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    Publication numberCN1965011 A
    Publication typeApplication
    Application numberCN 200580018733
    PCT numberPCT/EP2005/006106
    Publication date16 May 2007
    Filing date7 Jun 2005
    Priority date8 Jun 2004
    Also published asCA2567660A1, CA2567660C, CN100567358C, DE502005002170D1, EP1756188A1, EP1756188B1, US7872067, US20080287593, WO2005121201A1
    Publication number200580018733.7, CN 1965011 A, CN 1965011A, CN 200580018733, CN-A-1965011, CN1965011 A, CN1965011A, 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
    InventorsG·奥特, C·克吕格尔, H·克勒, M·舍勒尔, N·瓦格纳, M·布拉茨, R·贝格豪斯, R·范格尔德
    Applicant巴斯福股份公司
    Export CitationBiBTeX, EndNote, RefMan
    External Links: SIPO, Espacenet
    Amphiphilic polymer compositions and their use
    CN 1965011 A
    Abstract
    The invention relates to amphiphilic polymer compositions, to a method for their production and to their use for producing aqueous active ingredient compositions of water-insoluble active ingredients, in particular active ingredients for crop protection. The amphiphilic polymer compositions are obtained by reacting a) at least one hydrophobic polymer P1, which carries functional groups R<1> that are reactive in relation to isocyanate groups and which is composed of ethylenically unsaturated monomers M1, comprising: a1) at least 10 wt. %, (in relation to the total quantity of the monomers M1), of monomers M1a of general formula (I), in which X represents oxygen or an N-R<4> group; R<1>, R<2>, R<3>, and R4 are defined as cited in the claims and the description; a2) up to 90 wt. %, (in relation to the total quantity of the monomers M1) of neutral, monoethylenically unsaturated monomers M1b, whose solubility in water at 25 DEG C is less than 50 g/l and which differ from the monomers M1a; and a3) up to 30 wt. %, (in relation to the total quantity of the monomers M1, of ethylenically unsaturated monomers M1c, which differ from the monomers M1a and M1b, b) at least one hydrophilic polymer P2, which carries functional groups R<2> that are reactive in relation to isocyanate groups, c) with at least one compound V, which has a functionality of at least 1.5 in relation to the isocyanate groups.
    Claims(23)  translated from Chinese
    1.一种可以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: A component can be produced by the following reaction obtained amphiphilic polymer composition: a) at least one hydrophobic polymer P1, the polymer having an isocyanate group is in a reactive functional group RP1 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 a monomer of Formula I 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;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。 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 monomer 25 ℃ solubility in water at less than 50g / l and is different from the monomers M1a; and a3) based on the total amount of the monomers M1 is at most 30% by weight of ethylenically unsaturated monomers M1c, which is different from the monomers M1a monomer and M1b, b) at least one hydrophilic polymer P2, the polymer having an isocyanate group is in a reactive functional groups of RP2, c) at least one compound V, the compound containing isocyanate groups and isocyanate in terms of groups having a functionality of at least 1.5.
    2.根据权利要求1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F1为0.5-1.5。 2. The polymer composition according to claim 1, wherein the hydrophobic polymer having a functional group in terms of functionality RP1 F1 of 0.5-1.5.
    3.根据前述权利要求中任一项的聚合物组合物,其中疏水性聚合物P1的数均分子量为500-20000道尔顿。 3. the preceding claims polymer composition according to any one of, wherein the hydrophobic polymer P1 of the number average molecular weight of 500-20000 daltons.
    4.根据前述权利要求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。 4. The polymer composition according to any one of the preceding claims, wherein the hydrophilic polymer has no ionic groups.
    5.根据权利要求4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%的脂族聚醚由氧化乙烯基团构成。 5. The polymer composition according to claim 4, wherein the hydrophilic polymer P2 is an aliphatic polyether, wherein at least 70% by weight of aliphatic polyethers constituted by the ethylene oxide groups.
    6.根据前述权利要求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。 The polymer composition according to any one of the preceding claims, wherein the functionality of the hydrophilic polymer P2 having a functional group in terms of F2 RP2 0.5 to 3.0.
    7.根据前述权利要求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500-20000道尔顿。 7. A polymer composition according to any one of the preceding claims, wherein the number of the hydrophilic polymer P2 average molecular weight of 500-20000 daltons.
    8.根据前述权利要求中任一项的聚合物组合物,其中疏水性聚合物P1和亲水性聚合物P2以1∶10-10∶1的重量比P1∶P2使用。 According to the preceding claims polymer composition according to any one of, wherein the hydrophobic polymer P1 and the hydrophilic polymer P2 with a weight ratio of P1:P2 1:10-10:1 use.
    9.一种制备根据前述权利要求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构成且带有对异氰酸酯基团呈反应性的官能基团RP1的疏水性聚合物P1,ii)至少一种带有对异氰酸酯基团呈反应性的官能基团RP2的亲水性聚合物P2,iii)至少一种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的化合物V。 A preparation method according to any one amphiphilic polymer composition of the preceding claims, which comprises reacting components i) and ii) and iii) reaction of: i) at least one ethylenically unsaturated genus and with a single M1 constitute an isocyanate group is in a reactive functional groups of RP1 hydrophobic polymer P1, ii) having at least one isocyanate group to form hydrophilic polymeric functional group reactivity RP2 was P2, iii) at least one isocyanate-containing groups and for the purposes of the isocyanate groups of at least one compound having a functionality of 1.5 V.
    10.根据权利要求9的方法,其中使聚合物P1和聚合物P2依次与化合物V反应。 10. The method according to claim 9, wherein the polymer P1 and the polymer P2 in turn reacted with compound V.
    11.根据权利要求9的方法,其中使聚合物P1和聚合物P2在一步中与化合物V反应。 11. The method according to claim 9, wherein the polymer P1 and the polymer P2 are reacted in one step with a compound of V.
    12.根据权利要求1-8中任一项的两亲性聚合物组合物在将在25℃/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。 According to claim amphiphilic polymer composition according to any one of 1-8 in 25 ℃ / 1013 mbar solubility in water of less than 10g / l of the active compound and / or active substances in stabilized aqueous media use.
    13.根据权利要求1-8中任一项的两亲性聚合物组合物在制备在25℃/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。 According to claim amphiphilic polymer composition according to any one of 1-8 in the preparation of the 25 ℃ / 1013 mbar solubility in water of less than 10g / l of the active compound and / or the active substance formulation The uses.
    14.根据权利要求1-8中任一项的两亲性聚合物组合物在制备在25℃/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。 According to claim amphiphilic polymer composition according to any one of 1-8 in the preparation of the 25 ℃ / 1013 mbar lower than the solubility in water of the aqueous formulation 10g / l of the active compound and the active substance It uses.
    15.一种活性化合物组合物,包含至少一种在25℃/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1-8中任一项的两亲性聚合物组合物。 15. An active compound composition comprising at least one at 25 ℃ / 1013 mbar solubility in water of less than 10g / l of the active compound and / or at least one active substance according to any of claims 1-8 an amphiphilic polymer composition.
    16.一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℃/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1-8中任一项的两亲性聚合物组合物的分散相。 16. An aqueous active compound composition comprising an aqueous medium as continuous phase and at least one comprises at least one 25 ℃ / 1013 mbar is lower than the water solubility of the active compound 10g / l and / or active substances and a dispersed phase of at least one amphiphilic polymer composition according to any of claims 1-8.
    17.根据权利要求16的活性化合物组合物,其中分散相的颗粒具有的平均粒度通过动态光散射测定不超过300nm。 17. The active compound composition of claim 16, wherein the average particle size of the dispersed phase particles have measured by dynamic light scattering of not more than 300nm.
    18.根据权利要求15、16或17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。 18. The active compound composition of claim 15, 16 or 17, in a weight ratio 1:10-3:1 comprising the active compound and / or the active substance and the amphiphilic polymer composition.
    19.根据权利要求15-18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%。 19. A compound according to claim active composition according to any one of 15-18, wherein the content of volatile organic compounds based on the total weight of the composition is less than 10% by weight.
    20.一种制备根据权利要求15-19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。 20. A method for preparing a compound according to claim active composition according to any one of 15-19, including the preparation comprising amphiphilic polymer composition and active compound A and / or homogeneous non-aqueous mixture of at least the active substance .
    21.一种制备根据权利要求16-19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,和b)用水分散所得混合物。 21. A method for preparing an aqueous active compound composition according to any one of 16-19 claims, which method comprises: a) preparing a mixture comprising amphiphilic polymer composition and active compound and / or homogeneous active substance Non-water mixture, and b) dispersing the resulting mixture was washed with water.
    22.一种制备根据权利要求16-19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/或有效物质和合适的话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共聚物的水溶液混合,和c)除去有机溶剂。 22. A method for preparing an aqueous active compound composition according to any one of 16-19 claims, the method comprising: a) preparing active compounds and / or active substances and, if appropriate, amphiphilic polymer composition having a boiling point lower than the boiling point of water an organic solvent solution, and b) mixing an aqueous solution of the active compound and / or a solution of the active substance with water or amphiphilic copolymer and c) removing the organic solvent.
    23.一种制备根据权利要求16-19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。 23. A method for preparing an aqueous active compound composition according to any one of 16-19 claims, the method comprising the active compound at the melting point temperature above the active compound and / or amphiphilic active substances incorporated into the polymerization The composition of the aqueous 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”)。 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 plenty of water and diluted to the desired application concentration ("spray solution"). 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。 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 like. 同样的情形适用于有效物质(effect substance),即甚至在低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。 The same situation applies to the active substance (effect substance), and even play a technical role that is defined at low application rates low molecular weight compounds, such as colorants and UV stabilizers formulation.

    在含水活性化合物制剂情况下的常见问题是活性化合物在水中通常具有不良溶解度,该溶解度在23℃/1013毫巴下通常低于10g/l。 In the case of common problems aqueous preparation of the active compound is generally active compounds having poor solubility in water, the solubility in 23 ℃ / 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/或分散相存在于连续水相中。 Therefore, aqueous formulations of such active compounds are heterogeneous systems, wherein the active compound is emulsified and / or dispersed phase in the continuous aqueous phase. 为了稳定这些本身呈亚稳态的体系,通常使用乳化剂或分散剂。 In order to stabilize these metastable system itself was generally used emulsifier or dispersant. 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/或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 / or highly variable or near freezing point temperatures for a long time storage time. 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的溶解度。 Therefore, the water-miscible solvent is generally used as a solubilizer, i.e. increase the solubility of the active compound or the active substance in the aqueous phase. 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。 However, due to the known problems caused by the VOC, a relatively large amount of organic solvent and environmental reasons and for reasons of health-related work and in some cases also due to toxicological reasons it 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μm。 Another disadvantage of conventional aqueous active compound preparation is suspended in an aqueous phase, respectively, and the emulsified particles of the active compound and active compound droplets having a larger particle size, which size is usually several μm. 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”指通过使用溶解性传递物质(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,其中活性化合物分散相的颗粒通常小到很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 "solubilizing" refers to the solubility of transfer by using substances (adjuvants) to achieve a water-insoluble active compound or stabilizer of the active substance, evenly distributed, dispersed particles in which the active compound is usually small and difficult to scatter visible light so 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,该组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.

    WO 02/82900描述了将两亲性嵌段共聚物用于制备水不溶性作物保护剂的含水悬浮液。 WO 02/82900 describes amphiphilic block copolymers used in the preparation of water-insoluble crop protection agents in 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。 The block copolymers can be used an ethylenically unsaturated monomer "living" or "controlled" radical obtained by block copolymerization. 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。 Apart from the fact that such a method is more complex, the aqueous formulation containing the active compound a greater amount of water-soluble organic solvent. 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。 In addition, this method requires the use of toxic residues in the product transition metal catalyst. 此外,嵌段共聚物的颜色倾向于变成棕色。 In addition, the color of the block copolymer tends to become brown.

    US 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。 US 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: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: Surprisingly, this object is achieved by a component can be produced by the following reaction and the resulting polymer composition to achieve: a) at least one hydrophobic polymer P1, the polymer having an isocyanate group is in a reactive functional and RP1 by a group comprising the ethylenically unsaturated monomers constituting monomers M1: a1) based on the total amount of the monomers M1 is at least 10% by weight of a monomer of Formula I 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;和 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 monomer 25 Under ℃ solubility in water of less than 50g / l and different monomers M1a; and

    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。 a3) based on the total amount of the 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 tape There isocyanate group is in a reactive functional groups of RP2, 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,不良溶解性是活性化合物或有效物质在25℃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1g/l,特别是低于0.1g/l。 In this regard, poor solubility of the active compound or active substance at 1013 mbar and 25 ℃ solubility in water of less than 10g / l, usually less than 5g / l, in particular less than 1g / l, in particular less than 0.1 g / l.

    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散相,该分散相包含至少一种在25℃/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。 The preferred embodiment is directed to an aqueous composition, i.e., a liquid active compound composition, the composition comprising an aqueous medium as continuous phase and at least one dispersed phase, the dispersed phase comprises at least one 25 ℃ / 1013 mbar in solubility in water 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分散相,该分散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 the active substance dispersed phase is formed, the dispersed phase comprising an active compound or active substance and the amphiphilic polymer composition of the present invention is at least one. 在这些组合物中,分散相极为细碎,即分散相的颗粒具有的粒度显著小于1μm。 In these compositions, the dispersed phase is extremely finely divided, i.e. the dispersed phase particles having a particle size significantly smaller than 1μm. 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℃/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 ℃ / 1013 mbar solubility in water of less than 10g / l of 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,本发明组合物,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1μm,通常不超过500nm,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 smaller than 1μm, usually not more than 500nm, usually not more than 300nm, for example, particularly preferably 30-100nm containing phase active compound or active substance is 10-300nm, preferably 10-250nm, in particular 20-200nm or 20-150nm,.

    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,WssrigePolymerdispersionen[聚合物水分散体],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.Colloid Interf.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, WssrigePolymerdispersionen [aqueous polymer dispersion], Wiley-VCH 1999, Chapter 4.2.1, page 40 and subsequent pages and references cited therein, as well as H.Auweter, D.Horn, J.Colloid Interf.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-C4酮如丙酮和甲基乙基酮,环状醚如二烷和四氢呋喃,C1-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、二甘醇二甲醚、甘油,此外还有C2-C3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。 Examples of water-miscible solvents include C3-C4 ketones such as acetone and methyl ethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran  two, C1-C4 alkanol such as methanol, ethanol, n-propanol, isopropanol, n- butanol, tert-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 ether, glycerol, in addition C2-C3 nitriles such as acetonitrile and propionitrile, dimethylsulfoxide, dimethylformamide, formamide, acetamide, dimethylacetamide, butyrolactone, 2-pyrrolidone and N- methyl pyrrolidone.

