WO2018040863A1 - Zinc (meth)acrylate-silicon copolymer for self-polishing antifouling paint and preparation therefor - Google Patents

Zinc (meth)acrylate-silicon copolymer for self-polishing antifouling paint and preparation therefor Download PDF

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WO2018040863A1
WO2018040863A1 PCT/CN2017/096470 CN2017096470W WO2018040863A1 WO 2018040863 A1 WO2018040863 A1 WO 2018040863A1 CN 2017096470 W CN2017096470 W CN 2017096470W WO 2018040863 A1 WO2018040863 A1 WO 2018040863A1
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meth
acrylate
zinc
solvent
self
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PCT/CN2017/096470
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French (fr)
Chinese (zh)
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李春光
刘轶龙
苏雅丽
方大庆
王胜龙
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厦门双瑞船舶涂料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters

Definitions

  • the invention relates to the technical field of marine antifouling coatings, in particular to a zinc (meth)acrylate zinc-silicon copolymer for self-polishing antifouling paint and a preparation method thereof.
  • the release of the antifouling agent in the antifouling coating depends on the hydrolysis of the matrix antifouling resin, and the most commonly used matrix resin is a metal-based copolymer which can undergo ion exchange or a polymer of hydrolyzable silyl (meth)acrylate.
  • No. 5,795,374 discloses polymers containing silyl (meth)acrylate for use in marine antifouling coatings, but the polymer film produced has a very low hydrolysis rate. It cannot be applied to a “highly polluted environment” at all. “Highly polluted environment” refers to eutrophic sea areas, such as the inner sea or the national waters that allow ships to park in such environments, or sea areas where ships are frequently parked or at low speeds.
  • Chinese patent CN103131289B is a matrix resin obtained by copolymerizing organosilyl acrylate and fluorine-containing (meth) acrylate to obtain self-polishing property and low surface property, hydrophobic oil, but antifouling coating prepared by using the resin matrix. It is also heavily dependent on the speed of the ship.
  • a marine antifouling coating is disclosed in EP 0 802 243 B1.
  • the base resin used in the antifouling coating is an organosilyl acrylate based polymer and A rosin composition for improving the rate of hydrolysis thereof, but a coating using the matrix resin of the composition causes a new problem after a long period of application, and the physical and mechanical properties are poor, and the surface of the coating may be cracked and peeled off. .
  • the present invention provides a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint, and a preparation method thereof, the copolymer side chain containing zinc acrylate which can be used for ion exchange
  • the structure and structure of the hydrolyzable silane ester combine the advantages of zinc acrylate and organosilyl polymer, and have high hydrolysis rate and excellent toughness.
  • the structural formula of the zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint provided by the present invention is as follows:
  • R 1 , R 2 and R 3 represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 10;
  • R 4 , R 5 and R 6 represent H or CH 3 ;
  • X, Y represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 16;
  • n in the structural formula is 1 to 1000;
  • n 0 to 2000
  • k is from 1 to 1000.
  • n in the structural formula is 10 to 100;
  • n 20 to 200
  • k 20 to 200.
  • the present invention also provides a method for preparing a zinc (meth)acrylate-silicon copolymer for self-polishing antifouling paint according to any of the above, comprising the steps of:
  • Step 1 synthesizing zinc (meth) acrylate monomer, the raw materials thereof include: zinc oxide, (meth)acrylic acid monomer, monocarboxylic acid and A solvent;
  • Step 2 synthesizing a zinc (meth) acrylate-silicon copolymer, the raw materials thereof include: the zinc (meth) acrylate monomer, the silyl (meth) acrylate, the (meth) acrylate synthesized in the first step , B solvent and initiator;
  • the A solvent is a combination of any one or more of a hydrocarbon solvent, an alcohol solvent, a ketone solvent, or an ether solvent;
  • the B solvent is an aromatic hydrocarbon solvent, an ester solvent, a ketone A composition of any one or more of a solvent and an ether solvent.
  • the weight fraction of each raw material for synthesizing the zinc (meth) acrylate monomer is as follows: 5 to 25 parts of zinc oxide, 10 to 30 parts of (meth)acrylic acid monomer, and 15 to 25 parts of monocarboxylic acid. , A solvent 21 to 50 parts.
  • the method for synthesizing the zinc (meth) acrylate monomer is as follows: the solvent A and the zinc oxide are charged into a preparation container, and the container is heated to a temperature of 60 ° C to 110 ° C, and then in a preparation container within 3 to 6 hours. Evenly dropping the composition of the (meth)acrylic monomer and the monocarboxylic acid and maintaining the heating to obtain a colorless transparent substance, that is, synthesizing a zinc (meth) acrylate monomer; specifically, the preparation container is a four-necked flask or Other commonly used preparation containers.
  • the zinc oxide is primary zinc oxide, and the purity is 99%;
  • the (meth)acrylic monomer is selected from any one of methacrylic acid, itaconic acid, and acrylic acid.
  • the monocarboxylic acid is isostearic acid.
  • the monocarboxylic acid is a combination of isostearic acid and another monocarboxylic acid; wherein the other monocarboxylic acid is any one of formic acid, acetic acid, propionic acid, octanoic acid, and benzoic acid.
  • the weight fraction of each raw material of the synthetic zinc (meth) acrylate-silicon copolymer is as follows: 10 to 20 parts of the zinc (meth) acrylate monomer synthesized in the first step, (A) 6 to 25 parts of silyl acrylate, 20 to 40 parts of (meth) acrylate, 20 to 40 parts of B solvent, and 1 to 5 parts of initiator.
