: II.2 General preparation procedure:

    1. 增溶方法(液体活性化合物和活性化合物熔体): 1. The solubilization process (liquid active compounds and active compound melt):

    在使活性化合物以低粘度熔体存在的温度下将10g活性化合物搅入90g包含30g聚合物的两亲性聚合物组合物的水M体中。 In the case of the active compound in the presence of a low temperature melt viscosity of the active compound is stirred into 90g 10g 30g polymer comprising amphiphilic polymer composition of the body M of water. 取决于聚合物溶液和活性化合物熔体的粘度,使用磁力搅拌器或Ultraturrax进行搅拌。 Depending on the polymer solution and the melt viscosity of the active compound, or using a magnetic stirrer Ultraturrax stirring. 直到实现增溶平衡所需的时间取决于聚合物组合物和活性化合物且可以为几秒钟,还可以为数小时。 Until a solubilization time required depends on the balance and the polymer composition and active compound may be a few seconds, can also hours. 在活性化合物均匀分布于该混合物中且甚至在引入更多能量时也观察不到粒度变化时达到增溶平衡。 In the uniform distribution of the active compound to reach equilibrium solubilized in the mixture and the introduction of more energy even when the size changes are observed.

    2. 相反转方法: 2. inversion methods:

    将10g液态或固态活性化合物和30g两亲性聚合物组合物(聚合物含量>95重量%)溶于沸点低于10(TC的有机溶剂(例如四氢呋喃)中。然后在搅拌下加入水并随后通过蒸馏除去有机溶剂。加入的水量应使所得含水配制剂包含10重量%活性化合物和30重量%聚合物。 10g of the active compound and a liquid or solid 30g amphiphilic polymer composition (polymer content> 95% by weight) was dissolved in boiling point lower than 10 (TC organic solvent (e.g. tetrahydrofuran) was then added with stirring and then water the organic solvent was removed by distillation. The water should be added to the resulting aqueous formulation containing 10% by weight of active compound and 30 wt% polymer.

    3. 固溶液方法: 3. Solid solution process:

    将0.5g两亲性聚合物组合物(聚合物含量>95重量%)和O.lg活性化合物溶于约20ml二甲基甲酰胺中。 0.5g of amphiphilic polymer composition (polymer content> 95 wt%) and O.lg of the active compound is dissolved in about 20ml dimethyl formamide. 然后完全除去溶剂(例如在旋转蒸发器上), 从而得到疏水性活性化合物和两亲性聚合物组合物的固溶液。 The solvent is then completely removed (e.g., in a rotary evaporator), thereby obtaining a solid solution of the active compound and a hydrophobic amphiphilic polymer composition. 加入緩沖的水溶液(100ml, pH 6.8)并将该混合物搅拌24小时。 Was added a buffered solution (100ml, pH 6.8) was added and the mixture was stirred for 24 hours. 在过滤之后通过HPLC(UV检测器)分析该溶液并测定活性化合物浓度。 After filtration by HPLC (UV detector) analysis of the solution was measured and the concentration of the active compound.

    4. 喷嘴沉淀: The jet precipitation:

    使用两个泵经由混合喷嘴在混合设备中将浓度为30%的聚合物水分散体和浓度为40。 Using two pumps via a mixing nozzle in a mixing device in the concentration of 30% aqueous dispersion of a polymer and a concentration of 40. /。 /. 的活性化合物/THF溶液混合。 Active compound / THF solution was mixed. 聚合物^L体的流速为12kg/h, THF溶液的流速为3kg/h,从而使总流速为15kg/h。 ^ L flow rate of the polymer body was 12kg / h, the flow rate of THF solution was 3kg / h, so that the total flow rate of 15kg / h. 混合i殳备与"Handbook of Industrial Crystallization ,, (AS Myerson , 1993Butterworth画Heinemami,第139页,ISBN 0-7506-9155-7)中所述的设备相类似。得到包含8%活性化合物和24%聚合物的浅黄色乳状悬浮液。然后通过蒸馏除去THF和一些水,从而形成包含10%活性化合物和30%聚合物的含水纳米颗粒配制剂。 Preparation and mixing i Shu "Handbook of Industrial Crystallization ,, (AS Myerson, 1993Butterworth painting Heinemami, p. 139, ISBN 0-7506-9155-7) in the device are similar. Get active compound containing 8% and 24% The pale yellow polymer milky suspension. Then THF was removed and some of the water, thereby forming a compound comprising 10% active polymer and 30% aqueous nanoparticle formulation by distillation.