    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,该组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,由于分散相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 the particle size of the dispersed phase are very small with very fine distribution, increasing the 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)或甚至配制成不合溶剂的组合物(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 the present invention, the aqueous active compound compositions is that they may also be formulated as a low-solvent composition (volatile solvent content <10% by weight, based on the weight of the active compound composition) or even undesirable formulated as a solvent composition substance (volatile solvent content <1% by weight, 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P1和亲水性聚合物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。 Hydrophobic polymers P1 and P2 for the hydrophilic polymer amphiphilic polymer composition of the present invention were each 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羟基、巯基(SH)以及伯和仲氨基。 Examples of suitable functional groups are hydroxyl group, a thiol group (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P1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P1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 P1 of hydrophobic polymer in V and polymers P1 and 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P1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P1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 polymers P1 and / or P2 and the reaction product of the reaction product of symmetry, the symmetry is derived from a polymer having only P1 is a polymer block derived from a polymer or 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M1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%的单体M1a且具有所需数目的反应性基团RP1。 Is a suitable hydrophobic polymers P1 principle all polymers from ethylenically unsaturated monomers M1 constructed, based on the total amount of monomers M1 polymer comprises at least 10 wt%, preferably at least 30 wt%, especially at least 50 wt. %, particularly preferably at least 60% by weight of the monomers M1a and having the desired number of reactive groups RP1.

    优选的单体M1a是其中式I中R3为氢的那些。 Preferred monomers M1a are those of formula I wherein R3 is hydrogen. R2优选为氢或甲基。 R2 is preferably hydrogen or methyl. X优选为O、NH、NCH3或NC2H5。 X is preferably O, NH, NCH3 or NC2H5.

    R1优选为:-C1-C10烷基如甲基、乙基、正丙基、异丙基、正丁基、2-丁基、异丁基、叔丁基、1-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R2=H,R1尤其不为甲基;-C5-C10环烷基如环戊基、环己基或甲基环己基,或-苯基-C1-C4烷基如苄基,1-或2-苯基乙基,1-、2-或3-苯基丙基。 R1 is preferably: -C1-C10 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, 1-pentyl, 2-pentyl group, neopentyl, n-hexyl, 2-hexyl, n-octyl, 2-ethylhexyl, heptyl, 2-propyl or n-decyl, wherein for R2 = H, R1 in particular is not methyl; -C5- C10 cycloalkyl groups such as cyclopentyl, cyclohexyl or methylcyclohexyl, or - phenyl -C1-C4 alkyl such as benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenyl propyl.

    R1尤其为C1-C10烷基,其中对于R2=H,R1尤其不为甲基。 In particular R1 is C1-C10 alkyl, wherein for R2 = H, R1 is not methyl in particular.

    因此,特别优选的单体M1a为丙烯酸与C2-C10链烷醇的酯(=丙烯酸C2-C10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,甲基丙烯酸与C1-C10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、甲基丙烯酸叔丁基酯和甲基丙烯酸正己基酯。 Accordingly, particularly preferred acrylic monomers M1a and C2-C10 alkanols (= C2-C10 alkyl esters of acrylic acid), such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl yl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and 3-propyl-heptyl methacrylate, with C1-C10 alkanols, such as methyl methacrylate, ethyl methacrylate, methyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate and methyl acrylate, n-hexyl acrylate. 优选的单体M1a此外还是丙烯酸和甲基丙烯酸的N-(C2-C10烷基)酰胺,以及丙烯酸和甲基丙烯酸N-(C1-C2烷基)-N-(C2-C10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甲基丙烯酰胺。 Preferred monomers M1a addition of acrylic and methacrylic acid or N- (C2-C10 alkyl) amides, and acrylic and methacrylic acid N- (C1-C2 alkyl) -N- (C2-C10 alkyl) amide , 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 the corresponding methacrylamide. 基于单体M1a的总量,单体M1a尤其包含至少50重量%,特别是至少70重量%的至少一种甲基丙烯酸C1-C4烷基酯(R1=C1-C4烷基,R2=CH3和R3=H),其中特别优选甲基丙烯酸甲酯。 Based on the total amount of monomers M1a, the monomers M1a comprise in particular at least 50% by weight, in particular at least 70 wt% of at least one C1-C4 alkyl methacrylate ester (R1 = C1-C4 alkyl, R2 = CH3 and R3 = H), wherein the methyl methacrylate is particularly preferred.

    除了单体M1a外,疏水性聚合物P1还可以包含不同于单体M1a的单体M1b,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 M1a, the hydrophobic polymer P1 may further contain a monomer different from the monomers M1a M1b, based on the total amount of monomer M1 is at most 90% by weight, preferably up to 70% by weight, in particular up to 50 wt% , particularly preferably at most 40% by weight. 这些单体是在25℃和1013毫巴下在水中的溶解度<50g/l,通常<20g/l的单烯属不饱和单体。 These monomers are at 1013 mbar and 25 ℃ water solubility <50g / l, typically <20g / l of monoethylenically unsaturated monomers. 该类单体M1b的实例是乙烯基芳族单体如苯乙烯、α-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α-烯烃如丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和1-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,卤代烯烃如氯乙烯,优选具有3-6个碳原子的单烯属不饱和单羧酸的C11-C20烷基酯如丙烯酸C11-C20烷基酯和甲基丙烯酸C11-C20烷基酯,如丙烯酸月桂基酯、甲基丙烯酸月桂基酯、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-C1-C20烷基酯如富马酸和马来酸的二-C1-C20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。 Examples of such monomers M1b are vinyl aromatic monomers such as styrene, α- methyl styrene, vinyl toluene and the like, an olefin having 2 to 10 carbon atoms, preferably having α 3-10 carbon atoms, - olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, laurate vinyl acetate, vinyl esters of pelargonic acid, capric acid, vinyl acetate, vinyl laurate and vinyl stearate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, halogenated olefins such as vinyl chloride, preferably having 3-6 carbon atoms monoethylenically unsaturated monocarboxylic acids, such as C11-C20 alkyl esters of C11-C20 alkyl esters of acrylic and methacrylic acid esters of C11-C20 alkyl, such as lauryl acrylate, methacrylate, lauryl acrylate, isotridecyl methacrylate, isotridecyl acrylate, stearyl methacrylate, stearyl methacrylate, preferably 4-8 carbon atoms, ethylenically unsaturated dicarboxylic acids - C1-C20 alkyl esters such as fumaric acid and maleic acid di -C1-C20 alkyl esters, such as dimethyl fumarate, dimethyl maleate, dibutyl fumarate and maleate monoethylenically ester, preferably having 3-6 carbon atoms and an unsaturated monocarboxylic acid glycidyl ester such as glycidyl acrylate and glycidyl methacrylate. 优选的单体M1b是乙烯基芳族单体,其中尤其优选苯乙烯。 Preferred monomers are vinyl aromatic monomers M1b, wherein styrene is particularly preferred. 在一个实施方案中,单体M1b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 amount of monomers M1 M1b 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M1a和M1b的总量为单体M1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 monomers M1a and M1b of the monomers M1 is at least 80% by weight, especially at least 90% by weight, particularly preferably at least 95 wt%.

    除了单体M1a和合适的话M1b外,聚合物P1基于单体M1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M1a和M1b的烯属不饱和单体M1c。 In addition to the monomers M1a and M1b, if appropriate, the polymer based on the total amount of monomers M1 P1 may comprise 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 M1a and M1b ethylenically unsaturated monomer M1c.

    单体M1c优选选自在25℃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M1c.1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M1c.2。 M1c monomer is preferably selected at 25 ℃ solubility in water of at least 50g / l, especially at least 100g / l of neutral monoethylenically unsaturated monomers M1c.1 and having at least one ionic or ionizable monoethylenically unsaturated monomer group M1c.2.

    单体M1c.1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-羟基烷基酰胺,特别是N-羟甲基酰胺,尤其是N-羟甲基丙烯酰胺和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α,β-烯属不饱和C3-C8单羧酸和C4-C8二羧酸的羟烷基酯,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。 Examples of the above-mentioned monomer M1c.1 ethylenically unsaturated carboxylic acid amides, especially acrylamide and methacrylamide, and the above-described ethylenically unsaturated carboxylic acid amides of N- hydroxyalkyl, particularly hydroxyethyl N- methylamide, especially N- methylol acrylamide and N- methylol methacrylamide, ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile, said α, β- ethylenically unsaturated C3-C8 monocarboxylic acids and C4-C8 hydroxyalkyl esters of dicarboxylic acids, in particular hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, methacrylate, 2- and 3 - hydroxypropyl acrylate, polyethylene glycol or polyethylene glycol alkyl vinyl ether and allyl ether, said monoethylenically unsaturated monocarboxylic and dicarboxylic acids with C2-C4 polyalkylene glycol esters, especially those acids, especially acrylic acid or methacrylic acid with polyethylene glycol or polyethylene glycol alkyl esters, wherein the ester and ether class (alkyl) polyethylene glycol group generally have a molecular weight of 100-3000. 单体M1c.1进一步包括N-乙烯基酰胺,如N-乙烯基甲酰胺、N-乙烯基吡咯烷酮和N-乙烯基己内酰胺。 Further comprising the monomer M1c.1 N- vinyl amides, such as N- vinylformamide, N- vinyl pyrrolidone and N- vinyl caprolactam. 单体M1c.1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,以及含有醛基或酮基的单体,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。 M1c.1 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 aldehyde or keto 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M1c.1的比例基于单体M1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%。 M1c.1 based monomer ratio of the total amount of monomers M1 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M1c.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M1c.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。 M1c.2 monomers include, in particular at least one acid group or at least one anionic group monoethylenically unsaturated monomer M1c.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-丙烯酰氨基-2-甲基丙磺酸、2-丙烯酰氧基乙磺酸和2-甲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、乙烯基苯磺酸及其盐,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α,β-烯属不饱和C3-C8单-和C4-C8-二羧酸,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-2-methylpropanesulfonic acid, 2-acryloyloxy acetic acid and 2-methacryloxy ethyl sulfonate acid, 3-acryloxy - and 3-methacryloxy propane sulfonic acid, vinyl sulfonic acid and its salts, ethylenically unsaturated phosphonic acids, such as vinylphosphonic acid and vinylphosphonic acid dimethyl esters and salts, and α, β- ethylenically unsaturated C3-C8 single - and C4-C8- dicarboxylic acids, especially acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid . 单体M1c.2s的比例基于单体M1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%。 M1c.2s based monomer ratio of the total amount of monomers M1 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M1c.2s。 In a preferred embodiment, the polymer P1 does not contain or contains less than 0.1% by weight of the monomer M1c.2s.

    单体M1c.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M1c.2k。 Also included M1c.2 monomer having at least one cationic group and / or at least one can be protonated group in an aqueous medium monoethylenically unsaturated monomer M1c.2k. 单体M1c.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。 M1c.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-烷基乙烯基吡啶盐和N-烷基-N'-乙烯基咪唑啉盐,如N-甲基-N'-乙烯基咪唑啉氯化物或甲基硫酸盐。 Examples of alkylene having quaternized amino alkyl vinyl monomers are N-  pyridine salt and N- vinyl-alkyl imidazoline  -N'- salts, such as N- methyl vinyl imidazoline -N'-  chloride or methyl sulfate. 在单体M1c.2k中特别优选式II的单体: In particularly preferred monomer M1c.2k monomers of formula II:

    其中R5为氢或C1-C4烷基,尤其是氢或甲基,R6、R7相互独立地为C1-C4烷基,尤其是甲基,和R8为氢或C1-C4烷基,尤其是氢或甲基,Y为氧、NH或NR9,其中R9=C1-C4烷基,A为C2-C8亚烷基,例如1,2-亚乙基、1,2-或1,3-亚丙基、1,4-亚丁基或2-甲基-1,2-亚丙基,其可以被1、2或3个非相邻氧原子间隔,和Z-为阴离子等价物,例如Cl-、HSO4-、SO42-或CH3OSO3-等,以及对于R8=H,还有式II单体的游离碱。 Wherein R5 is hydrogen or C1-C4 alkyl, especially hydrogen or methyl, R6, R7 are independently C1-C4 alkyl, especially methyl, and R8 is hydrogen or C1-C4 alkyl, especially hydrogen or methyl, Y is oxygen, NH or NR9, wherein R9 = C1-C4 alkyl, A is C2-C8 alkylene, e.g., ethylene, 1,2- or 1,3-propylene group, tetramethylene or 2-methyl-1,2-propylene, which may be 1, 2, or 3 non-adjacent oxygen atoms, and Z- is an anion equivalent, such as Cl-, HSO4 -, SO42- CH3OSO3-, or the like, and for R8 = H, as well as a free base monomer of formula II.

    该类单体M1c.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-二甲氨基)乙基酯、2-(N,N-二甲氨基)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)乙基甲基丙烯酰胺氯化物、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 M1c.2k 2- (N, N- dimethylamino) ethyl methacrylate, 2- (N, N- dimethylamino) ethyl acrylate, 2- (N, N - dimethylamino) 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 methacrylamide 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 corresponding methyl sulphate salt and sulfates. 其他合适的单体M1c.2k是乙烯基吡啶和乙烯基咪唑及其季铵化产物。 M1c.2k other suitable monomers are vinyl pyridine and vinyl imidazole and quaternized product.

    单体M1c.2k的比例基于单体M1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%。 Advantageously the proportion of the monomer M1c.2k is based on the total amount of monomers M1 does not exceed 20% by weight, e.g., 0.1 to 20% by weight, in particular 0.5 to 15% by weight, in particular 1-10% by weight. 在优选实施方案中,聚合物P1不包含或包含不超过0.1重量%的单体M1c.2k。 In a preferred embodiment, the polymer P1 does not contain or contains no more than 0.1% by weight of the monomer M1c.2k.

    单体M1c还包括具有两个或更多个非共轭烯属不饱和双键的单体M1c.3。 Further comprising the monomer M1c having two or more non-conjugated ethylenically unsaturated double bonds monomer M1c.3. 该类单体M1c.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 M1c.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(羟甲基)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、邻苯二甲酸二烯丙基酯。 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 diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol trimethacrylate, tris (hydroxymethyl) ethane triacrylate and tris (hydroxymethyl) ethane trimethacrylate, pentaerythritol triacrylate and pentaerythritol trimethoxyphenyl acrylate, polyfunctional carboxylic acids in addition to the allyl and methallyl esters such as diallyl maleate, fumarate, diallyl phthalate, diallyl ester . 典型的单体M1c.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甲基丙烯酰胺的化合物。 Typical monomers such as divinylbenzene or M1c.3, divinyl urea, diallyl urea, cyanuric acid triallyl ester, N, N'- divinyl - and N, N'- two allyl-imidazolidin-2-one, and methylene bis acrylamide and methylene bis methacrylamide.

    根据本发明,聚合物P1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 P1 with a reaction with an isocyanate group to form bonds reactive functional groups RP1. 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P1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。 Number amphiphilic polymer composition of the present invention in the formulation of the active compound in the use, P1 hydrophobic polymer preferably has a number average molecular weight is taken into account 500-20000 Dalton, especially 1500-15000 Daltons.