  • the method for synthesizing the zinc (meth) acrylate-silicon copolymer is as follows: adding a solvent B to the preparation vessel, heating the preparation vessel to 80 to 115 ° C, and then within 5 to 10 hours, to The mixture of the (meth)acrylic acid zinc monomer, the (meth) acrylate, the (meth)acrylic acid silyl ester and the initiator is uniformly dropped into the preparation vessel and kept heated; after the dropwise addition is completed, at 1 to Continue to add 0.1-0.8 parts of initiator in 2 hours, and then continue to add 0.1-0.8 parts of initiator to fully react the last remaining monomer to obtain a colorless transparent substance, ie, synthesize zinc (meth)acrylate-silicon. Copolymer.
  • the initiator is any one of benzoyl peroxide, benzoyl peroxide, terephthalate peroxide, azobisisobutyronitrile, azobisisoheptanenitrile or azobisisovaleronitrile. Species or any combination of the two.
  • silyl (meth)acrylate is as follows:
  • R is H or CH 3 ;
  • R 1 , R 2 and R 3 represent an alkyl group having a carbon number of 1 to 10, a cycloalkyl group, an aryl group or an aralkyl group.
  • silyl (meth)acrylate is trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethyl methacrylate
  • the (meth) acrylate is any one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and isooctyl acrylate.
  • the (meth) acrylate is a hydroxylated monomer; the hydroxylated monomer is selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( Any of 2-hydroxybutyl methacrylate.
  • the hydrocarbon solvent is any one of toluene, xylene, and trimethylbenzene.
  • the alcohol solvent is a combination of any one or two of n-butanol, isobutanol, and phenylethyl alcohol
  • the ketone solvent is methyl ethyl ketone, methyl ethyl ketone, and A composition of either or both of cyclohexanone.
  • the aromatic hydrocarbon solvent is any one or a combination of two of toluene and xylene
  • the ketone solvent is any one of methyl ethyl ketone, methyl ethyl ketone, and cyclohexanone.
  • the ester solvent is a combination of either or both of butyl acetate and ethyl acetate
  • the ether solvent is one of propylene glycol methyl ether and propylene glycol diethyl ether.
  • the invention provides a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint and a preparation method thereof.
  • the prepared zinc (meth) acrylate-silicon copolymer side chain contains a zinc-based acrylate structure and a hydrolyzable silane ester structure which can be used for ion exchange, and the copolymer combines zinc acrylate and silyl (meth) acrylate.
  • the advantage of the polymer is that it can be hydrolyzed at a predetermined rate, and the rate of hydrolysis of the zinc (meth) acrylate-silicon copolymer can be adjusted by the ratio of the zinc (meth) acrylate monomer to the silyl (meth) acrylate.
  • the copolymer has excellent toughness.
  • 1 is a comparison chart of weight loss ratios of a zinc (meth)acrylate-silicon copolymer and a (meth)acrylic acid silyl ester polymer as a comparative sample according to the present invention.
  • Table 1 shows four examples provided by the present invention, wherein each raw material is proportioned by weight, and the specifications of each raw material are industrial grade.
  • Step 1 synthesizing zinc (meth) acrylate monomer, the raw materials thereof include: zinc oxide, (meth)acrylic acid monomer, monocarboxylic acid and A solvent;
  • the method for synthesizing the zinc (meth) acrylate monomer is as follows: the A solvent and the zinc oxide are placed in a preparation vessel, and the four-necked flask is heated to 60 ° C to 110 ° C, and then the preparation vessel is in a range of 3 to 6 hours. The composition of the (meth)acrylic monomer and the monocarboxylic acid is uniformly dropped into the inside and kept heated to obtain a colorless transparent substance, that is, a zinc (meth) acrylate monomer is synthesized.
  • Step 2 synthesizing a zinc (meth) acrylate-silicon copolymer, the raw materials thereof include: the zinc (meth) acrylate monomer, the silyl (meth) acrylate, the (meth) acrylate synthesized in the first step , B solvent and initiator;
  • a B solvent is added to a four-necked flask, and the container is heated to 80 to 115 ° C, and then the zinc (meth) acrylate monomer is uniformly dropped into the four-necked flask within 5 to 10 hours.
  • a mixture of acrylate, silyl (meth) acrylate and initiator is kept warm; after the addition is completed, 0.1 to 0.8 parts of the initiator is further added within 1 to 2 hours, and further 0.1 to 0.1 0.8 parts of the initiator can sufficiently react the last remaining monomer to obtain a colorless transparent substance, that is, a zinc (meth) acrylate-silicon copolymer is synthesized.
  • the sample to be tested and the comparative sample were respectively coated on a 2.5 cm ⁇ 6 cm glass slide with a coating area of 2.5 cm ⁇ 6 cm, and the sample to be tested was placed in a dry 30° C. environment to be coated. It is completely dry, the dry film thickness is kept at about 100 ⁇ m, and it is tested in flowing artificial seawater (25 ° C), and the hydrolysis rate is expressed by the weight loss rate per unit time of the copolymer, wherein:
  • Weight loss rate (100 ⁇ (W 0 - W dry )) / W 0 ,
  • W 0 is the total dry film weight before the test
  • W dry is the total dry film weight after a certain test time of the film.
  • the relationship between the weight loss rate and time is plotted as a line graph, that is, the obtained hydrolysis rate test results are shown in Fig. 1.
  • the coating areas of the five experimental samples are the same, and the weight loss rate per unit time is expressed as the hydrolysis rate, and the slope of the image is As a result of the hydrolysis rate, it can be seen from the slope of the image that the image of the four zinc (meth) acrylate-silicon copolymers provided by the present invention is almost straight in a period of 10 weeks.