    II.3配制实施例l:通过相反转方法增溶唑菌胺酯(通用程序2) II.3 Formulation Example l: inversion method by solubilizing pyraclostrobin (general procedure 2)

    将10g唑菌胺酯和30g来自实施例2的两亲性聚合物组合物一起溶于100g THF中。 The 10g and 30g pyraclostrobin amphiphilic polymer composition from Example 2 is dissolved together in 100g THF. 然后在搅拌下加入水并在减压下除去THF。 Water is then added with stirring and under reduced pressure to remove THF. 水量的选择应使所得含水配制剂包含10重量%活性化合物和30重量%两亲性聚合物组合物。 Water should be selected so that the resulting aqueous formulation comprises 10 wt% and 30 wt% of the active compound amphiphilic polymer composition.

    所得活性化合物组合物均匀,基^L觉上透明,沉降稳定至少几个月且能够用水稀释(去离子水和10。d [德国硬度】的水均可)而不发生活性化合物的沉降或结晶。 The resulting homogeneous composition of the active compound, based on the transparent feel ^ L, sedimentation stable for at least several months and can be diluted with water (deionized water and 10.d [German hardness] water may be) sedimentation or crystallization of the active compound without the risk of . ^相(聚合物/活性化合物颗粒)具有球形结构且由光散射测定的平均直径为约30nm。 ^ Phase (polymer / active compound particles) having a spherical structure determined by light scattering and an average diameter of about 30nm.

    II.4配制实施例2:通过增溶方法增溶唑菌胺酯(通用程序1) II.4 Formulation Example 2: Method by solubilization solubilizing pyraclostrobin (General Procedure 1)

    在70'C下唑菌胺酯为易于流动的熔体(粘度为2200mPas)且因此使用 At 70'C under pyraclostrobin melt to flow easily (viscosity 2200mPas) and therefore the use of

    通用程序1在70。 General Procedure 1 in 70. C的温度下配制。 Temperature C under preparation. 所得活性化合物组合物均匀,基本视觉 The resulting homogeneous composition of the active compound, the basic visual

    上透明,沉降稳定至少几个月且能够用水稀释(去离子水和10°d的水均可) Transparent, sedimentation stable for at least several months and can be diluted with water (deionized water and water 10 ° d may be)

    而不发生活性化合物的沉降或结晶。 Sedimentation or crystallization of the active compound without the risk.

    絲相(聚合物/活性化合物颗粒)具有球性结构且由光散射测定的平均 The average wire phase (polymer / active compound particles) has a spherical structure and measured by a light scattering

    直径为约30nm。 Diameter of about 30nm.

    H.5配制实施例3:通过喷嘴沉淀增'溶唑菌胺酯(通用程序4) H.5 Formulation Example 3: precipitation through the nozzle by 'dissolving pyraclostrobin (General Procedure 4)

    使用通用程序4配制唑菌胺酯。 4 generic program formulated pyraclostrobin. 所得活性化合物组合物均匀,基a 觉上透明,沉降稳定至少几个月且能够用水稀释(去离子水和10°d的水均可)而不发生活性化合物的沉降或结晶。 The resulting homogeneous composition of the active compound, based on a transparent feel, sedimentation stable for at least several months and can be diluted with water (deionized water and the water can be 10 ° d) sedimentation or crystallization of the active compound without occurrence.

    II.6配制实施例4:通过相反转方法增溶环戊唑菌(通用程序2) II.6 Formulation Example 4: solubilized metconazole by inversion method (general procedure 2)

    将10g环戊唑菌(熔点为110-113t:的固体)和30g来自实施例1的两亲性聚合物组合物一起溶于100g THF中。 10g of metconazole (m.p. 110-113t: solids), and 30g from amphiphilic polymer composition of Example 1 was dissolved in 100g THF together. 然后在搅拌下加入水并在减压下除去THF。 Water is then added with stirring and under reduced pressure to remove THF. 水量的选择应使所得含水配制剂包含10重量%活性化合物和30重量%两亲性聚合物组合物。 Water should be selected so that the resulting aqueous formulation comprises 10 wt% and 30 wt% of the active compound amphiphilic polymer composition. 所得活性化合物组合物均匀,基«觉上透明,沉降稳定至少几个月 The resulting active compound composition uniformity, group «feel transparent, sedimentation stable for at least several months

    且能够用水稀释(去离子水和10°d的水均可)而不发生活性化合物的沉降或 And can be diluted with water (deionized water and the water can be 10 ° d) without the risk of sedimentation of the active compound or

    結晶。 Crystallization. M相(聚合物/活性化合物颗粒)具有球形结构且由光散射测定的平 M phase (polymer / active compound particles) having a spherical structure and level as measured by a light scattering

    均直径为约30nm。 Average diameter of about 30nm.

    列于表1中的其他活性化合物也可以以类似方式配制。 Other active compounds listed in Table 1 may also be formulated in a similar manner.