    原则上讲,聚合物P1由现有技术已知,例如由US 5,556,918和EP-A742 238已知。 In principle, polymers P1 are known from the prior art, such as is known from the US 5,556,918 and EP-A742 238. 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 the initiator containing hydroxyl radicals upon decomposition (· OH radical), and / or modulators containing OH groups group or NH2 group. 合适的引发剂是有机氢过氧化物,如氢过氧化叔丁基、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 t-butyl hydroperoxide, hydrogen peroxide, tetrahydrofuran, cumene hydroperoxide, or 2,2'-azobis (2-methyl -N- (2- hydroxy- ethyl) propanamide). 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,所述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、过氧化二苯甲酰、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 conventional initiators such as organic peroxides or azo initiators, such as azobis (isobutyronitrile), peroxide (t butyl) decanoyl peroxide, dibenzoyl peroxide, 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M1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 M1 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、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25℃/1013毫巴下在水中的溶解度>50g/l,尤其>100g/l。 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 at 25 ℃ / 1013 mbar solubility in water> 50g / l, in particular> 100g / l. 合适的单体M2a是作为单体M1c.1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,如甲基丙烯酰胺、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唑啉)和聚(2-乙基唑啉),和-聚(α-羟基羧酸)酯,如聚乙交酯和聚丙交酯。 Suitable monomers are monomers as monomer M2a M1c.1 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 methacrylamide, acrylamide, 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  oxazoline) and poly (2-ethyl-  oxazoline), and - poly (α- hydroxy carboxylic 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%带有酸基如羧酸基团、磺酸基团、磷酸酯基团或膦酸基团的单烯属不饱和单体M2b的那些。 Examples of suitable anionic polymers P2 are based on the total weight of the polymer P2 it contains at least 30, preferably at least 50% by weight with an acid group such as a carboxylic acid group, a sulfonic acid group, a phosphate group or a phosphonate group monoethylenically unsaturated monomer M2b of those. 合适单体M2b的实例是就聚合物P1提到的单体M1c.2s,例如α,β-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、甲代烯丙基磺酸、苯乙烯磺酸、2-丙烯酰氨基-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-丙烯酰氨基-2-甲基丙烷膦酸和膦酸2-丙烯酰氧乙基酯。 Examples of suitable monomers are monomers M2b mentioned on M1c.2s polymer P1, such as α, β- ethylenically unsaturated mono - and dicarboxylic acids, such as acrylic acid, methacrylic acid, vinyl acetate, monoethylenically unsaturated sulfonic acids, such as vinyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-methacryloyloxyethyl sulfonate, olefinic unsaturated acid, such as vinyl phosphonate, allyl phosphonic acid, acid methallyl ester, 2-acrylamido-2-methyl propane acid and phosphonic acid 2-acryloyloxyethyl ester. 除了上述单体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M1a和M1b以及至多70重量%的单体M2a。 In addition to the above-mentioned monomers M2b, P2 suitable anionic polymers may contain up to 50% by weight, in particular at most 30% by weight of the monomers M1a and M1b 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M1c.2k的均聚物和共聚物以及单体M1c.2k与单烯属不饱和中性单体M1c.1的共聚物。 Examples of suitable cationic polymers P2 is the above monoethylenically unsaturated monomer M1c.2k and homopolymers and copolymers with monomers M1c.2k monoethylenically unsaturated neutral monomers M1c.1 copolymer.

    在聚合物P2中特别优选的是对于官能基团RP2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 polymer P2 for RP2 functional group having a functionality F2 in terms of 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%,特别优选至少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% by weight of aliphatic polyethers of ethylene oxide units. 此外,脂族聚醚可以具有衍生于C3-C4烯化氧的结构单元。 In addition, the aliphatic polyethers may have derived from C3-C4 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:Ra-X-(CHRb-CH2-O)pH (III)其中Ra为氢、C1-C20烷基或苄基,X为氧或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,p为平均值为10-500,优选20-250,尤其是25-100的整数(数均)。 Particularly preferred polyethers in particular those of formula III: Ra-X- (CHRb-CH2-O) pH (III) wherein Ra is hydrogen, C1-C20 alkyl or benzyl, X is oxygen or NH, Rb is hydrogen or methyl, wherein at least 50mol%, especially at least 70mol%, preferably at least 90mol% group R2 is hydrogen, 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且它们中的大多数可以市购,例如以商品名Pluriol和Pluronic(BASF Aktiengesellschaft的聚醚)、Sokalan、Kollidon(单体M2a、M2b和M1c.2k的均聚物和共聚物)市购,或者它们可以通过标准方法制备。 Skilled personnel familiar with suitable hydrophilic polymers P2 and most of them are commercially available, for example under the trade name Pluriol and Pluronic (BASF Aktiengesellschaft polyether), Sokalan, Kollidon (monomer M2a , M2b and M1c.2k homopolymers and copolymers) are commercially available, or they can be prepared by standard methods.

    疏水性聚合物P1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P1的总量,基于聚合物P1、聚合物P2和化合物V的总重量优选为9-90重量%,尤其是20-68重量%。 The total proportion of hydrophobic polymer P1 in the amphiphilic total polymer composition, i.e., the reaction and the unreacted polymer P1, based on the total weight of the polymer P1, a polymer P2 and the compound V is preferably 9- 90% by weight, in particular 20-68% by weight.

    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的总重量优选为9-90重量%,尤其是30-78重量%。 The total amount of the polymer of the hydrophilic polymer P2 P2 proportion of the total amphiphilic polymer composition, i.e., the reaction and unreacted, based on the total weight of the polymer P1, a polymer P2 and the compound V is preferably 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P1、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 P1, a polymer P2 and the compound V is preferably 1 to 20% by weight, in particular 2-15 wt. %.

    聚合物P1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 P1 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.

    对于异氰酸酯基团而言具有的官能度为至少1.5,尤其是15.-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 isocyanate groups having a functionality of at least 1.5, especially 15-4.5, in particular 1.8 to 3.5 V Suitable compounds include aliphatic, cycloaliphatic and aromatic di - and polyisocyanates and aliphatic, cyclic isocyanurate of aliphatic and aromatic diisocyanate and allophanate, uretdione (uretdione) and biuret.

    化合物V优选平均每分子具有1.8-3.5个异氰酸酯基团。 Compound V is preferably 1.8 to 3.5 per molecule isocyanate groups. 合适化合物V的实例是芳族二异氰酸酯,如甲苯-2,4-二异氰酸酯,甲苯-2,6-二异氰酸酯,甲苯-2,4-和2,6-二异氰酸酯的市购混合物(TDI),n-亚苯基二异氰酸酯,3,3'-二苯基-4,4'-亚联苯基二异氰酸酯,4,4'-亚联苯基二异氰酸酯,4,4'-二苯基甲烷二异氰酸酯,3,3'-二氯-4,4'-亚联苯基二异氰酸酯,枯烯2,4-二异氰酸酯,1,5-萘二异氰酸酯,对苯二亚甲基二异氰酸酯,对亚苯基二异氰酸酯,4-甲氧基-1,3-亚苯基二异氰酸酯,4-氯-1,3-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,5,6-二甲基-1,3-亚苯基异氰酸酯,2,4-二异氰酸酯基二苯基醚,脂族二异氰酸酯,如乙撑二异氰酸酯,乙叉二异氰酸酯,亚丙基1,2-二异氰酸酯,1,6-六亚甲基二异氰酸酯,1,4-四亚甲基二异氰酸酯,1,10-十亚甲基二异氰酸酯,以及环脂族二异氰酸酯,如异佛尔酮二异氰酸酯(IPDI)、亚环己基1,2-二异氰酸酯、亚环己基1,4-二异氰酸酯和二(4,4'-异氰酸酯基环己基)甲烷。 Examples of suitable compounds V are aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, toluene-2,4 and 2,6-diisocyanate City purchase mixture (TDI) , n- phenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4' methane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, cumene 2,4-diisocyanate, 1,5-naphthalene diisocyanate, of xylylene diisocyanate, p-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene diisocyanate, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether aliphatic diisocyanate, such as ethylene diisocyanate, ethylidene diisocyanate, propylene 1,2-diisocyanate, hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1 , 10-decamethylene diisocyanate, and cycloaliphatic diisocyanates, such as isophorone diisocyanate (IPDI), cyclohexylene 1,2-diisocyanate, cyclohexylene 1,4-diisocyanate 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-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、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, toluene-2,6-diisocyanate, mixtures thereof, and cis - and trans - 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。 In another preferred embodiment of the present invention, the biuret aliphatic or cycloaliphatic diisocyanate compound or isocyanurate, such as cyanuric acid, tetramethylene diisocyanate or hexamethylene diisocyanate esters for the amphiphilic polymer composition of the present invention.

    为了制备本发明的两亲性聚合物组合物,使疏水性聚合物P1和亲水性聚合物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。 To prepare the amphiphilic polymer composition of the present invention, the hydrophobic polymer P1 and the hydrophilic polymer P2 sequentially or simultaneously in which the group RP1 with a compound V and / or RP2 with isocyanate groups to form bonds under reaction conditions.

    该反应可以在不存在或存在少量促进尿烷或脲形成的常规催化剂下进行。 The reaction can be carried absence or presence of a small amount of a conventional catalyst to promote the urethane or urea formation under. 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RP1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 RP1 or RP2 functional groups and reactive 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℃,尤其是15-85℃。 The temperature is usually 10-120 ℃, especially 15-85 ℃.

    不言而喻的是聚合物P1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 000ppm,尤其<2000ppm)。 It goes without saying that the polymer P1 and P2 react with the isocyanate compound V is carried out in the absence of moisture (water content preferably <10 000ppm, in particular <2000ppm).

    该反应可以以纯的形式进行或在对化合物V的异氰酸酯基团呈惰性的有机溶剂中进行。 This reaction can be carried out or in compounds V isocyanate group inert organic solvent in pure form. 合适溶剂的实例是脂族酮,如丙酮、甲基乙基酮、环己酮,脂族羧酸的烷基酯,如乙酸甲酯、乙酸乙酯、丙酸甲酯、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、四氢呋喃,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, methyl ethyl ketone, cyclohexanone, aliphatic carboxylic acid alkyl esters, such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-butyl acetate, alicyclic and cyclic ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, aromatic, aliphatic and alicyclic hydrocarbons such as toluene, xylene, hexane, cyclohexane, and the N- alkyl amide, such as methylpyrrolidone, and mixtures of these solvents N-.

    聚合物P1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P1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。 Polymers P1 and P2 with the compound V reacted polymer can be sequentially or simultaneously, ie polymers P1 and P2 can take a while to react with a compound V with a compound V reaction or both.

    若聚合物P1和P2一个接一个与化合物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 polymers P1 and P2 one after the 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P1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P1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20-80mol%已经与官能基团R1和/或R2反应,且存在的异氰酸酯基团中10-90mol%,尤其是20-80mol%仍可利用。 If the polymers P1 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 P1 or P2, V of the isocyanate groups of at least 10-90mol%, especially 20- 80mol% have functional groups R1 and / or R2 react with, and there are isocyanate groups 10-90mol%, especially 20-80mol% 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的用量优选应使反应性基团RP1和/或RP2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。 Accordingly, the first polymer P1 or P2 preferably used in amounts such that the reactive groups RP1 and / or isocyanate, ester groups per molecule RP2 V molar ratio of 0.1:1-0.9:1, especially 0.2:1- 0.8. 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P1或P2的用量优选应使反应性基团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 P1 or P2 preferably used in amounts such that the reactive groups RP1 + RP2 corresponds to the total number of compound V isocyanate group at least. 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 does not exceed the value of 1.2.

    若使聚合物P1和P2同时与异氰酸酯化合物V反应,则聚合物P1和P2的用量优选应使反应性基团RP1+RP2与异氰酸酯基团的摩尔比为至少1∶1。 Ruoshi polymers P1 and P2 simultaneously reacted with the isocyanate compound V, the amount of polymer P1 and P2 should preferably be so reactive groups RP1 + RP2 and the molar ratio of isocyanate groups is at least 1:1. 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 does not exceed the value of 1.2.

    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ZWWicks,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],第XIV/2卷,第61页及随后各页,Georg Thieme Verlag,Stuttgart 1963)。 Document number of compounds have been described in a closed (capped or protected) isocyanate groups (see, for example ZWWicks, Prog.Org.Coat.3 (1975) 73-99 and 9 (1981) 3-28 or Houben-Weyl , Methoden der Organischen Chemie [Methods of Organic Chemistry], p. XIV / 2, pp. 61 ff, Georg Thieme 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,二酮基哌嗪类,丙二酸酯类和肟类。 It may be mentioned isocyanate group blocking reagent examples are phenols, caprolactam, imidazoles, pyrazoles, pyrazolones, 1,2,4-triazole, diketopiperazine class, malonate esters and oximes. 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P1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 polymerizable hydrophobic polymer P1 prepared by radical solvent and the resultant liquid reaction mixture in the manner described herein to react with an isocyanate of 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P1中,然后与化合物V反应。 Or may be added to the required amount of polymer P1 to polymer P2 prepared in this manner, and then reacted with compound 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散体。 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 obtain an aqueous composition amphiphilic polymer dispersions. 这例如可以通过首先通过蒸馏除去溶剂并随后将残余物分散在水或含水介质中而实现。 This example, by first removing the solvent by distillation and the residue was then dispersed in water or an aqueous medium is achieved. 还可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剂。 It may also be added to the aqueous solution of the polymer composition and, after addition of water or solvent is removed 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. 通常而言,本发明活性化合物或有效物质组合物的制备包括制备或提供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。 Generally speaking, the preparation of the active compound or active substance of the present invention comprises a composition or preparation comprising providing amphiphilic polymer composition and at least one active compound and / or a non-aqueous homogeneous mixture of the 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随后将所得混合物分散在水或含水介质中而制备。 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 the resulting mixture is then dispersed in water or an aqueous medium 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,例如四氢呋喃,卤代烃类如二氯甲烷、二氯乙烷,以及上述溶剂的混合物。 On principle suitable for this purpose is a solvent capable of dissolving both the active compound and the polymer that, for example, aliphatic nitriles such as acetonitrile and propionitrile, aliphatic carboxylic acids of N, N- dialkylamides such as dimethylformamide amides and dimethyl acetamide, N- alkyl lactams such as N- methylpyrrolidone, said aliphatic and cycloaliphatic ethers, such as tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, dichloroethane, and the above-mentioned solvents mixtures thereof. 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10-80℃,尤其是20-50℃的温度下进行。 It was stirred at room temperature or may be heated, for example at 10-80 ℃, especially at a temperature of 20-50 ℃ performed.

    在本发明的第二实施方案中,通过将活性化合物和/或有效物质掺入两亲性聚合物组合物的水溶液/水分散体中而制备含水活性化合物组合物。 In a second embodiment of the present invention, by incorporating the active compound and / or an aqueous solution of active substance incorporated in the amphiphilic polymer composition / aqueous dispersion prepared aqueous active compound composition. 这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1-1000mPa.s(根据DIN53019-2,25℃)的温度下进行掺入而实现。 This is typically at a temperature above the melting point by the active compound or the temperature of the active substance, preferably in which the active compound or the active substance having a low melt viscosity, i.e. a viscosity of 1-1000mPa.s (according DIN53019-2,25 ℃) temperature performed under incorporation and implementation. 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: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,和c)除去溶剂。 In the third embodiment of the present invention, by including ac method comprising the steps of preparing an aqueous active compound composition: a) preparing active compounds and / or active substances and, if appropriate, amphiphilic polymer composition having a boiling point lower than water the boiling point of the organic solvent solution, b) mixing an aqueous solution of the active compound and / or a solution with water or the active substance amphiphilic copolymer and c) removing the solvent.