  • the line indicates that the hydrolysis rate is stable, and the comparative sample (silto) methacrylate polymer has an image of a broken line, indicating that the hydrolysis rate is unstable; within four weeks, the four (methyl) groups provided by the present invention
  • the image slope of the zinc acrylate-silicon copolymer embodiment is larger than the image slope of the comparative sample (meth) acrylate polymer, which can indicate the zinc (meth) acrylate-silicon copolymer and the comparative sample provided by the present invention.
  • the hydrolysis rate is significantly improved.
  • the hydrolysis rates in Comparative Examples 1 to 4 are different, and the hydrolysis rate of the zinc (meth)acrylate-silicon copolymer provided by the present invention can be further adjusted by adjusting the ratio of the components in the raw materials. Specifically, the hydrolysis rate can be adjusted by adjusting the ratio of the zinc (meth) acrylate monomer to the silyl (meth) acrylate.
  • the zinc (meth) acrylate-silicon copolymer and the comparative sample (meth) acrylate silyl polymer were tested in accordance with the national standard GB/T 6742-2007 "Color paint and varnish bending test", the test results are shown in Table 2. Shown.

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Abstract

A zinc (meth)acrylate-silicon copolymer for self-polishing antifouling paint and preparation therefor relate to the technical field of marine antifouling paint. The preparation method comprises the steps: synthesizing zinc acrylate monomers, the raw materials thereof comprising zinc oxide, (meth)acrylic acid monomer, monocarboxylic acid, and A solvent; synthesizing the zinc (meth)acrylate-silicon copolymer, the raw materials thereof comprising zinc (meth)acrylate monomer, silyl (meth)acrylate, (meth)acrylate, B solvent and an initiator. The copolymer comprises a zinc-based acrylate structure available for ion exchange and a hydrolysable silane ester structure in side chains, integrates the advantages of zinc acrylate and silyl (meth)acrylate polymer, has a high, stable and adjustable hydrolysis speed and very good toughness.

Description

[根据细则37.2由ISA制定的发明名称]　自抛光防污漆用的（甲基）丙烯酸锌-硅共聚物及其制备方法[Invention name established by ISA according to Rule 37.2] Zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint and preparation method thereof
交叉引用cross reference
本申请引用于2016年08月30日递交的名称为“一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物及其制备方法”的第201610769067.0号中国专利申请，其通过引用被全部并入本申请。This application cites the Chinese Patent Application No. 201610769067.0, filed on Aug. 30, 2016, entitled "Zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paints and its preparation method", which is incorporated by reference. It is fully incorporated into this application.
技术领域Technical field
本发明涉及海洋防污涂料技术领域，特别是指一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物及其制备方法。The invention relates to the technical field of marine antifouling coatings, in particular to a zinc (meth)acrylate zinc-silicon copolymer for self-polishing antifouling paint and a preparation method thereof.
背景技术Background technique
防污涂料中防污剂的释放依赖于基体防污树脂的水解，最常用的基体树脂是可发生离子交换的金属基共聚物或者是可水解的(甲基)丙烯酸甲硅烷酯的聚合物。The release of the antifouling agent in the antifouling coating depends on the hydrolysis of the matrix antifouling resin, and the most commonly used matrix resin is a metal-based copolymer which can undergo ion exchange or a polymer of hydrolyzable silyl (meth)acrylate.
US5795374公开了由船舶防污涂料用的含有(甲基)丙烯酸甲硅烷酯的聚合物，但是所制备的聚合物薄膜水解速率非常低。根本无法应用于“高污染环境”中。“高污染环境”是指富营养的海区，如内海或者允许船舶停在这种环境的国家海域，或者船舶频繁停泊或船舶低速行驶的海域。No. 5,795,374 discloses polymers containing silyl (meth)acrylate for use in marine antifouling coatings, but the polymer film produced has a very low hydrolysis rate. It cannot be applied to a “highly polluted environment” at all. “Highly polluted environment” refers to eutrophic sea areas, such as the inner sea or the national waters that allow ships to park in such environments, or sea areas where ships are frequently parked or at low speeds.
EP1127902中介绍了(甲基)丙烯酸甲硅烷酯的聚合物在PH＝13的碱溶液中的水解速度大约是在0到很小的范围之间，而且几乎不依赖可水解硅基团的含量，根本无法满足高抛光速率用的防污涂料需求。 EP 1 127 902 describes that the hydrolysis rate of a polymer of silyl (meth) acrylate in an alkaline solution of pH = 13 is in the range of from about 0 to a small extent, and is almost independent of the content of hydrolyzable silicon groups. The need for antifouling coatings for high polishing rates is simply not met.
中国专利CN103131289B中以有机甲硅烷基丙烯酸酯和含氟(甲基)丙烯酸酯共聚来获得自抛光性能及低表面性能的基体树脂，憎水憎油，但是以此树脂基体制备的防污涂料又严重依赖船速。Chinese patent CN103131289B is a matrix resin obtained by copolymerizing organosilyl acrylate and fluorine-containing (meth) acrylate to obtain self-polishing property and low surface property, hydrophobic oil, but antifouling coating prepared by using the resin matrix. It is also heavily dependent on the speed of the ship.
为了提高(甲基)丙烯酸甲硅烷酯的聚合物水解速率，EP0802243B1中公开了一种船舶防污涂料，这种防污涂料采用的基体树脂是一种有机甲硅烷基丙烯酸酯基聚合物和一种用于改善其水解速率的松香组合物，但是使用这种组合物基体树脂的涂料经过长时间应用后，带来了新的问题，其物理机械性能不佳，涂料表面会发生破裂和剥离。In order to increase the rate of polymer hydrolysis of silyl (meth) acrylate, a marine antifouling coating is disclosed in EP 0 802 243 B1. The base resin used in the antifouling coating is an organosilyl acrylate based polymer and A rosin composition for improving the rate of hydrolysis thereof, but a coating using the matrix resin of the composition causes a new problem after a long period of application, and the physical and mechanical properties are poor, and the surface of the coating may be cracked and peeled off. .