    表l Table l

    活性化合物 在蒸馏水中的溶解度【mg/1】 The solubility of the active compound in distilled water [mg / 1]

    氧咬菌(epoxyconazole) 6.63 Oxygen bite bacteria (epoxyconazole) 6.63

    夂酰菌胺 4.6 Fan acid bacteria amine 4.6

    唑菌胺酯 2.4 Pyraclostrobin 2.4

    环戊唑菌 15 Metconazole 15

    曱体氯氛菊酯 0.01 Zadtilvfen permethrin 0.01

    II.7配制实施例5:通过相反转方法增溶维生素A乙酸酯(通用程序2) Formulation Example II.7 5: solubilization of vitamin A acetate by phase inversion method (general procedure 2)

    将10g维生素A乙酸酯和30g来自实施例1的两亲性聚合物組合物一起溶于100gTHF中。 10g of vitamin A acetate and 30g from amphiphilic polymer composition of Example 1 was dissolved in 100gTHF together. 然后在搅拌下加入水并在减压下除去THF。 Water is then added with stirring and under reduced pressure to remove THF. 水量的选择应使所得含水配制剂包含10重量%活性化合物和30重量%两亲性聚合物组合物。 Water should be selected so that the resulting aqueous formulation comprises 10 wt% and 30 wt% of the active compound amphiphilic polymer composition.

    所得活性化合物组合物均匀,基«觉上透明,沉f^^急定至少几个月且能够用7JC稀释(去离子水和10。d的水均可)而不发生活性化合物的沉降或结晶。 The resulting active compound composition uniformity, group «feel transparent, Shen f ^^ urgent given at least several months and can be diluted with 7JC (deionized water and 10.d of water can be) sedimentation or crystallization of the active compound without the risk .

    III 应用测试 III Application Testing

    in.i杀真菌活性的评价 in.i kill fungal activity evaluation

    根据下列程序比较来自配制实施例i的含水活性化合物组合物和相同活性化合物唑菌胺酯的两种市售配制剂在温室中对西红柿上的致病疫霉 According to the following procedure from the preparation of Comparative Example i two commercial formulations of aqueous active compound compositions of the same active compound pyraclostrobin implemented in the greenhouse of Phytophthora infestans on tomatoes

    (Phytophthora infestans)的活性(预防试验,保护性活性): (Phytophthora infestans) activity (prevention trial, protective activity):

    使用自来水将活性化合物配制剂稀释至所需活性化合物浓度(4-250ppm)。 Using tap the active compound formulation diluted to the desired concentration of active compound (4-250ppm). 使用体积为25ml的喷雾枪施用于西红柿植物上,这对应于水的量为5001/ha,该量是实践中常用的量。 A volume of 25ml spray gun applied to the tomato plant, the amount of which corresponds to the water is 5001 / ha, the amount is the amount of practice commonly used. 在处理7天后接种标准真菌(致病疫霉)。 7 days after the inoculation standards in dealing with fungi (Phytophthora infestans). 将测试植物放于18-20X:和90%相对大气湿度的温室中。 The test plants are kept at 18-20X: and 90% relative atmospheric humidity in the greenhouse. 接种5 天后通过测定叶子的侵染百分数而进行评价。 5 days after inoculation by measuring the percentage of infected leaves and evaluated. 生物学试验的结果总结于表2中。 The results of biological tests are summarized in Table 2 below. 结果表明稳定在聚合物颗粒中的活性化合物的杀真菌活性与市售产品处于相同水平。 The results show that stabilization in commercial products and fungicidal activity of the active compound in the polymer particles is at the same level.

    表2:致病疫霉-5天后在西红柿上的侵染【%】,为活性化合物含量的函数 Table 2: Phytophthora infestans infection -5 days on tomato [%], the active compound content of function

    <table>table see original document page 51</column></row> <table> <Table> table see original document page 51 </ column> </ row> <table>

    1) EC配制剂 1) EC formulation

    23.5重量°/。 23.5 wt ° /. 唑菌胺酯, 4.7重量%阴离子润湿剂,和4.7重量%非离子润湿剂, Pyraclostrobin, 4.7% by weight of an anionic wetting agent, and 4.7% by weight of a nonionic wetting agent,

    在67.1重量%芳族溶剂中。 At 67.1% by weight of an aromatic solvent.

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    Classifications
    International ClassificationC08G18/38, A01N25/30, C08L75/04, A01N25/04, C08L33/06, C08G18/28, C08G18/62, C08G18/75, C08G18/78
    Cooperative ClassificationA01N25/04, C08L75/04, C08G18/7831, A01N25/30, C08G18/3876, C08G18/283, C08L33/06
    European ClassificationC08L75/04, C08G18/28D5F, A01N25/30, C08G18/38H30, C08G18/78B4F, A01N25/04
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