    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分散体混合。 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 dispersion of the solution with amphiphilic polymer composition mixed with water or an aqueous solution. 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续混合的设备适于该目的。 In principle, all allow liquid stream continuous 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”(ASMyerson,1993Butterworth-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 is "Handbook of Industrial Crystallization" (ASMyerson, 1993Butterworth-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 preferably 10:1-1:20, especially 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C2-C4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烷、四氢呋喃,酮类如丙酮、甲基乙基酮。 Examples of suitable solvents are C2-C4 alkanol, such as ethanol, n-propanol, n-butanol, isobutanol, said aliphatic and cycloaliphatic ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether , two  dioxane, tetrahydrofuran, 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合物和/或有效物质的均相非水混合物而制备非水活性化合物组合物。 In another embodiment of the present invention, by preparing an amphiphilic polymer composition of the active compound and / or a non-aqueous homogeneous mixture of the active substance and prepared by non-aqueous active compound composition. 如果该组合物不含任何液体组分,则它通常为固体。 If the composition does not contain any liquid component it is generally solid. 对于该类组合物的制备,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。 For preparing such compositions, described above, is made in the first embodiment comprises an amphiphilic polymer composition of the active compound and / or a non-aqueous homogeneous mixture of active substance was prepared in a similar manner applicable; however, the 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.

    已经发现有利的是本发明含水活性化合物组合物中活性化合物和/或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。 It has been found advantageous that the aqueous active compound compositions of the present invention the active compound and / or weight of the active substance and the amphiphilic polymer composition ratio 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,本发明组合物,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℃的那些。 Here its volatile components under atmospheric pressure boiling point below 200 ℃ of 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括:·酰基丙氨酸类,例如苯霜灵(benalaxyl)、甲霜灵(metalaxyl)、甲呋酰胺(ofurace)、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)、吗菌灵(dodemorph)、丁苯吗啉(fenpropimorph)、苯锈啶(fenpropidin)、双胍盐(guazatine)、双胍辛醋酸盐(iminoctadine)、螺茂胺(spiroxamine)、克啉菌(tridemorph), Examples of fungicidal active compounds of the invention may be formulated into the active compound composition include: · acylalanines, such as benalaxyl (benalaxyl), metalaxyl (metalaxyl), ofurace (ofurace),  Cream Spirit ( oxadixyl), · amine derivatives, such as 4-dodecyl-2,6-dimethyl morpholine (aldimorph), dodine (dodine), it benomyl (dodemorph), fenpropimorph (fenpropimorph) , fenpropidin (fenpropidin), guazatine (guazatine), Iminoctadine acetate (iminoctadine), spiro  metallocene amine (spiroxamine), g morpholine bacteria (tridemorph),

    ·苯胺基嘧啶类,例如二甲嘧菌胺(pyrimethanil)、嘧菌胺(mepanipyrim)或环丙嘧啶(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),·唑类,例如双苯三唑醇(bitertanol)、糠菌唑(bromoconazole)、氰霜唑(cyazofamid)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(dinitroconazole)、氧唑菌(epoxiconazole)、氯唑灵(etridazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、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)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、戊菌唑(penconazole)、perfuazorate、丙环唑(propiconazole)、丙氯灵(prochloraz)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、涕必灵(thiabendazole)、三唑酮(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-溴-6-氟-2-甲基吲哚-1-磺酰基)-[1,2,4]三唑-1-磺酰胺;·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);·二羧酰亚胺类,如异丙定(iprodione)、甲菌利(myclozolin)、杀菌利(procymidone)、烯菌酮(vinclozolin),·二硫代氨基甲酸盐类,如福美铁(ferbam)、代森钠(nabam)、代森锰(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),·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)、唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异嘧菌醇(fenarimol)、麦穗宁(fuberidazole)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、稻瘟灵(isoprothiolane)、丙氧灭绣胺(mepronil)、氟苯嘧啶醇(nuarimol)、异噻菌酮(octhilinone)、氟吡菌胺(picobenzamid)、噻菌灵(probenazole)、丙氧喹啉(proquinazid)、啶斑肟(pyrifenox)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、硅噻菌胺(silthiofam)、涕必灵(thiabendazole)、溴氟唑菌(thifluzamide)、甲基托布津(thiophanate-methyl)、噻酰菌胺(tiadinil)、三环唑(tricyclazole)、嗪氨灵(triforine)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶和磺嘧菌灵(bupirimate);·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);·苯基吡咯类,如拌种咯(fenpiclonil)和氟菌(fludioxonil);·不属于任何其他类别的杀真菌剂,如噻二唑素(acibenzolar-S-methyl)、苯噻菌胺(benthiavalicarb)、氯环丙酰胺(carpropamid)、百菌清(chlorothalonil)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、哒菌清(diclomezine)、双氯氰菌胺(diclocymet)、乙霉威(diethofencarb)、克瘟散(edifenphos)、噻唑菌胺(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-aluminum)、异丙菌胺(iprovalicarb)、六氯苯(hexachlorobenzol)、苯菌酮(metrafenone)、戊菌隆(pencycuron)、百维灵(propamocarb)、四氯苯酞(phthalide)、甲基立枯磷(tolclofos-methyl)、五氯硝基苯(quintozene)、苯酰菌胺(zoxamide)、稻瘟灵(isoprothiolane)、fluopicolide(氟吡菌胺);氯环丙酰胺(carpropamid)、双炔酰菌胺(mandipropamid)、N-(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、N-(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;呋吡唑灵(furametpyr)、溴氟唑菌(thifluzamide)、吡噻菌胺(penthiopyrad)、环酰菌胺(fenhexamid)、N-(2-氰基苯基)-3,4-二氯异噻唑-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}氨基甲酸甲酯、磺菌胺(flusulfamide)、下式的酰胺: · Anilino pyrimidines, e.g., dimethyl mepanipyrim (pyrimethanil), mepanipyrim (mepanipyrim) or cyclopropylmethyl pyrimidine (cyprodinil), · antibiotics, e.g. CHX (cycloheximide), griseofulvin (griseofulvin), Jubilee hormone (kasugamycin), Thomas ADM (natamycin), Polyoxins (polyoxin), streptomycin (streptomycin) or Jinggangmycin (validamycin A), · azoles, such as bitertanol (bitertanol) , bromuconazole (bromoconazole), Cyazofamid (cyazofamid), cyproconazole (cyproconazole),  difenoconazole (difenoconazole), diniconazole (dinitroconazole), epoxiconazole (epoxiconazole), chlorazol Spirit (etridazole), fenbuconazole (fenbuconazole), quinazolinone cycloheximide (fluquinconazole), Flusilazole (flusilazole), Flutriafol (flutriafol), fuberidazole (fuberidazole), hexaconazole (hexaconazole), hymexazol (hymexazole), ene benomyl (imizalil), cyclopentyl Hexaconazole (ipconazole), amide azole (imibenconazole), metconazole (metconazole), myclobutanil (myclobutanil), penconazole (penconazole), perfuazorate, propiconazole (propiconazole ), prochloraz (prochloraz), prothioconazole (prothioconazole), simeconazole (simeconazole), tebuconazole (tebuconazole), fluorine difenoconazole (tetraconazole), thiabendazole (thiabendazole), triadimefon (triadimefon ), Triadimenol (triadimenol), triflumizole (triflumizole), pentyl fork yl bacteria (triticonazole), 2- butoxy-6-iodo-3-propyl-benzopyran-4-one, N, N - dimethyl-3- (3-bromo-6-fluoro-2-methyl-indol-1-sulfonyl) - [1,2,4] triazol-1-sulfonamide; * in EP-A 897904 as described in Formula I to 2-methoxy-benzophenones, for example metrafenone (metrafenone); · dicarboximide type, such as isopropyl set (iprodione), A bacterium Lee (myclozolin), procymidone ( procymidone), ene cycloheximide (vinclozolin), · dithiocarbamate salts such as ferbam (ferbam), Dyson sodium (nabam), maneb (maneb), mancozeb (mancozeb), 100 Granville mu (metam), metiram (metiram), methyl zineb (propineb), zinc Fordyce (polycarbamate), thiram (thiram), ziram (ziram), Zineb (zineb), · 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),  trazodone bacteria (famoxadone), fenamidone (fenamidone), iso triarimol (fenarimol), fuberidazole (fuberidazole), flutolanil (flutolanil), furosemide pyrazole Spirit (furametpyr), Isoprothiolane (isoprothiolane), propoxyphene off embroidered amine (mepronil), nuarimol (nuarimol), iso thiodiazole ketone (octhilinone), Fluopicolide (picobenzamid), thiabendazole (probenazole), propoxyphene quinoline (proquinazid), pyrifenox (pyrifenox), pyroquilon (pyroquilon), quinoxyfen (quinoxyfen) , silthiofam (silthiofam), thiabendazole (thiabendazole), thifluzamide (thifluzamide), thiophanate-methyl (thiophanate-methyl), tiadinil (tiadinil), tricyclazole (tricyclazole), piperazine Ammonia Spirit (triforine), 3- [5- (4- chlorophenyl) -2,3-dimethyl-oxazolidine-3-isobutyl  yl] pyridine and sulfur azoxystrobin Spirit (bupirimate); · nitrophenyl Derivatives, such as binapacryl (binapacryl), dinocap (dinocap), enemy mites through (dinobuton), isopropyl elimination (nitrophthal-isopropyl); · phenylpyrroles as fenpiclonil (fenpiclonil) and fluorine  bacteria (fludioxonil); · does not belong to any other class of fungicides, such as acibenzolar (acibenzolar-S-methyl), benzene thiodiazole amine (benthiavalicarb), chlorine cyclopropane amide (carpropamid), chlorothalonil (chlorothalonil ), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), da bacterial clearance (diclomezine), double cyanuric bacteria amine (diclocymet), diethofencarb (diethofencarb), g blast scattered (edifenphos), ethaboxam (ethaboxam), fenhexamid (fenhexamid), potato plague tin (fentin-acetate), Fenoxanil (fenoxanil), azoxystrobin hydrazone (ferimzone), Fluazinam (fluazinam), phycomycetes phosphorus (fosetyl), B phosphine aluminum (fosetyl-aluminum), iprovalicarb (iprovalicarb), hexachlorobenzene (hexachlorobenzol), Metrafenone (metrafenone), pencycuron (pencycuron), Broadway Ling (propamocarb), four chlorobenzene phthalate (phthalide ), tolclofos (tolclofos-methyl), PCNB (quintozene), zoxamide (zoxamide), Isoprothiolane (isoprothiolane), fluopicolide (fluopicolide); chlorine cyclopropane amide ( carpropamid), bis alkynyl amine acid bacteria (mandipropamid), N- (2- {4- [3- (4- chlorophenyl) prop-2-yn-yloxy] -3-methoxy phenyl} ethyl) -2-methyl-3- methylbutanamide, N- (2- {4- [3- (4- chlorophenyl) prop-2-yn-yloxy] -3-methoxy-phenyl } ethyl) -2-ethyl-3- methylbutanamide; furosemide pyrazole spirit (furametpyr), thifluzamide (thifluzamide), penthiopyrad (penthiopyrad), fenhexamid (fenhexamid ), N- (2- cyanophenyl) -3,4-dichloro-isothiazole-5-carboxamide, flubenthiavalicarb, 3- (4- chlorophenyl) -3- (2-isopropyl oxycarbonylamino - 3- methylbutyrylamino) propionate, chloro-5- {2- [1- (6-methyl-pyridin-2-yl-methoxy imino) ethyl] benzyl} carbamate, { 2-chloro-5- [1- (3-benzyloxy-imino-methyl) ethyl] benzyl} carbamate, flusulfamide (flusulfamide), an amide of the formula: 其中X为CHF2或CH3;和R1、R2相互独立地为卤素、甲基或卤代甲基,例如CF3;·由WO 03/075663以通式I描述的嗜球果伞素类(strobilurins),如腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)和肟菌酯(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)、氟吗啉(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[1,2,4]三唑并[1,5-a]嘧啶,例如5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4 ]三唑并[1,5-a]嘧啶;.酰胺杀真菌剂,如cyclofenamid以及(z)-N-[α-(环丙基甲氧亚氨基)-2,3-二氟-6-(二氟甲氧基)苄基]-2-苯基乙酰胺。 Wherein X is CHF2 or CH3; and R1, R2 are each independently halo, methyl or halomethyl, such as CF3; · strobilurin class (strobilurins) WO 03/075663 by the general formula I described, such as azoxystrobin (azoxystrobin), ether amine bacteria (dimoxystrobin), fluoxastrobin (fluoxastrobin), imide bacteria (kresoxim-methyl), fork benzamide (metominostrobin), orysastrobin (orysastrobin), pyridine oxygen bacteria ester (picoxystrobin), pyraclostrobin (pyraclostrobin) and trifloxystrobin (trifloxystrobin), · sulfenic acid derivatives, such as captafol (captafol), captan (captan), antibacterial Ling (dichlofluanid) , folpet (folpet), for tolylfluanid (tolylfluanid); · cinnamide and similar compounds, such as dimethomorph (dimethomorph), flurbiprofen bacteria (flumetover), flumorph (flumorph); · for example 6-aryl in each case by the WO 98/46608, WO 99/41255 or WO 03/004465 described by formula I [1,2,4] triazolo [1,5-a] pyrimidines, e.g., 5 - chloro-7- (4-methylpiperazin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine; amide fungicides, such as cyclofenamid and (z) -N- [α- (cyclopropyl methoxy imino) -2,3-difluoro-6- (difluoromethoxy) benzyl] - 2-phenyl acetamide.