为了改善共聚物性能，公布号为US5436284的专利中建议使用三烷基甲硅烷基单体和醚共聚单体的共聚物。公布号为EP0714957的专利建议使用三烷基单体和含有半缩醛酯的共聚单体的共聚物。In order to improve the properties of the copolymer, it is proposed to use a copolymer of a trialkylsilyl monomer and an ether comonomer in the publication US Pat. No. 5,436,284. The publication No. EP0714957 proposes the use of a copolymer of a trialkyl monomer and a acetal containing a acetal ester.
发明内容Summary of the invention
本发明为了克服现有技术的缺点，提供一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物及其制备方法，该共聚物侧链含有可用于离子交换的锌基丙烯酸酯结构和可水解的硅烷酯的结构，综合了丙烯酸锌及有机甲硅烷基聚合物的优点，其水解速度高，并且韧性极佳。In order to overcome the shortcomings of the prior art, the present invention provides a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint, and a preparation method thereof, the copolymer side chain containing zinc acrylate which can be used for ion exchange The structure and structure of the hydrolyzable silane ester combine the advantages of zinc acrylate and organosilyl polymer, and have high hydrolysis rate and excellent toughness.
本发明提供的自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物结构式如下所示： The structural formula of the zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint provided by the present invention is as follows:
Figure PCTCN2017096470-appb-000001
Figure PCTCN2017096470-appb-000001
所述结构式中R1，R2，R3代表碳数为1～10的烷基、环烷基、芳基或芳烷基；In the formula, R 1 , R 2 and R 3 represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 10;
所述结构式中R4，R5，R6代表H或者CH3；In the formula, R 4 , R 5 and R 6 represent H or CH 3 ;
所述结构式中X，Y代表碳数为1～16的烷基、环烷基、芳基或芳烷基；In the formula, X, Y represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 16;
所述结构式中的m为1～1000；m in the structural formula is 1 to 1000;
所述结构式中n为0～2000；In the structural formula, n is 0 to 2000;
所述结构式中k为1～1000。In the structural formula, k is from 1 to 1000.
进一步地，所述结构式中的m为10～100；Further, m in the structural formula is 10 to 100;
所述结构式中n为20～200；In the structural formula, n is 20 to 200;
所述结构式中k为20～200。In the structural formula, k is 20 to 200.
进一步地，所述结构式中m:k＝1:5～4:1。Further, in the structural formula, m:k=1:5 to 4:1.
本发明还提供一种如上任意所述的自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，包括以下步骤：The present invention also provides a method for preparing a zinc (meth)acrylate-silicon copolymer for self-polishing antifouling paint according to any of the above, comprising the steps of:
步骤一、合成(甲基)丙烯酸锌单体，其原料包括：氧化锌、(甲基)丙烯酸单体、一元羧酸和A溶剂；Step 1: synthesizing zinc (meth) acrylate monomer, the raw materials thereof include: zinc oxide, (meth)acrylic acid monomer, monocarboxylic acid and A solvent;
步骤二、合成(甲基)丙烯酸锌-硅共聚物，其原料包括：步骤一中合成的所述(甲基)丙烯酸锌单体、(甲基)丙烯酸甲硅烷酯、(甲基)丙烯酸酯、B溶剂和引发剂； Step 2, synthesizing a zinc (meth) acrylate-silicon copolymer, the raw materials thereof include: the zinc (meth) acrylate monomer, the silyl (meth) acrylate, the (meth) acrylate synthesized in the first step , B solvent and initiator;
其中，所述A溶剂是烃类溶剂、醇类溶剂、酮类溶剂、或醚类溶剂的任一种或多种的组合物；所述B溶剂是芳香烃类溶剂、酯类溶剂、酮类溶剂、醚类溶剂中的任一种或多种的组合物。Wherein the A solvent is a combination of any one or more of a hydrocarbon solvent, an alcohol solvent, a ketone solvent, or an ether solvent; the B solvent is an aromatic hydrocarbon solvent, an ester solvent, a ketone A composition of any one or more of a solvent and an ether solvent.
进一步地，步骤一中，合成(甲基)丙烯酸锌单体的各原料重量份数如下：氧化锌5～25份、(甲基)丙烯酸单体10～30份、一元羧酸15～25份、A溶剂21～50份。Further, in the first step, the weight fraction of each raw material for synthesizing the zinc (meth) acrylate monomer is as follows: 5 to 25 parts of zinc oxide, 10 to 30 parts of (meth)acrylic acid monomer, and 15 to 25 parts of monocarboxylic acid. , A solvent 21 to 50 parts.
进一步地，所述(甲基)丙烯酸锌单体的合成方法如下：将A溶剂和氧化锌装入制备容器内，加热制备容器至60℃～110℃,之后在3～6小时内向制备容器内均匀滴入(甲基)丙烯酸单体和一元羧酸的组合物并保持加热，得到无色透明物质，即合成出(甲基)丙烯酸锌单体；具体而言，制备容器为四口烧瓶或其它常用的制备容器。Further, the method for synthesizing the zinc (meth) acrylate monomer is as follows: the solvent A and the zinc oxide are charged into a preparation container, and the container is heated to a temperature of 60 ° C to 110 ° C, and then in a preparation container within 3 to 6 hours. Evenly dropping the composition of the (meth)acrylic monomer and the monocarboxylic acid and maintaining the heating to obtain a colorless transparent substance, that is, synthesizing a zinc (meth) acrylate monomer; specifically, the preparation container is a four-necked flask or Other commonly used preparation containers.
进一步地，所述氧化锌为一级氧化锌，纯度为99％；Further, the zinc oxide is primary zinc oxide, and the purity is 99%;
所述(甲基)丙烯酸单体选自甲基丙烯酸、衣康酸和丙烯酸中的任一种。The (meth)acrylic monomer is selected from any one of methacrylic acid, itaconic acid, and acrylic acid.
进一步地，所述一元羧酸为异硬脂酸。Further, the monocarboxylic acid is isostearic acid.
进一步地，所述一元羧酸为异硬脂酸与其它一元羧酸的组合物；其中，所述其它一元羧酸为甲酸、乙酸、丙酸、辛酸、苯甲酸中的任一种。Further, the monocarboxylic acid is a combination of isostearic acid and another monocarboxylic acid; wherein the other monocarboxylic acid is any one of formic acid, acetic acid, propionic acid, octanoic acid, and benzoic acid.
进一步地，所述异硬脂酸与其它一元羧酸的组合物按重量份的配制比例为异硬脂酸:其它一元羧酸＝1：0～1。Further, the composition of the isostearic acid and the other monocarboxylic acid is isostearic acid in a ratio by weight: other monocarboxylic acid = 1:0 to 1.
进一步地，步骤二中，所述合成(甲基)丙烯酸锌-硅共聚物的各原料重量份数如下：步骤一中合成的所述(甲基)丙烯酸锌单体10～20份，(甲基)丙烯酸甲硅烷酯6～25份，(甲基)丙烯酸酯20～40份，B溶剂20～40份，引发剂1～5份。Further, in the second step, the weight fraction of each raw material of the synthetic zinc (meth) acrylate-silicon copolymer is as follows: 10 to 20 parts of the zinc (meth) acrylate monomer synthesized in the first step, (A) 6 to 25 parts of silyl acrylate, 20 to 40 parts of (meth) acrylate, 20 to 40 parts of B solvent, and 1 to 5 parts of initiator.
进一步地，所述(甲基)丙烯酸锌-硅共聚物的合成方法如下：向制备容器内加入B溶剂，加热制备容器至80～115℃，之后在5～10小时内，向 制备容器内均匀滴入所述(甲基)丙烯酸锌单体、(甲基)丙烯酸酯、(甲基)丙烯酸甲硅烷酯和引发剂的混合液并保持加热；滴加完毕后，于1～2小时内继续再加入0.1～0.8份引发剂，可继续再加入0.1～0.8份引发剂能够使最后残留的单体充分反应，得到无色透明物质，即合成出(甲基)丙烯酸锌-硅共聚物。Further, the method for synthesizing the zinc (meth) acrylate-silicon copolymer is as follows: adding a solvent B to the preparation vessel, heating the preparation vessel to 80 to 115 ° C, and then within 5 to 10 hours, to The mixture of the (meth)acrylic acid zinc monomer, the (meth) acrylate, the (meth)acrylic acid silyl ester and the initiator is uniformly dropped into the preparation vessel and kept heated; after the dropwise addition is completed, at 1 to Continue to add 0.1-0.8 parts of initiator in 2 hours, and then continue to add 0.1-0.8 parts of initiator to fully react the last remaining monomer to obtain a colorless transparent substance, ie, synthesize zinc (meth)acrylate-silicon. Copolymer.
其中，所述引发剂是过氧化苯甲酰、过氧化苯甲酰叔丁酯、过氧化甲乙酮、偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈中的任一种或任意两种的组合物。Wherein the initiator is any one of benzoyl peroxide, benzoyl peroxide, terephthalate peroxide, azobisisobutyronitrile, azobisisoheptanenitrile or azobisisovaleronitrile. Species or any combination of the two.
进一步地，所述(甲基)丙烯酸甲硅烷酯结构式如下：Further, the structural formula of the silyl (meth)acrylate is as follows:
Figure PCTCN2017096470-appb-000002
Figure PCTCN2017096470-appb-000002
上述结构式中R为H或者CH3；R1，R2，R3代表碳数为1-10的烷基、环烷基、芳基、芳烷基。In the above formula, R is H or CH 3 ; R 1 , R 2 and R 3 represent an alkyl group having a carbon number of 1 to 10, a cycloalkyl group, an aryl group or an aralkyl group.
进一步地，所述(甲基)丙烯酸甲硅烷酯是丙烯酸三甲基甲硅烷酯、丙烯酸三乙基甲硅烷酯、丙烯酸三异丙基甲硅烷酯、丙烯酸三丁基甲硅烷酯、甲基丙烯酸三甲基甲硅烷酯、甲基丙烯酸三乙基甲硅烷酯、甲基丙烯酸三异丙基甲硅烷酯、甲基丙烯酸三丁基甲硅烷酯的任意一种或多种的组合物。Further, the silyl (meth)acrylate is trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethyl methacrylate A composition of any one or more of silyl silyl ester, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate.
进一步地，所述(甲基)丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、丙烯酸异辛酯中任一种或多种组合物。Further, the (meth) acrylate is any one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and isooctyl acrylate.
进一步地，所述(甲基)丙烯酸酯为羟基化的单体；所述羟基化的单体选自(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸2-羟基丁酯中的任一种。Further, the (meth) acrylate is a hydroxylated monomer; the hydroxylated monomer is selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( Any of 2-hydroxybutyl methacrylate.
进一步地，所述A溶剂中，烃类溶剂是甲苯、二甲苯、三甲苯中的任一 种或两种的组合物，所述醇类溶剂是正丁醇、异丁醇、苯乙醇中的任一种或两种的组合物，所述酮类溶剂是甲基乙基酮、丁酮和环己酮中的任一种或两种的组合物。Further, in the A solvent, the hydrocarbon solvent is any one of toluene, xylene, and trimethylbenzene. Or a combination of two or more, the alcohol solvent is a combination of any one or two of n-butanol, isobutanol, and phenylethyl alcohol, and the ketone solvent is methyl ethyl ketone, methyl ethyl ketone, and A composition of either or both of cyclohexanone.