    可以配制成本发明的含水活性化合物组合物的除草剂的实例包括:·1,3,4-噻二唑类,如草噻咪(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)、哌草丹(dimepiperate)、噻吩草胺(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);·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)、草硫膦(sulfosate);·氨基三唑类,如杀草强(amitrole);·酰替苯胺类,如莎稗磷(anilofos)、苯噻草胺(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(dichlorprop-P)、2,4,5-滴丙酸(fenoprop)、氟草烟(fluroxypyr)、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(triclopyr);·苯甲酸类,如草灭平(chloramben)、麦草畏(dicamba);·苯并噻二嗪酮类,如噻草平(bentazone);·漂白剂,如异恶草酮(clomazone)、吡氟草胺(diflufenican)、氟咯草酮(fluorochloridone)、胺草唑(flupoxam)、氟草同(fluridone)、吡唑特(pyrazolate)、磺草酮(sulcotrione);·氨基甲酸酯类,如长杀草(carbetamide)、氯草灵(chlorbufam)、氯苯胺灵(chlorpropham)、异苯敌草(desmedipham)、苯敌草(phenmedipham)、灭草猛(vernolate);·喹啉酸类,如二氯喹啉酸(quinclorac)、喹草酸(quinmerac);·二氯丙酸类,如茅草枯(dalapon);·二氢苯并呋喃类,如乙呋草黄(ethofumesate);·二氢呋喃-3-酮类,如呋草酮(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)、磺乐灵(nitralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、卡乐施(profluralin)、氟乐灵(trifluralin);·二硝基酚类,如杀草全(bromofenoxim)、地乐酚(dinoseb)、地乐酯(dinoseb-acetate)、地乐消酚(dinoterb)、二硝甲酚(DNOC)、minoterb-acetate;·二苯基醚类,如氟锁草醚(acifluorfen-sodium)、苯草醚(aclonifen)、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(fomesafen)、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);·联吡啶类,如莎草快(cyperquat)、苯敌快(difenzoquat-methyl sulfate)、敌草快(diquat)、对草快(paraquat-dichloride);·咪唑类,如丁环隆(isocarbamid);·咪唑啉酮类,如imazamethapyr、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草酯(imazethabenz-methyl)、咪草烟(imazethapyr)、甲咪唑烟酸(imazapic)、咪草啶酸(imazamox);·二唑类,如灭草定(methazole)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon);·环氧乙烷类,如灭草环(tridiphane);·酚类,如溴苯腈(bromoxynil)、碘苯腈(ioxynil);·苯氧基苯氧基丙酸酯类,如炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、禾草灵(diclofop-methyl)、唑禾草灵(fenoxaprop-ethyl)、高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)、喔草酯(propaquizafop)、喹禾灵(quizalofop-ethyl)、精喹禾灵(quizalofop-p-ethyl)、喹禾灵四氢糠基酯(quizalofop-tefuryl);·苯基乙酸类,如伐草克(chlorfenac);·苯基丙酸类,如chlorophenprop-methyl; Examples of the invention may be formulated into an aqueous active compound composition herbicides include: 1,3,4-thiadiazoles, such as grass thiophene microphone (buthidazole) and Epoxiconazole alachlor (cyprazole); · amides, such as Grass poisoned (allidochlor), the new Yan Ling (benzoylprop-ethyl), bromine butyrylcholinesterase alachlor (bromobutide), grass Kele (chlorthiamid), dimepiperate (dimepiperate), dimethenamid (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); · amino phosphoric acids, such as bialaphos phosphine (bilanafos), Turk grass (buminafos), glufosinate (glufosinate-ammonium), glyphosate (glyphosate), grass phosphinothioyl (sulfosate); · amino triazoles, such as amitrole (amitrole); · anilide class, such as anilofos (anilofos), mefenacet (mefenacet); · 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 (dichlorprop-P), 2,4,5- Dichlorprop (fenoprop), Fluroxypyr (fluroxypyr), 2 MCPA (MCPA), 2 MCPA butyric acid (MCPB), 2 mecoprop (mecoprop), 2 A 4-chloropropyl high salt (mecoprop-P), Napropamide (napropamide), Napropamide (napropanilide), fixed grass ester (triclopyr) ; · benzoic acids, such as grass off the flat (chloramben), dicamba (dicamba); · benzothiadiazine ketones, such as thiophene grass flat (bentazone); · bleach, such as clomazone (clomazone), topiramate fluorine alachlor (diflufenican), fluorine slightly oxadiazon (fluorochloridone), amine grass azole (flupoxam), fluoride grass with (fluridone), pyrazolinates (pyrazolate), sulcotrione (sulcotrione); · carbamates, such as Long herbicide (carbetamide), chlorine grass Ling (chlorbufam), Chlorpropham (chlorpropham), different phenmedipham (desmedipham), phenmedipham (phenmedipham), herbicides, Meng (vernolate); · quinoline acids, such as Quinclorac (quinclorac), quinmerac (quinmerac); · dichloro-propionic acids, such as dry grass (dalapon); · dihydrobenzofuran class, such as ethylene furosemide grass yellow (ethofumesate); · dihydrofuran - 3- ketones, such as flurtamone (flurtamone); · dinitroanilines, such as fluorine alachlor (benefin), Butralin (butralin), Le enemy amine (dinitramine), Ding fluorine eliminate grass (ethalfluralin), fluorine eliminate grass (fluchloralin), different trifluralin (isopropalin), sulfur trifluralin (nitralin), oryzalin (oryzalin), pendimethalin (pendimethalin), aminopropylether F Ling (prodiamine), card Oxfam (profluralin), Treflan (trifluralin); · dinitrophenols, such as herbicide-wide (bromofenoxim), dinoseb (dinoseb), to music ester (dinoseb-acetate), to the music consumer phenol (dinoterb), dinitro-p-cresol (DNOC), minoterb-acetate; · diphenyl ethers such as acifluorfen (acifluorfen-sodium), aclonifen (aclonifen), Bifenox (bifenox), CNP (chlornitrofen), dry herbicides Long (difenoxuran), fluorine milk ether (ethoxyfen), eliminate grass ether (fluorodifen), B fluoroglycofen (fluoroglycofen-ethyl), fluoro yellow grass ether amine (fomesafen), furosemide fluorine grass ether (furyloxyfen), Lactofen Ling (lactofen), weeding ether (nitrofen), nitric fluoroglycofen (nitrofluorfen), flunitrazepam grass ether (oxyfluorfen); · bipyridine-based, such as sedge fast (cyperquat), benzene enemy fast (difenzoquat-methyl sulfate), diquat (diquat), paraquat (paraquat-dichloride); · imidazole class, such as Ding USI (isocarbamid); · imidazolinones, such as imazamethapyr, imazapyr (imazapyr), imazaquin (imazaquin) , imazethapyr ester (imazethabenz-methyl), imazethapyr (imazethapyr), imazapic (imazapic), imazamox (imazamox); ·  two azoles, such as methazole (methazole), propargyl  carfentrazone (oxadiargyl), oxadiazon (oxadiazon); · ethylene oxides, such as herbicides ring (tridiphane); · phenols, such as bromoxynil (bromoxynil), ioxynil (ioxynil); · phenoxy phenoxy acid esters, such as clodinafop-propargyl (clodinafop), cyhalofop (cyhalofop-butyl), diclofop (diclofop-methyl),  oxazole diclofop (fenoxaprop-ethyl), high  azole diclofop (fenoxaprop-p-ethyl), thiazole diclofop (fenthiaprop-ethyl), fluazifop (fluazifop-butyl), fine fluazifop (fluazifop-p-butyl), haloxyfop Ling (haloxyfop-ethoxyethyl), haloxyfop (haloxyfop-methyl), fine haloxyfop (haloxyfop-p-methyl), cockle ether (isoxapyrifop), propaquizafop (propaquizafop), quizalofop ( quizalofop-ethyl), Quizalofop (quizalofop-p-ethyl), quizalofop tetrahydrofurfuryl ester (quizalofop-tefuryl); · phenyl acetic acids, such as cutting the grass g (chlorfenac); · phenyl propionate class, such as chlorophenprop-methyl;

    ·ppi-活性化合物,如吡草酮(benzofenap)、酰亚胺苯氧乙酸戊酯(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、炔草胺(flumipropyn)、flupropacil、苄草唑(pyrazoxyfen)、磺胺草唑(sulfentrazone)、噻二唑草胺(thidiazimin);·吡唑类,如吡氯草胺(nipyraclofen);·哒嗪类,如杀草敏(chloridazon)、抑芽丹(maleic hydrazide)、达草灭(norflurazon)、达草止(pyridate);·吡啶羧酸类,如二氯皮考啉酸(clopyralid)、氟硫草定(dithiopyr)、毒莠定(picloram)、噻氟啶草(thiazopyr);·嘧啶基醚类,如嘧硫苯甲酸(pyrithiobac-acid)、嘧硫苯甲酸钠(pyrithiobac-sodium)、双嘧苯甲酸(KIH-2023)、肟啶草(KIH-6127);·磺酰胺类,如氟唑啶草(flumetsulam)、唑草磺胺(metosulam);·三唑羧酰胺类,如triazofenamide;·尿嘧啶类,如除草定(bromacil)、环草定(lenacil)、特草定(terbacil);·此外还有草除灵(benazolin)、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)、环庚草醚(cinmethylin)、敌草腈(dichlobenil)、草藻灭(endothall)、fluorbentranil、氟草磺(mefluidide)、氟草磺胺(perfluidone)、哌草磷(piperophos)、topramezone和环己酮酸钙(prohexadione-calcium);·磺酰脲类,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron-methyl)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯黄隆(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)、噻黄隆(thifensulfuron-methyl)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron-methyl)、氟胺黄隆(triflusulfuron-methyl)、三氟甲磺隆(tritosulfuron);·环己烯酮类作物保护剂,如枯杀达(alloxydim)、烯草酮(clethodim)、环己烯草酮(cloproxydim)、噻草酮(cycloxydim)、稀禾定(sethoxydim)和肟草酮(tralkoxydim)。 · Ppi- active compounds, such as pyridine oxadiazon (benzofenap), flumiclorac amyl acetate (flumiclorac-pentyl), fluorine  oxazinone (flumioxazin), flumipropyn (flumipropyn), flupropacil, benzyl grass azole (pyrazoxyfen ), sulfa grass azole (sulfentrazone), thiadiazole alachlor (thidiazimin); · pyrazoles, such as chlorine topiramate alachlor (nipyraclofen); · pyridazine, such as herbicide-sensitive (chloridazon), maleic hydrazide (maleic hydrazide), norflurazon (norflurazon), up grass only (pyridate); · pyridine carboxylic acids, such as dichloro picolinic acid (clopyralid), dithiopyr (dithiopyr), picloram (picloram), thiophene fluorine pyridine grass (thiazopyr); · pyrimidine ethers, such as pyrithiobac (pyrithiobac-acid), sodium benzoate pyrithiobac (pyrithiobac-sodium), bispyribac (KIH-2023), pyridine oxime grass (KIH-6127 ); - sulfonamides, such as fluorine yl pyridine grass (flumetsulam), carfentrazone sulfonamide (metosulam); · triazole carboxamides, e.g. triazofenamide; · uracils, such as bromacil (bromacil), grass ring set (lenacil ), terbacil (terbacil); · in addition Benazolin (benazolin), furosemide grass yellow (benfuresate), bensulide (bensulide), fomesafen (benzofluor), thiophene grass flat (bentazon), glufosinate (butamifos), benzene sulfone azole (cafenstrole), diuron cable (chlorthal-dimethyl), cycloheptyl grass ether (cinmethylin), diuron nitrile (dichlobenil), grass algae off (endothall), fluorbentranil, fluorine grass sulfonamide (mefluidide) fluoride sulfa grass (perfluidone), piperazine grass phosphorus (piperophos), topramezone and cyclohexanone calcium (prohexadione-calcium); · sulfonylureas, such as acesulfame Huang Long (amidosulfuron), tetrazole Huang Long (azimsulfuron) , bensulfuron (bensulfuron-methyl), chlorimuron-ethyl (chlorimuron-ethyl), chlorsulfuron (chlorsulfuron), ether Huang Long (cinosulfuron), cyproterone Huang Long (cyclosulfamuron), amine benzene 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), thifensulfuron (thifensulfuron-methyl), ether, benzene Huang Long (triasulfuron), benzene Huang Long (tribenuron-methyl), amine fluoride Huang Long (triflusulfuron-methyl), trifluoromethanesulfonic Long (tritosulfuron); · Cyclohexenone crop protection agents, such as dry kill up (alloxydim ), clethodim (clethodim), cyclohexanone clethodim (cloproxydim), 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-1-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-[三氟甲基]-1,3,5-三嗪-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} propoxy imino] butyl) -3-hydroxy -5- (2H- tetrahydro-thiopyran-3-yl) -2-cyclohexen-1-one , and very particularly preferred sulfonylurea herbicidal active compound is N - (((4- methoxy-6- [trifluoromethyl] -1,3,5-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:·有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorphos)、甲基毒虫畏(dimethylvinphos)、杀抗松(dioxabenzofos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、苯硫磷(EPN)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基一六零五(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(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)、丙溴磷(profenofos)、丙硫磷(prothiofos)、primiphos-ethyl、吡唑硫磷(pyraclofos)、打杀磷(pyridaphenthion)、乙丙硫磷(sulprophos)、三唑磷(triazophos)、敌百虫(trichlorfon)、杀虫畏(tetrachlorvinphos)、蚜灭多(vamidothion);·氨基甲酸酯类:棉铃威(alanycarb)、丙硫克百威(benfuracarb)、虫威(bendiocarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、二唑虫(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)、唑蚜威(triazamate);·合成除虫菊酯类:丙烯菊酯(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、苯醚氰菊酯(cyphenothrin)、乙氰菊酯(cycloprothrin)、氯氰菊酯(cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(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)、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-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、氯菊酯(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)、灭蝇胺(cyromacin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentazine);b)蜕皮激素拮抗剂,如特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(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,如螺螨酯(spirodiclofen);·新烟碱类(neonicotinoids),如氟啶虫酰胺(flonicamid)、噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、硝虫噻嗪(nithiazine)、吡虫清(acetamiprid)、噻虫啉(thiacloprid);·不属于上述类别的其它杀虫剂,如齐墩螨素(abamectin)、灭螨醌(acequinocyl)、吡虫清(acetamiprid)、虫螨脒(amitraz)、艾扎丁(azadirachtin)、杀虫磺(bensultap)、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟唑虫清(chlorfenapyr)、杀虫脒(chlordimeform)、灭蝇胺(cyromazine)、杀螨硫隆(diafenthiuron)、呋虫胺(dinetofuran)、茂醚(diofenolan)、埃玛菌素(emamectin)、硫丹(endosulfan)、乙虫清(ethiprole)、喹螨醚(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)、吡虫啉(imidacloprid)、二唑虫(indoxacarb)、异丙威(isoprocarb)、速灭威(metolcarb)、哒螨酮(pyridaben)、拒嗪酮(pymetrozine)、艾克敌105(spinosad)、吡螨胺(tebufenpyrad)、噻虫嗪(thiamethoxam)、硫环杀(thiocyclam)、啶虫丙醚(pyridalyl)、氟啶虫酰胺(flonicamid)、fluacypyrim、米尔螨素(milbemectin)、螺甲螨酯(spiromesifen)、flupyrazofos、NC 512、唑虫酰胺(tolfenpyrad)、flubendiamide、双三氟虫脲(bistrifluron)、benclothiaz、pyrafluprole、pyriprole、amidoflumet、flufenerim、cyflumetofen、灭螨醌(acequinocyl)、lepimectin、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin)、氨基腙(amidrazonr)、metaflumizone、NR′-2,2-二卤代-1-R″-环丙烷甲酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙、NR′-2,2-二(R)丙酰胺-2-(2,6-二氯-α,α,α-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: Examples of the invention may be formulated pesticide costs aqueous active compound composition include: organic (thio) phosphates: acephate (acephate), oxazole piperidine phosphorus (azamethiphos), azinphos-methyl (azinphos-methyl), Chlorpyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), chlorfenvinphos (chlorfenvinphos), diazinon (diazinon), dichlorvos (dichlorphos), methyl chlorfenvinphos (dimethylvinphos), kill anti-pine (dioxabenzofos), Dicrotophos (dicrotophos), dimethoate (dimethoate), Disulfoton (disulfoton), ethion (ethion), benzene parathion (EPN), fenitrothion (fenitrothion), Fenthion (fenthion), different  Triazophos ( isoxathion), malathion (malathion), methamidophos (methamidophos), methidathion (methidathion), methyl one thousand six hundred and five (methyl-parathion), mevinphos (mevinphos), monocrotophos (monocrotophos) , oxydemeton (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), profenofos (profenofos), propionic parathion (prothiofos), primiphos-ethyl, pyrazole parathion (pyraclofos ), imputed phosphorus (pyridaphenthion), ethylene-propylene parathion (sulprophos), Triazophos (triazophos), trichlorfon (trichlorfon), tetrachlorvinphos (tetrachlorvinphos), aphid methomyl (vamidothion); · carbamate : alanycarb (alanycarb), benfuracarb (benfuracarb),  insect Granville (bendiocarb), carbaryl (carbaryl), carbofuran (carbofuran), carbosulfan (carbosulfan), fenoxycarb ( fenoxycarb), furathiocarb (furathiocarb),  oxadiazole insects (indoxacarb), methiocarb (methiocarb), methomyl (methomyl), carbamoyl fork K (oxamyl), pirimicarb (pirimicarb), propoxur ( propoxur), thiodicarb (thiodicarb), azole pirimicarb (triazamate); · synthetic pyrethroids: allethrin (allethrin), bifenthrin (bifenthrin), cyfluthrin (cyfluthrin), phenothrin ( cyphenothrin), B cyhalothrin (cycloprothrin), cypermethrin (cypermethrin), deltamethrin (deltamethrin), esfenvalerate (esfenvalerate), phenothrin (ethofenprox), fenpropathrin (fenpropathrin), kill pyrethroid (fenvalerate), (RS) cyhalothrin (cyhalothrin), cyhalothrin (lambda-cyhalothrin), imiprothrin (imoprothrin), permethrin (permethrin), alkynone permethrin (prallethrin ), alkynone permethrin I, alkynone permethrin II, pest silicon ether (silafluofen), fluvalinate (tau-fluvalinate), tefluthrin (tefluthrin), tralomethrin (tralomethrin), four fluorine permethrin (transfluthrin), A-cypermethrin (alpha-cypermethrin), has cypermethrin (zeta-cypermethrin), permethrin (permethrin); · arthropod growth regulators: a) chitin synthesis inhibitors: benzyl ureide class, such as Chlorfluazuron (chlorfluazuron), cyromazine (cyromacin), fluorouracil kill (diflubenzuron), fluorine mites urea (flucycloxuron), flufenoxuron (flufenoxuron), hexaflumuron (hexaflumuron), fluorine propoxyphene Urea (lufenuron), novaluron (novaluron), teflubenzuron (teflubenzuron), insecticide-long (triflumuron); buprofezin (buprofezin),  Mao ether (diofenolan), hexythiazox (hexythiazox), especially benzene  oxazole (etoxazole), clofentezine (clofentazine); b) ecdysone antagonists, such as halofenozide (halofenozide), methicillin hydrazide (methoxyfenozide), tebufenozide (tebufenozide); c) Paul juvenile hormone analogues such as pyriproxyfen (pyriproxyfen), methoprene (methoprene), fenoxycarb (fenoxycarb); d) lipid biosynthesis inhibitors, such as spirodiclofen (spirodiclofen); · neonicotinoids (neonicotinoids), such as flonicamid (flonicamid), clothianidin (clothianidin), dinotefuran (dinotefuran), imidacloprid (imidacloprid), thiamethoxam (thiamethoxam), nitenpyram (nitenpyram), nitro worms thiophene triazine (nithiazine), acetamiprid (acetamiprid), thiacloprid (thiacloprid); · does not belong to the above category of other insecticides, such as abamectin (abamectin), mites quinone (acequinocyl), acetamiprid ( acetamiprid), amitraz (amitraz), Yi Zhading (azadirachtin), bensultap (bensultap), BIFENAZATE (bifenazate), cartap (cartap), chlorfenapyr (chlorfenapyr), chlordimeform (chlordimeform), cyromazine (cyromazine), acaricide sulfur Long (diafenthiuron), dinotefuran (dinetofuran),  Mao ether (diofenolan), emamectin (emamectin), endosulfan (endosulfan), ethiprole (ethiprole), Fenazaquin (fenazaquin), fipronil (fipronil), cutting acetamiprid (formetanate), cutting worm hydrochloride (formetanate hydrochloride), lindane (gamma-HCH), mirex hydrazone (hydramethylnon), Imidacloprid (imidacloprid),  oxadiazole insects (indoxacarb), isoprocarb (isoprocarb), metolcarb (metolcarb), pyridaben (pyridaben), pymetrozine (pymetrozine), spinosad 105 (spinosad), topiramate mites amine (tebufenpyrad), thiamethoxam (thiamethoxam), sulfur ring kill (thiocyclam), Acetamiprid propyl ether (pyridalyl), Flonicamid (flonicamid), fluacypyrim, Mill mites hormone (milbemectin), spiromesifen ( spiromesifen), flupyrazofos, NC 512, azole insect amide (tolfenpyrad), flubendiamide, bistrifluoromethyl worm urea (bistrifluron), benclothiaz, pyrafluprole, pyriprole, amidoflumet, flufenerim, cyflumetofen, mites quinone (acequinocyl), lepimectin, propionic fluorine-ju ester (profluthrin), tetrafluoroethylene pyrethroid ether (dimefluthrin), amidrazone (amidrazonr), metaflumizone, NR'-2,2- dihalo -1-R "- ​​cyclopropanecarboxamide -2- (2,6 - dichloro -α, α, α- trifluoro-p-tolyl) hydrazone, NR'-2,2- two (R) propionamide-2- (2,6-dichloro -α, α, α- three fluorine-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:

    下式的氨基异噻唑: The formula aminoisothiazole: 其中R=-CH2O-CH3或H,和R'=-CF2CF2CF3;下式的邻氨基苯甲酰胺: Wherein R = -CH2O-CH3 or H, and R '= - CF2CF2CF3; formula anthranilamide: 其中R为C1-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 C1-C4 alkyl such as methyl, ethyl, isopropyl or n-butyl, and the compound of the formula: ·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R11和R12相互独立地为氢、卤素、CN、C1-C4烷基、C1-C4烷氧基、C1-C4卤代烷基或C1-C4卤代烷氧基且R13为C1-C4烷氧基、C1-C4卤代烷基或C1-C4卤代烷氧基,例如其中R11为3-CF3、R12为4-CN且R13为4-OCF3的化合物IV(=metaflumizone)。 Wherein R11 and R12 are independently hydrogen, halogen, CN, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, and R13 is C1-C4 alkoxy, C1 -C4 haloalkyl or C1-C4 haloalkoxy, e.g., wherein R11 is 3-CF3, R12 and R13 is 4-CN Compound IV 4-OCF3 of (= metaflumizone).

    有用的生长调节剂例如为矮壮素(chlormequat-chloride)、助壮素(mepiquat-chloride)、环己酮酸钙(prohexadione-calcium)或赤霉素类。 Useful growth regulators, for example, chlormequat (chlormequat-chloride), mepiquat (mepiquat-chloride), cyclohexanone calcium (prohexadione-calcium) or gibberellins. 这些例如包括赤霉素GA1、GA3、GA4、GA5和GA7等,对应的外-16,17-二氢赤霉素,及其衍生物,例如与C1-C4羧酸的酯。 These include, for example gibberellin GA1, GA3, GA4, GA5 and GA7 etc., corresponding foreign 16,17-dihydro GA, and its derivatives, for example, C1-C4 esters of carboxylic acids. 本发明优选外-16,17-二氢-GA513-乙酸酯,此外还有1-萘基乙酰胺、1-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)、氯甲丹(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)、噻节因(dimethipin)、杀螨醇(chlorfenethol)、硅长素(etacelasil)、乙烯利(ethephon)、果宝素(ethychlozate)、2,4,5-涕丙酸(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)、吲哚丁酸(indolylbutyric acid)、吲哚乙酸(indolylaceticacid)、karetazan、动力精(kinetin)、lactidichlor-ethyl、抑芽丹(maleichydrazide)、氟草磺(mefluidide)、抑草生(naptalam)、多效唑(paclobutrazole)、喹草酸(quinmerac)、杀雄啉(sintofen)、调环烯(tetcyclacis)、赛二唑素(thidiazuron)、三碘苯甲酸、抑芽唑(triapenthenol)、triazethan、丁硫亚磷(tribufos)、抗倒酯(trinexapac-ethyl)和烯效唑(uniconazole)。 The present invention preferably 16,17-dihydro outer -GA513- acetate, in addition to 1-naphthyl acetamide, 1-naphthyl acetate, 2-naphthoxy acetic acid, adjusted acid (3-CPA), Promoting creatures (4-CPA), pyrimidine alcohol (ancymidol), anthraquinone, benzylamino purine (BAP), defoliation phosphorous (butifos), Ding sulfur phosphorous (tribufos), Butralin (butralin), chloromethyl Dan ( chlorflurenol), benzene da acid (clofencet), cyclic acid amide (cyclanilide), daminozide (daminozide), dicamba (dicamba), double the ancient sodium (dikegulac sodium), thiophene section because (dimethipin), mites alcohol (chlorfenethol), silicon auxin (etacelasil), ethephon (ethephon), fruit Po plain (ethychlozate), 2,4,5- tears propionic acid (fenoprop), 2,4,5-TP, fomesafen hormone (fluoridamid ), adjusting ethyl alcohol (flurprimidol), Flutriafol (flutriafol), guazatine (guazatin), ene benomyl (imazalil), indole butyric acid (indolylbutyric acid), indole acetic acid (indolylaceticacid), karetazan, dynamic fine ( kinetin), lactidichlor-ethyl, maleic hydrazide (maleichydrazide), fluoride grass sulfonamide (mefluidide), naptalam (naptalam), MET (paclobutrazole), quinmerac (quinmerac), CHA morpholine (sintofen), adjust cyclic olefin (tetcyclacis ), race oxadiazole hormone (thidiazuron), triiodobenzoic acid, suckering azole (triapenthenol), triazethan, Ding sulfur phosphorous (tribufos), trinexapac (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WO03/004465中以式I描述的嗜球果伞素类、唑类和6-芳基三唑并[1,5a]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 WO03 / 004465 to formula I as described strobilurin type, azoles and 6-aryl-triazolo [1,5a] pyrimidine, especially an aqueous active compound composition of the active compound of formula V in use: 其中Rx为基团NR14R15或任选被卤素、OH、C1-C4烷氧基、苯基或C3-C6环烷基取代的线性或支化C1-C8烷基,为C2-C6链烯基、C3-C6环烷基、C3-C6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个选自卤素、OH、C1-C4烷基、C1-C4卤代烷氧基、C1-C4烷氧基和C1-C4卤代烷基的取代基;R14、R15相互独立地为氢、C1-C8烷基、C1-C8卤代烷基、C3-C10环烷基、C3-C6卤代环烷基、C2-C8链烯基、C4-C10链二烯基、C2-C8卤代链烯基、C3-C6环烯基、C2-C8卤代环烯基、C2-C8炔基、C2-C8卤代炔基或C3-C6环炔基,R14和R15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、C1-C6烷基、C1-C6卤代烷基、C2-C6链烯基、C2-C6卤代链烯基、C1-C6烷氧基、C1-C6卤代烷氧基、C3-C6链烯氧基、C3-C6卤代链烯氧基、(外)-C1-C6亚烷基和氧基-C1-C3亚烷氧基的取代基;L选自卤素、氰基、C1-C6烷基、C1-C4卤代烷基、C1-C6烷氧基、C1-C4卤代烷氧基和C1-C6烷氧羰基;L1为卤素、C1-C6烷基或C1-C6卤代烷基,尤其是氟或氯;X为卤素、C1-C4烷基、氰基、C1-C4烷氧基或C1-C4卤代烷基,优选卤素或甲基,尤其是氯。 Wherein Rx is a group NR14R15 or optionally substituted with halogen, OH, C1-C4 alkoxy, phenyl or C3-C6 cycloalkyl substituted linear or branched C1-C8 alkyl, a C2-C6 alkenyl group, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl or naphthyl, wherein the 4 last mentioned radicals may have two, three or four substituents selected from halo, OH, C1-C4 alkyl , C1-C4 haloalkoxy, C1-C4 alkoxy and C1-C4 haloalkyl substituents; R14, R15 independently of one another are hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, C3-C10 cycloalkyl group, C3-C6 halocycloalkyl, C2-C8 alkenyl, C4-C10 alkadienyl, C2-C8 haloalkenyl group, C3-C6 cycloalkenyl, C2-C8 haloalkyl cycloalkenyl , C2-C8 alkynyl group, a nitrogen atom, C2-C8 alkynyl or halo C3-C6 cycloalkyl alkynyl, R14 and R15 which they are attached a 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 atoms as ring members and / or may carry one or more substituents selected from halo, C1-C6 alkyl, C1-C6 haloalkyl, C2- C6 alkenyl, C2-C6 haloalkenyl group, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy, (exo) - C1-C6 alkylene and alkylene groups -C1-C3 alkoxy substituent; L is selected from halo, cyano, C1-C6 alkyl, C1-C4 haloalkyl, C1-C6 alkoxy, C1- C4 haloalkoxy and C1-C6 alkoxycarbonyl group; L1 is halogen, C1-C6 alkyl or C1-C6 haloalkyl, in particular fluorine or chlorine; X is halogen, C1-C4 alkyl, cyano, C1-C4 alkoxy or C1-C4 haloalkyl, preferably halo or methyl, in particular chlorine.