进一步地，B溶剂中，所述芳香烃类溶剂是甲苯、二甲苯的任一种或两种的组合物，所述酮类溶剂是甲基乙基酮、丁酮、环己酮中的任一种或两种的组合物，所述酯类溶剂是醋酸丁酯、乙酸乙酯的任一种或两种的组合物；所述醚类溶剂是丙二醇甲醚，丙二醇乙醚中的一种。Further, in the B solvent, the aromatic hydrocarbon solvent is any one or a combination of two of toluene and xylene, and the ketone solvent is any one of methyl ethyl ketone, methyl ethyl ketone, and cyclohexanone. One or two of the compositions, the ester solvent is a combination of either or both of butyl acetate and ethyl acetate; and the ether solvent is one of propylene glycol methyl ether and propylene glycol diethyl ether.
本发明提供了一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物及其制备方法。所制备的(甲基)丙烯酸锌-硅共聚物侧链含有可用于离子交换的锌基丙烯酸酯结构和可水解的硅烷酯结构，该共聚物综合了丙烯酸锌及(甲基)丙烯酸甲硅烷酯聚合物的优点，能以预定速度水解，并且通过(甲基)丙烯酸锌单体和(甲基)丙烯酸甲硅烷酯的比例，可以调节(甲基)丙烯酸锌-硅共聚物的水解速度，同时该共聚物具有极佳的韧性。The invention provides a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint and a preparation method thereof. The prepared zinc (meth) acrylate-silicon copolymer side chain contains a zinc-based acrylate structure and a hydrolyzable silane ester structure which can be used for ion exchange, and the copolymer combines zinc acrylate and silyl (meth) acrylate. The advantage of the polymer is that it can be hydrolyzed at a predetermined rate, and the rate of hydrolysis of the zinc (meth) acrylate-silicon copolymer can be adjusted by the ratio of the zinc (meth) acrylate monomer to the silyl (meth) acrylate. The copolymer has excellent toughness.
附图说明DRAWINGS
图1为本发明提供的(甲基)丙烯酸锌-硅共聚物与(甲基)丙烯酸甲硅烷酯聚合物作为对比样的失重率对比图。1 is a comparison chart of weight loss ratios of a zinc (meth)acrylate-silicon copolymer and a (meth)acrylic acid silyl ester polymer as a comparative sample according to the present invention.
具体实施方式detailed description
以下用实施例对本发明进一步说明。表1为本发明提供的四个实施例，其中各原料均按照重量份数配比，各原料所采用的规格均为工业级。 The invention is further illustrated by the following examples. Table 1 shows four examples provided by the present invention, wherein each raw material is proportioned by weight, and the specifications of each raw material are industrial grade.
表1实施例Table 1 embodiment
Figure PCTCN2017096470-appb-000003
Figure PCTCN2017096470-appb-000003
本发明按照以上实施例提供的各原料重量配比，并按照以下制备方法：The invention according to the weight ratio of each raw material provided by the above examples, and according to the following preparation method:
步骤一、合成(甲基)丙烯酸锌单体，其原料包括：氧化锌、(甲基)丙烯酸单体、一元羧酸和A溶剂；Step 1: synthesizing zinc (meth) acrylate monomer, the raw materials thereof include: zinc oxide, (meth)acrylic acid monomer, monocarboxylic acid and A solvent;
其中，(甲基)丙烯酸锌单体的合成方法如下：将A溶剂和氧化锌装入制备容器内，加热四口烧瓶至60℃～110℃,之后在3～6小时内向制备容器 内均匀滴入(甲基)丙烯酸单体和一元羧酸的组合物并保持加热，得到无色透明物质，即合成出(甲基)丙烯酸锌单体。The method for synthesizing the zinc (meth) acrylate monomer is as follows: the A solvent and the zinc oxide are placed in a preparation vessel, and the four-necked flask is heated to 60 ° C to 110 ° C, and then the preparation vessel is in a range of 3 to 6 hours. The composition of the (meth)acrylic monomer and the monocarboxylic acid is uniformly dropped into the inside and kept heated to obtain a colorless transparent substance, that is, a zinc (meth) acrylate monomer is synthesized.
步骤二、合成(甲基)丙烯酸锌-硅共聚物，其原料包括：步骤一中合成的所述(甲基)丙烯酸锌单体、(甲基)丙烯酸甲硅烷酯、(甲基)丙烯酸酯、B溶剂和引发剂； Step 2, synthesizing a zinc (meth) acrylate-silicon copolymer, the raw materials thereof include: the zinc (meth) acrylate monomer, the silyl (meth) acrylate, the (meth) acrylate synthesized in the first step , B solvent and initiator;
具体地，向四口烧瓶内加入B溶剂，加热制备容器至80～115℃，之后在5～10小时内，向四口烧瓶内均匀滴入所述(甲基)丙烯酸锌单体、(甲基)丙烯酸酯、(甲基)丙烯酸甲硅烷酯和引发剂的混合液并保持加热；滴加完毕后，于1～2小时内继续再加入0.1～0.8份引发剂，可继续再加入0.1～0.8份引发剂能够使最后残留的单体充分反应，得到无色透明物质，即合成出(甲基)丙烯酸锌-硅共聚物。Specifically, a B solvent is added to a four-necked flask, and the container is heated to 80 to 115 ° C, and then the zinc (meth) acrylate monomer is uniformly dropped into the four-necked flask within 5 to 10 hours. a mixture of acrylate, silyl (meth) acrylate and initiator is kept warm; after the addition is completed, 0.1 to 0.8 parts of the initiator is further added within 1 to 2 hours, and further 0.1 to 0.1 0.8 parts of the initiator can sufficiently react the last remaining monomer to obtain a colorless transparent substance, that is, a zinc (meth) acrylate-silicon copolymer is synthesized.
将以上方法制备的四个实施例和现有技术中防污漆常用的(甲基)丙烯酸甲硅烷酯聚合物作为对比样品，进行共聚物水解率测试，水解率测试的方法为：The four examples prepared by the above method and the commonly used silyl (meth)acrylate polymer of the antifouling paint in the prior art were used as comparative samples to carry out the copolymer hydrolysis rate test, and the hydrolysis rate test method was as follows:
将待测的实施例和对比样品分别涂布在2.5cm×6cm的载玻片上，涂布面积为2.5cm×6cm，将待测的试样放在干燥的30℃环境中放置，待涂膜完全干燥，干膜厚度保持在100μm左右，放置进流动的人工海水(25℃)中测试，以共聚物的单位时间的失重率表示水解速率，其中：The sample to be tested and the comparative sample were respectively coated on a 2.5 cm×6 cm glass slide with a coating area of 2.5 cm×6 cm, and the sample to be tested was placed in a dry 30° C. environment to be coated. It is completely dry, the dry film thickness is kept at about 100 μm, and it is tested in flowing artificial seawater (25 ° C), and the hydrolysis rate is expressed by the weight loss rate per unit time of the copolymer, wherein:
失重率＝(100×(W0-Wdry))/W0，Weight loss rate = (100 × (W 0 - W dry )) / W 0 ,
W0为测试前干膜总重量，Wdry为涂膜经过一定测试时间后，干膜总重量。W 0 is the total dry film weight before the test, and W dry is the total dry film weight after a certain test time of the film.
将失重率与时间的关系绘制成折线图，即得到的水解率测试测试结果如图1所示，五个实验样品的涂装面积相同，单位时间内失重率表示为水解速率，图像的斜率即为水解速率，通过图像的斜率可以看出，在10周时间内，本发明提供的四个(甲基)丙烯酸锌-硅共聚物的实施例图像几乎为一条直 线，说明其水解速率稳定，而对比样品(甲基)丙烯酸甲硅烷酯聚合物得图像为折线形，说明其水解速率不稳定；在10周时间内，本发明提供的四个(甲基)丙烯酸锌-硅共聚物实施例的图像斜率均大于对比样品(甲基)丙烯酸甲硅烷酯聚合物的图像斜率，可以表明本发明提供的(甲基)丙烯酸锌-硅共聚物与对比样品(甲基)丙烯酸甲硅烷酯聚合物相比，其水解速率有显著的提高。此外，对比例1～4中的水解速率不同可以看出，通过调节原料中各组分的配比，可以进一步调节本发明提供的(甲基)丙烯酸锌-硅共聚物水解速率。具体而言可以通过调节(甲基)丙烯酸锌单体和(甲基)丙烯酸甲硅烷酯的比例来调节水解速率。The relationship between the weight loss rate and time is plotted as a line graph, that is, the obtained hydrolysis rate test results are shown in Fig. 1. The coating areas of the five experimental samples are the same, and the weight loss rate per unit time is expressed as the hydrolysis rate, and the slope of the image is As a result of the hydrolysis rate, it can be seen from the slope of the image that the image of the four zinc (meth) acrylate-silicon copolymers provided by the present invention is almost straight in a period of 10 weeks. The line indicates that the hydrolysis rate is stable, and the comparative sample (silto) methacrylate polymer has an image of a broken line, indicating that the hydrolysis rate is unstable; within four weeks, the four (methyl) groups provided by the present invention The image slope of the zinc acrylate-silicon copolymer embodiment is larger than the image slope of the comparative sample (meth) acrylate polymer, which can indicate the zinc (meth) acrylate-silicon copolymer and the comparative sample provided by the present invention. Compared to the silyl acrylate polymer, the hydrolysis rate is significantly improved. Further, it can be seen that the hydrolysis rates in Comparative Examples 1 to 4 are different, and the hydrolysis rate of the zinc (meth)acrylate-silicon copolymer provided by the present invention can be further adjusted by adjusting the ratio of the components in the raw materials. Specifically, the hydrolysis rate can be adjusted by adjusting the ratio of the zinc (meth) acrylate monomer to the silyl (meth) acrylate.
将(甲基)丙烯酸锌-硅共聚物与对比样品(甲基)丙烯酸甲硅烷酯聚合物按照国家标准GB/T 6742-2007《色漆和清漆弯曲试验》进行性能测试，测试结果如表2所示。The zinc (meth) acrylate-silicon copolymer and the comparative sample (meth) acrylate silyl polymer were tested in accordance with the national standard GB/T 6742-2007 "Color paint and varnish bending test", the test results are shown in Table 2. Shown.
表2韧性测试结果Table 2 toughness test results
Figure PCTCN2017096470-appb-000004
Figure PCTCN2017096470-appb-000004
由表2看出，实施例1～4的弯曲性的轴半径均为3mm，而对比样品为6mm，说明与对比样品相比，本发明制备的(甲基)丙烯酸锌-硅共聚物具有更加显著的韧性。As seen from Table 2, the axial radii of the bends of Examples 1 to 4 were both 3 mm, and the comparative sample was 6 mm, indicating that the zinc (meth) acrylate-silicon copolymer prepared by the present invention has a more comparative effect than the comparative sample. Significant resilience.
上述仅为本发明的具体实施方式，但本发明的设计构思并不局限于此，凡利用此构思对本发明进行非实质性的改动，均应属于侵犯本发明保护范围的行为。 The above is only a specific embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modification of the present invention by this concept should be an infringement of the scope of protection of the present invention.