    式V化合物的实例是5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(4-甲基哌嗪-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(吗啉-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-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-氯-7-(吗啉-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(异丙基氨基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(环戊基氨基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]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-a]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-a]嘧啶,5-氯-7-(3,3-二甲基丁-2-基氨基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-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-氯-7-(环己基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(2-甲基丁-3-基)-6-(2,4,6-三氟苯基)-[1,2,4]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)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(4-甲基环己-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(己-3-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-氯-7-(2-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-(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-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-(4-甲基哌啶-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-(4-甲基哌嗪-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)-[1,2,4]三唑并[1,5-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)-[1,2,4]三唑并[1,5-a]嘧啶,5-甲基-7-(异丙基氨基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-甲基-7-(环戊基氨基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-甲基-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-a]嘧啶,5-甲基-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-a]嘧啶,5-甲基-7-(3,3-二甲基丁-2-基氨基)-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)-[1,2,4]三唑并[1,5-a]嘧啶,5-甲基-7-(2-甲基丁-3-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-甲基-7-(3-甲基丙-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-(4-甲基环己-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-(己-3-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶,5-甲基-7-(2-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-甲基-7-(3-甲基丁-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶和5-甲基-7-(1-甲基丙-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶。 Examples of compounds of formula V is 5-chloro-7- (4-methylpiperazin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (4-methyl-piperazin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (morpholin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] pyrazolo [1,5-a] pyrimidine, 5-chloro-7- (piperidin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazole and [1,5-a] pyrimidine, 5-chloro-7- (morpholin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (isopropylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1, 5-a] pyrimidine, 5-chloro-7- (cyclopentylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a ] pyrimidine, 5-chloro-7- (2,2,2-trifluoroethyl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1 , 5-a] pyrimidine, 5-chloro-7- (1,1,1-trifluoro-2-ylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2, 4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (3,3-dimethyl-2-ylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (cyclohexylmethyl) -6- (2,4,6-trifluoro-phenyl) - [1 , 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (cyclohexyl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (2-methylbut-3-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2, 4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (3-methyl-propan-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (4-methyl-cyclohex-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (hex-3-yl) -6- (2,4,6-trifluoro-phenyl) - [1 , 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (2-methyl-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (3-methylbut-1-yl) -6- (2,4,6-trifluorophenyl ) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (1-methyl-prop-1-yl) -6- (2,4,6-trifluoro- phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (4-methylpiperazin-1-yl) -6- (2,4, 6-trifluoromethyl-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (4-methyl-piperazin-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) - [1,2,4] triazolo [1,5-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) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (isopropylamino) -6- (2, 4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclopentylamino) -6- (2,4, 6-trifluoromethyl-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (2,2,2-trifluoroethyl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (1,1,1-trifluoro-propan - 2- ylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (3, 3-dimethylamino-2-ylamino) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl -7- (cyclohexylmethyl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl - 7- (cyclohexyl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (2 - methylbut-3-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methyl-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl -7- (4-methyl-cyclohex-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine , 5-methyl-7- (hex-3-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (2-methyl-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a ] pyrimidine, 5-methyl-7- (3-methylbut-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1, 5-a] pyrimidine and 5-methyl-7- (1-methyl-prop-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-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(chlorfenapyr),合成除虫菊酯类如氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、乙氰菊酯(cycloprothrin)、氯氰菊酯(cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(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的缩氨基脲的活性化合物组合物,尤其是含水活性化合物组合物中的用途。 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 (chlorfenapyr), synthetic pyrethroid such as bifenthrin ( bifenthrin), cyfluthrin (cyfluthrin), B cyhalothrin (cycloprothrin), cypermethrin (cypermethrin), deltamethrin (deltamethrin), esfenvalerate (esfenvalerate), phenothrin (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 semicarbazone of formula IV in the compositions of the active compound, 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、抗高血压药、维生素、细胞抑制剂—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、胆碱药、胆用治疗药、平喘药、支气管解痉药(bronchospasmolytics)、β受体阻断剂、钙拮抗剂、ACE抑制剂、抗动脉硬化药、抗炎药、抗凝血药、抗低血压药、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。 These include benzodiazepine , antihypertensives, vitamins, cytostatics - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungal agents, fungicides, chemotherapeutics, urinary system medication, platelet aggregation inhibitors, sulfonamides, antispasmodics, hormones, immunoglobulins, sera, thyroid therapeutic drugs, psychotropic drugs, anti-Parkinson's drugs and other anti-hyperkinetic drug, ophthalmic, neurological use products, calcium metabolic 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 drugs, fibrinolytic agents, enzyme products and transport proteins, enzyme inhibitors, emetics, blood flow stimulation, diuretics, diagnostic aids, corticosteroids, anticholinergics, gall therapeutic drugs, asthma drugs, bronchial antispasmodic drugs (bronchospasmolytics), β-blockers, calcium antagonists, ACE inhibitors, anti-atherogenic agents, anti-inflammatory, anti-clotting drugs, anti-hypotensive drugs, anti-low blood sugar, anti-hypertensive drugs , antifibrinolytic drugs, antiepileptics, anti-emetic drugs, antidotes, anti-diabetic drugs, anti-arrhythmic drugs, anti-anemia drug, allergy medication, anthelmintics, analgesics, stimulants, aldosterone antagonists and weight loss products. 合适药物活性化合物的实例尤其是在US2003/0157170第0105-0131段提到的活性化合物。 Examples of suitable pharmaceutically active compounds, especially in US2003 / 0157170 mentioned in paragraph 0105-0131 of the active compound.

    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、桉耐油、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。 Further, suitable for the preparation of food additives such as water-insoluble vitamins and provitamins according amphiphilic polymer composition of the present invention, such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopheryl acetate esters 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称为分散染料和溶剂染料和也称为分散体染料的化合物。 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 according to Color Index called disperse and solvent dyes and also called dispersion dyes. 合适的分散体染料的汇总例如可以在Ullmanns Enzyklopdie der technischen Chemie[Ullmann工业化学百科全书],第4版,第10卷,第155-165页(还参见第7卷,第585页及随后各页-蒽醌染料;第8卷,第244页及随后各页-偶氮染料;第9卷,第313页及随后各页-喹酞酮染料)中找到。 Summary of suitable dispersion dyes for example, Chemie [Ullmann Encyclopedia of Industrial Chemistry], 4th Edition, Vol. 10, pages 155-165 (see also Vol. 7, pp. 585 technischen in Ullmanns Enzyklopdie der and then Each page - anthraquinone dye; Vol. 8, pp. 244 ff - dyes; Vol. 9, p. 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、次甲基和偶氮次甲基染料、萘二甲酰亚胺染料、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, methine and azomethine methyl dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes. 根据本发明合适的分散体染料的实例是下列Color Index的分散体染料:CI分散黄1-228,CI分散橙1-148,CI分散红1-349,CI分散紫1-97,CI分散蓝1-349,CI分散绿1-9,CI分散棕1-21,CI分散黑1-36。 Examples of suitable dispersion according to the invention are the following dye dispersion dye Color Index: CI Disperse Yellow 1-228, CI Disperse Orange 1-148, CI Disperse Red 1-349, CI Disperse Violet 1-97, CI Disperse Blue 1-349, CI disperse Green 1-9, CI disperse Brown 1-21, CI Disperse 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1-35,CI溶剂棕1-63,CI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 1-35, CI Solvent Brown 1-63, CI Solvent Black 3-50. 根据本发明合适的其他染料是萘、蒽、苝、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,酞菁和萘酞菁染料;和UV吸收剂:尤其是选自如下a)-g)组的化合物。 According to the present invention, other suitable dyes are naphthalene, anthracene, perylene, and three benzene (terylene), and four benzene (quarterylene) derivatives, as well as diketo-pyrrolo-pyrrole dyes, perinone dyes, coumarin dyes , isoindoline and isoindolinone ketone dyes, porphyrin dyes, phthalocyanine and naphthalocyanine dyes; and UV absorbers: in particular compounds selected from a) -g) group.

    a)4,4-二芳基丁二烯,b)肉桂酸酯类,c)苯并三唑类, a) 4,4- diaryl-butadiene, b) cinnamic esters, c) benzotriazoles,

    d)羟基二苯甲酮类,e)二苯基氰基丙烯酸酯类,f)草酰胺类,g)2-苯基-1,3,5-三嗪类;a)组的4,4-二芳基丁二烯例如包括式A化合物: d) hydroxy benzophenones, e) diphenyl cyanoacrylate, f) oxamide class, g) 2- phenyl-1,3,5-triazines; a) group 4,4 - diaryl compounds include butadiene, e.g., 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R10和/或R11优选为C1-C8烷基和C5-C8环烷基。 Substituents R10 and / or R11 is preferably C1-C8 alkyl and C5-C8 cycloalkyl.

    b)组的肉桂酸酯类例如包括4-甲氧基肉桂酸2-异戊基酯、4-甲氧基肉桂酸2-乙基己基酯、α-甲氧羰基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸丁酯和α-甲氧羰基对甲氧基肉桂酸甲酯。 b) group of cinnamic acid esters include, for example 4-methoxy cinnamic acid 2-iso-amyl, 4-methoxy cinnamic acid 2-ethylhexyl acrylate, α- cinnamate methoxycarbonyl, α- cyano -β- methyl - methyl p-methoxy cinnamic, α- cyano -β- methyl - p-methoxy cinnamic acid ester and α- 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′-(1,1,3,3-四甲基丁基)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-氯苯并三唑,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(α,α-二甲基苄基)-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′-[2-(2-乙基己氧基)羰基乙基]-2′-羟基苯基)-5-氯苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧羰基乙基)苯基)-5-氯苯并三唑,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)苯并三唑,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[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚|;2-[3′-叔丁基-5′-(2-甲氧羰基乙基)-2′-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯化产物;[R-CH2CH2-COO(CH2)3]2,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。 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 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-t-butyl-2'-hydroxyphenyl yl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec- butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di (α, α- dimethylbenzyl) -2'-hydroxyphenyl) benzene benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '- (2-octyloxy-carbonyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert- butyl-5 '- [2- (2-ethyl-hexyloxy) carbonyl ethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 '- hydroxy-5' - (2-methoxycarbonyl) phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '- (2- oxycarbonyl) phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '- (2-octyloxy-carbonyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethyl-hexyl-oxy) 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 benzene benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl phenol |; 2- [3 ' - tert-butyl-5 '- (2-methoxycarbonyl-ethyl) -2'-hydroxyphenyl] -2H- benzotriazole with polyethylene glycol esterification product 300; [R-CH2CH2-COO ( CH2) 3] 2, wherein R = 3'- tert-butyl-4'-hydroxy -5'-2H- benzotriazol-2-yl-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′-二甲氧基二苯甲酮,2-羟基-4-(2-乙基己氧基)二苯甲酮,2-羟基-4-(正辛氧基)二苯甲酮,2-羟基-4-甲氧基-4′-甲基二苯甲酮,2-羟基-3-羧基二苯甲酮,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 benzophenone, 2-hydroxy-4- (2-ethyl-hexyloxy) benzophenone, 2-hydroxy - 4- (n-octyloxy) benzophenone, 2-hydroxy-4-methoxy-4'-methyl benzophenone, 2-hydroxy-3-carboxy 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)组的二苯基氰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-氰基-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[(2′-氰基-3′,3′-二苯基丙烯酰基)氧基]-2,2-二{[2′-氰基-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 of diphenyl cyanoacrylate include, for example 2-cyano-3,3-diphenyl acrylate, which may for example by a name Uvinul3035 BASF AG, Ludwigshafen commercially available, 2-cyano- 3,3-diphenyl acrylate, 2-ethylhexyl acrylate, which may for example by a name Uvinul3039 BASF AG, Ludwigshafen commercially available, and 1,3-bis [(2'-cyano-3 ', 3 '- diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-phenyl-acryloyl] oxy} methyl} propane, which may be for example 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′-二叔丁草酰二苯胺的混合物,还有邻-、对-甲氧基二取代草酰二苯胺的混合物以及邻-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'-octyloxy 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-oxalic acid bis 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 oxanilide, as well as o - on - methoxy-disubstituted oxanilides and mixtures of o - and p - ethoxy disubstituted grass a mixture of acid diphenylamine.

    g)组的2-苯基-1,3,5-三嗪类例如包括2-(2-羟基苯基)-1,3,5-三嗪,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)-1,3,5-三嗪、2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2,4-二(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-二(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-丁氧基丙氧基)苯基]-4,6-二(2,4-二甲基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-二(2,4-二甲基)-1,3,5-三嗪、2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基苯基]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-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-1,3,5-三嗪、2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-1,3,5-三嗪和2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪。 g) the group of 2-phenyl-1,3,5-triazines include, for example 2- (2-hydroxyphenyl) -1,3,5-triazine, 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) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2,4-bis (2-hydroxy-4-propoxy-phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy - 4-octyloxy-phenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy-phenyl) - 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyl-phenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy - butoxy propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propoxy) phenyl] -4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyl-2-hydroxypropoxy) -2-hydroxyphenyl yl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy- propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy-phenyl) - 4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine and 2- (2-hydroxyphenyl) 4- (4-methoxyphenyl) -6-phenyl-1,3,5-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规表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 comprise surfactant and other conventional additives. 表面活性物质包括表面活性剂、分散剂和润湿剂。 Surface-active substances include surfactants, dispersants 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,尤其是烷基硫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、烷基苯磺酸如木素-和苯酚磺酸、萘-和二丁基萘磺酸的碱金属、碱土金属和铵盐,或十二烷基苯磺酸盐,烷基萘磺酸盐,烷基甲基酯磺酸盐,磺化萘及其衍生物与甲醛的缩合物,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 esters of phosphoric acid; sulfates, in particular alkyl sulfates and alkyl ether sulfates; acid salt, in addition to alkyl sulfonates and alkyl aryl sulfonates, aryl sulfonates and especially alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acid such as lignin - and phenolsulfonic acid, naphthalene- - dibutyl naphthalene sulfonic acid and alkali metal, alkaline earth metal and ammonium salts, or dodecylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl methyl ester sulfonates, sulfonated naphthalene and its derivatives thereof with formaldehyde 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,尤其是烷基三甲基卤化铵,二烷基二甲基卤化铵,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卤化物。 Cationic surfactants such as quaternary ammonium compounds include, in particular, alkyl trimethyl ammonium halides, dialkyl dimethyl ammonium halides, alkyl trimethyl ammonium alkyl sulfates, dialkyl dimethyl ammonium dioxane sulfates, and pyridine and imidazoline derivatives, in particular alkylpyridinium halides .

    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,-烷基芳基醇聚氧乙烯醚,例如辛基苯酚聚氧乙烯醚,-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,-脂肪醇烷氧基化物和羰基合成醇烷氧基化物,尤其是RO-(R18O)r(R19O)sR20类型的烷氧基化物,其中R18和R19相互独立地为C2H4、C3H6、C4H8且 R20为H或C1-C12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,-烷基酚烷氧基化物,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,-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,烷基聚糖苷,N-烷基葡糖酰胺,-烷基甲基亚砜,-烷基二甲基氧化膦,如十四烷基二甲基氧化膦。 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, - alkyl aryl alcohol ethoxylates, such as octyl phenol ethoxylates, - alkoxylated animal and / or vegetable fats and / or oils, such as corn oil ethoxylates , castor oil ethoxylates, tallow fat ethoxylates, - glycerides, such as glyceryl monostearate, - fatty alcohol alkoxylates and oxo-alcohol alkoxylates, especially RO- (R18O ) r (R19O) sR20 type alkoxylates wherein R18 and R19 are independently C2H4, C3H6, C4H8 and R20 is H or C1-C12 alkyl, R is C3-C30 alkyl or C6-C30 alkenyl group, 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 alkoxylates, such as ethoxylated of isooctylphenol, octylphenol or nonylphenol, tributyltin phenol ethoxylates, - fatty amine alkoxylates, fatty acid amide alkoxylates and fatty acid diethanolamide alkoxylates, in particular their ethoxylates, - a saccharide surfactants, sorbitol esters such as sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate alcohol), polyoxyethylene sorbitan sugar alcohol fatty acid esters, alkyl polyglycosides, N- alkyl glucamides, - alkyl methyl sulfoxide, - 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、羧基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, alkyl carboxy betaine and 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物组合物的总量。 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 total amount of the active compound and the polymer composition. 在该情况下,常规表面活性物质优选基于组合物的总重量不超过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%。 In this case, the conventional surface-active substances based on the total weight of the composition preferably 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低这一事实,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:-石蜡油,芳族烃及芳族烃的混合物,例如二甲苯混合物,Solvesso 100、150或200等,-酚类和烷基酚,例如苯酚、氢醌、壬基酚等,-具有4个以上碳原子的酮类,如环己酮、异佛尔酮、isopherone、苯乙酮、萘乙酮,-具有4个以上碳原子的醇类,如乙酰化羊毛脂醇、鲸蜡醇、1-癸醇、1-庚醇、1-己醇、异十八烷醇、异丙醇、油醇、苄醇,-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,乙酸烷基酯(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、甘油单硬脂酸酯,柠檬酸酯,如乙酰柠檬酸三丁酯,此外还有辛酸鲸蜡基酯、油酸甲酯、对羟基苯甲酸甲酯、十四烷酸甲酯、对羟基苯甲酸丙酯、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,-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,橄榄油,花生油,红花油,芝麻油,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, Although one advantage of the compositions of the present invention is their low content of volatile organic compounds that fact, but for example, may need to be mixed composition of the present invention for some applications with organic solvents, oils and fats, preferably environmentally friendly or biocompatible solvent or oil and fat, 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: - paraffin oil, aromatic hydrocarbons and aromatic mixture of aromatic hydrocarbons, such as xylene mixtures thereof, Solvesso 100,150 or 200, etc., - phenols and alkyl phenols, such as phenol, hydroquinone, nonylphenol, etc., - ketones having 4 or more carbon atoms, such as a ring cyclohexanone, isophorone, isopherone, acetophenone, acetonaphthone - alcohols having 4 or more carbon atoms, such as acetylated lanolin alcohol, cetyl alcohol, 1-decanol, 1-heptanol, 1-hexanol, isostearyl alcohol, isopropyl alcohol, oleyl alcohol, benzyl alcohol, - carboxylic acid esters, such as adipic acid dialkyl esters such as adipic acid di (2-ethylhexyl) phthalate, alkyl esters of dicarboxylic acid, such as phthalic acid di (2-ethylhexyl) ester, acetic acid alkyl ester (also branched alkyl group), such as ethyl acetate and ethyl acetoacetate, stearate , such as butyl stearate, glyceryl monostearate, citric acid esters, such as acetyl tributyl citrate, in addition to an ester cetyl octanoate, methyl oleate, methyl paraben, myristyl methyl ester, propyl paraben, methyl benzoate, lactic acid esters such as lactic acid, isopropyl, butyl lactate and lactic acid, 2-ethylhexyl acrylate, - vegetable oils, such as palm oil, rapeseed oil, castor sesame oil and derivatives thereof, such as castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame 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,

    -氢化植物油,如氢化棕榈油、氢化菜籽油、氢化大豆油,-动物油,如猪油、鱼油,-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。 - Hydrogenated vegetable oils, such as hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated soybean oil, - animal oils, such as lard, fish oils, - medium-chain to long chain fatty acid dialkyl amides, e.g. Hallcomides, and - esters of vegetable oils, such as vegetable seed 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 Gum(购自Kelco的Kelzan),Rhodopol23(RhonePoulenc)或Veegum(购自RTVanderbilt)或Attaclay(购自Engelhardt),优选Xanthan Gum。 In this regard, for example it may be mentioned polysaccharides or organic flake minerals, such as Xanthan Gum (available from Kelco's Kelzan), Rhodopol23 (RhonePoulenc) or Veegum (available from RTVanderbilt) or Attaclay (available from Engelhardt), preferably Xanthan Gum.

    适于本发明分散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Rhodorsil),长链醇,脂肪酸,有机氟化合物及其混合物。 Dispersions of the present invention is suitable, for example, silicone antifoam emulsion (e.g., available from Wacker of SilikonSRE or Rhodorsil available from Rhodia), 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被微生物侵袭。 Fungicides can be added to stabilize the composition of the present invention and prevent microbial invasion. 合适的杀菌剂例如为购自ICI的Proxel或购自Thor Chemie的ActicideRS和购自Rohm&amp;Haas的KathonMK。 Suitable fungicides, for example, available from ICI's Proxel or purchased from ActicideRS from Thor Chemie and commercially available from Rohm & amp; Haas of 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%的缓冲剂,以调节pH,其中所用缓冲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. 缓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组合物或有效物质组合物可以以本身与相应活性化合物或有效物质的常规配制剂相当的方式使用。 Wherein the active compound depends on the nature of or containing the active substance, the active compound composition or active substance compositions of the invention may be a conventional formulation or the active compound itself with the corresponding active substance 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:I.1制备实施例1:将1444g四氢呋喃在回流下加热。 I. amphiphilic polymer composition: I.1 Preparation Example 1: 1444g of tetrahydrofuran 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1a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1b,并将混合物在回流下保持24小时。 Within two hours while adding the 2109g and 703g of methyl methacrylate styrene feed 1a and the 1444g of tetrahydrofuran (THF), 18.6g of azobisisobutyronitrile (AIBN) and 58.4g mercaptoethanol feed 1b, 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℃下的粘度为4.0Pa.s)和0.1g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 added 430g of commercially available hexamethylene diisocyanate biuret (NCO content of 22% and a viscosity at 23 ℃ for 4.0Pa.s) and 0.1g of dibutyl tin dilaurate, and the reaction mixture at the same temperature Under stirring, 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50nm(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 50nm (as measured by dynamic light scattering).

    I.2制备实施例2:将1444g THF在回流下加热。 I.2 Preparation Example 2: 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1a和由1444g四氢呋喃、18.6g AIBN和58.4g巯基乙醇组成的进料1b,并将混合物在回流下保持24小时。 It was added over 2 hours while the feed 1a 703g 2109g of methyl methacrylate and styrene and 1b by the feed 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167g异佛尔酮二异氰酸酯和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 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%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.3制备实施例3:将1444g THF在回流下加热。 I.3 Preparation Example 3: 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1a和由1444g四氢呋喃、18.6g AIBN和58.4g巯基乙醇组成的进料1b,并将混合物在回流下保持24小时。 It was added over 2 hours while the feed 1a 703g 2109g of methyl methacrylate and styrene and 1b by the feed 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市售六亚甲基二异氰酸酯的缩二脲(NCO含量为22%,在23℃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 hexamethylene diisocyanate biuret (NCO content of 22% and a viscosity at 23 ℃ for 4.0Pa.s), polyoxyethylene 3000g methyl-terminated (number average molecular weight of 2000 Hamilton, 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: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。 I.4 Preparation Example 4: polyoxyethylene biuret 430g Preparation Example 1 was used in a commercial hexamethylene diisocyanate, 3000g terminated methyl (OH number of 33mg KOH / g solids) and 117mg dibutyl tin dissolved in 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1a和由1444g四氢呋喃、18.6g AIBN和58.4g巯基乙醇组成的进料1b,并将混合物在回流下保持24小时。 It was added over 2 hours while the feed 1a 703g 2109g of methyl methacrylate and styrene and 1b by the feed 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氧乙烯的反应产物,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-capped polyoxyethylene been prepared was then added while 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分散体(粒度为129nm,由动态光散射测定)。 To give a concentration of 30% by weight of amphiphilic polymer composition an aqueous dispersion (particle size of 129nm, as determined by dynamic light scattering).

    II.制备本发明的含水活性化合物制剂II.1分析:这里所述的粘度在旋转粘度计中根据DIN 53019-2测定。 . II II.1 aqueous preparation of active compound of the present invention is prepared Analysis: The viscosity herein rotational viscometer in accordance with DIN 53019-2 measured.

    平均粒径使用含水活性化合物配制剂的稀样品在20℃下由静态光散射方法测定。 The average particle diameter using an aqueous active compound formulation diluted sample at 20 ℃ measured by the 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℃下储存2周并在5℃下储存2周。 To test the storage stability, the aqueous active compound compositions were stored two weeks at 54 ℃ and stored at 5 ℃ 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观察到沉降也没有观察到分层,则样品是储存稳定的。 If under these conditions neither sedimentation was observed delamination was not observed, the sample is storage stable.

    II.2通用制备程序:1.增溶方法(液体活性化合物和活性化合物熔体):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分散体中。 II.2 General preparation procedure: 1 solubilization process (liquid active compounds and active compound melt): In the active compounds present in the low viscosity of the melt temperature of the active compound is stirred into 90g 10g 30g polymer comprising amphiphilic an aqueous polymer dispersion composition. 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: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100℃的有机溶剂(例如四氢呋喃)中。 2. The inversion method: 10g of the active compound and a liquid or solid 30g amphiphilic polymer composition (polymer content> 95% by weight) was dissolved in boiling below 100 ℃ organic solvent (e.g. tetrahydrofuran). 然后在搅拌下加入水并随后通过蒸馏除去有机溶剂。 Water is then added with stirring and then the organic solvent was removed by distillation. 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。 The amount of water should be added so that the resulting aqueous formulation containing 10% by weight of active compound and 30 wt% polymer.

    3.固溶液方法:将0.5g两亲性聚合物组合物(聚合物含量>95重量%)和0.1g活性化合物溶于约20ml二甲基甲酰胺中。 3. The method of solid solution: 0.5g of amphiphilic polymer composition (polymer content> 95 wt%) and 0.1g 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. 加入缓冲的水溶液(100ml,pH6.8)并将该混合物搅拌24小时。 Was added a buffered solution (100ml, pH6.8) 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: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%的活性化合物/THF溶液混合。 4. Nozzle precipitation: the use of two pumps via a mixing nozzle dispersion mixing device in the concentration of 30% water and a polymer concentration of 40% of the active compound is mixed / THF solution. 聚合物分散体的流速为12kg/h,THF溶液的流速为3kg/h,从而使总流速为15kg/h。 The flow rate of the polymer dispersion was 12kg / h, the flow rate of THF solution was 3kg / h, so that the total flow rate of 15kg / h. 混合设备与“Handbook of Industrial Crystallization”(ASMyerson,1993Butterworth-Heinemann,第139页,ISBN 0-7506-9155-7)中所述的设备相类似。 Mixing equipment and "Handbook of Industrial Crystallization" (ASMyerson, 1993Butterworth-Heinemann, p. 139, ISBN 0-7506-9155-7) in the device are similar. 得到包含8%活性化合物和24%聚合物的浅黄色乳状悬浮液。 Obtained containing 8% and 24% active polymer compound as a pale yellow milky suspension. 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。 THF was removed by distillation and then some of the water, thereby forming a compound comprising 10% active polymer and 30% aqueous nanoparticle formulations.

    II.3配制实施例1:通过相反转方法增溶唑菌胺酯(通用程序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。 II.3 Formulation Example 1: Solubilization pyraclostrobin by inversion method (general procedure 2) to 10g and 30g pyraclostrobin from Example amphiphilic polymer composition 2 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,基本视觉上透明,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, the basic visualizing transparent, 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 occurrence. 分散相(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。 The dispersed phase (polymer / active compound particles) having a spherical structure and an average diameter of the light scattering measurement was 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)在70℃下唑菌胺酯为易于流动的熔体(粘度为2200mPas)且因此使用通用程序1在70℃的温度下配制。 II.4 Formulation Example 2: Solubilization pyraclostrobin (general procedure 1) The method of solubilization at 70 ℃ for ease pyraclostrobin melt flow (viscosity 2200mPas) using General Procedure 1 and thus 70 Temperature ℃ under preparation. 所得活性化合物组合物均匀,基本视觉上透明,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, the basic visualizing transparent, 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.

    分散相(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直径为约30nm。 The dispersed phase (polymer / active compound particles) has a spherical structure and an average diameter of the light scattering measurement was about 30nm.

    II.5配制实施例3:通过喷嘴沉淀增溶唑菌胺酯(通用程序4)使用通用程序4配制唑菌胺酯。 II.5 Formulation Example 3: solubilizing the precipitate through a nozzle pyraclostrobin (General Procedure 4) using General Procedure 4 formulated pyraclostrobin. 所得活性化合物组合物均匀,基本视觉上透明,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, the basic visualizing transparent, 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)将10g环戊唑菌(熔点为110-113℃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。 II.6 Formulation Example 4: solubilized metconazole by inversion method (general procedure 2) 10g of metconazole (m.p. 110-113 ℃ solids) from Example 30g and amphiphilic Polymerization Example 1 composition 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,基本视觉上透明,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, the basic visualizing transparent, 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. 分散相(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。 The dispersed phase (polymer / active compound particles) having a spherical structure and an average diameter of the light scattering measurement was 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1 Table 1

    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)将10g维生素A乙酸酯和30g来自实施例1的两亲性聚合物组合物一起溶于100g THF中。 It was dissolved in 100g THF together by inversion method solubilizing vitamin A acetate (general procedure 2) to 10g and 30g of vitamin A acetate from Example amphiphilic polymer composition of Example 1: II.7 Formulation Example 5 in. 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,基本视觉上透明,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, the basic visualizing transparent, 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.

    III 应用测试III.1杀真菌活性的评价根据下列程序比较来自配制实施例1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(Phytophthora infestans)的活性(预防试验,保护性活性):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)。 III.1 III Application Testing Evaluation and comparison of fungicidal activity according to the following procedure from two commercially available aqueous formulations of the active compound composition of Example 1 and the same active compound pyraclostrobin is formulated to implement in the greenhouse pathogenicity on tomato Phytophthora (Phytophthora infestans) activity (prevention trial, protective activity): using tap the active compound formulation diluted to the desired concentration of active compound (4-250ppm). 使用体积为25ml的喷雾舱施用于西红柿植物上,这对应于水的量为500l/ha,该量是实践中常用的量。 A volume of 25ml spray tanks applied to the tomato plant, the amount of which corresponds to the water of 500l / ha, this amount is common practice amounts. 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18-20℃和90%相对大气湿度的温室中。 The test plants are kept at 18-20 ℃ 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 on tomato -5 days after infection [%] as a function of the content of the active compound

    1)EC配制剂23.5重量%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,在67.1重量%芳族溶剂中。 1) EC formulation 23.5 wt% pyraclostrobin, 4.7% by weight of an anionic wetting agent, and 4.7% by weight of a nonionic wetting agent, 67.1 wt.% In an aromatic solvent.

    Classifications
    International ClassificationC08G18/28, C08G18/78, C08G18/75, A01N25/04, C08L75/04, C08G18/62, C08L33/06, C08G18/38, A01N25/30
    Cooperative ClassificationC08L33/06, C08G18/3876, C08G18/283, C08L75/04, A01N25/30, A01N25/04, C08G18/7831
    European ClassificationC08L75/04, C08G18/78B4F, C08G18/28D5F, A01N25/04, A01N25/30, C08G18/38H30
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