Claims (18)

  1. 一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物，其特征在于：其结构式如下所示：A zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint, characterized in that the structural formula is as follows:
    Figure PCTCN2017096470-appb-100001
    Figure PCTCN2017096470-appb-100001
    所述结构式中R1，R2，R3代表碳数为1～10的烷基、环烷基、芳基或芳烷基；In the formula, R 1 , R 2 and R 3 represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 10;
    所述结构式中R4，R5，R6代表H或者CH3；In the formula, R 4 , R 5 and R 6 represent H or CH 3 ;
    所述结构式中X，Y代表碳数为1～16的烷基、环烷基、芳基或芳烷基；In the formula, X, Y represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 16;
    所述结构式中的m为1～1000；m in the structural formula is 1 to 1000;
    所述结构式中n为0～2000；In the structural formula, n is 0 to 2000;
    所述结构式中k为1～1000。In the structural formula, k is from 1 to 1000.
  2. 根据权利要求1所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物，其特征在于：A zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 1, wherein:
    所述结构式中的m为10～100；m in the structural formula is 10 to 100;
    所述结构式中n为20～200；In the structural formula, n is 20 to 200;
    所述结构式中k为20～200。In the structural formula, k is 20 to 200.
  3. 根据权利要求1或2任一项所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物，其特征在于：所述结构式中m:k＝1:5～4:1。The zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to any one of claims 1 to 2, wherein m:k=1:5-4 in the structural formula: 1.
  4. 一种如权利要求1所述的自抛光防污漆用的(甲基)丙烯酸锌-硅共 聚物的制备方法，其特征在于，包括以下步骤：A zinc (meth)acrylate-silicon composite for self-polishing antifouling paint according to claim 1. A method for preparing a polymer, comprising the steps of:
    步骤一、合成(甲基)丙烯酸锌单体，其原料包括：氧化锌、(甲基)丙烯酸单体、一元羧酸和A溶剂；Step 1: synthesizing zinc (meth) acrylate monomer, the raw materials thereof include: zinc oxide, (meth)acrylic acid monomer, monocarboxylic acid and A solvent;
    步骤二、合成(甲基)丙烯酸锌-硅共聚物，其原料包括：步骤一中合成的所述(甲基)丙烯酸锌单体、(甲基)丙烯酸甲硅烷酯、(甲基)丙烯酸酯、B溶剂和引发剂；Step 2, synthesizing a zinc (meth) acrylate-silicon copolymer, the raw materials thereof include: the zinc (meth) acrylate monomer, the silyl (meth) acrylate, the (meth) acrylate synthesized in the first step , B solvent and initiator;
    其中，所述A溶剂是烃类溶剂、醇类溶剂、酮类溶剂的任一种或多种的组合物；所述B溶剂是芳香烃类溶剂、酯类溶剂、酮类溶剂、醚类溶剂中的任一种或多种的组合物。Wherein the A solvent is a combination of any one or more of a hydrocarbon solvent, an alcohol solvent, and a ketone solvent; the B solvent is an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, or an ether solvent. A composition of any one or more of the following.
  5. 如权利要求4所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，步骤一中，合成(甲基)丙烯酸锌单体的各原料重量份数如下：氧化锌5～25份、(甲基)丙烯酸单体10～30份、一元羧酸15～25份、A溶剂21～50份。A method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein in the first step, each raw material of the zinc (meth) acrylate monomer is synthesized. The parts by weight are as follows: 5 to 25 parts of zinc oxide, 10 to 30 parts of a (meth)acrylic acid monomer, 15 to 25 parts of a monocarboxylic acid, and 21 to 50 parts of an A solvent.
  6. 如权利要求5所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，所述(甲基)丙烯酸锌单体的合成方法如下：将A溶剂和氧化锌装入制备容器内，加热制备容器至60℃～110℃,之后在3～6小时内向制备容器内滴入(甲基)丙烯酸单体和一元羧酸的组合物并保持加热，得到无色透明物质，即合成出(甲基)丙烯酸锌单体。The method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 5, wherein the method for synthesizing the zinc (meth) acrylate monomer is as follows: A solvent and zinc oxide are placed in a preparation vessel, and the vessel is heated to a temperature of 60 ° C to 110 ° C, and then a composition of (meth)acrylic acid monomer and a monocarboxylic acid is dropped into the preparation vessel within 3 to 6 hours and kept heated. A colorless transparent substance is obtained, that is, a zinc (meth) acrylate monomer is synthesized.
  7. 如权利要求6所述一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于：A method for preparing a zinc (meth)acrylate-silicon copolymer for self-polishing antifouling paint according to claim 6, wherein:
    所述(甲基)丙烯酸单体选自甲基丙烯酸、衣康酸和丙烯酸中的任一种。The (meth)acrylic monomer is selected from any one of methacrylic acid, itaconic acid, and acrylic acid.
  8. 如权利要求4所述一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于：所述一元羧酸为异硬脂酸。A method of producing a zinc (meth) acrylate-silicon copolymer for use in a self-polishing antifouling paint according to claim 4, wherein the monocarboxylic acid is isostearic acid.
  9. 如权利要求4所述一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚 物的制备方法，其特征在于：所述一元羧酸为异硬脂酸与其它一元羧酸的组合物；其中，所述其它一元羧酸为甲酸、乙酸、丙酸、辛酸、苯甲酸中的任一种。A (meth)acrylic acid zinc-silicon copolymer for self-polishing antifouling paint according to claim 4. The method for preparing a substance, wherein the monocarboxylic acid is a combination of isostearic acid and another monocarboxylic acid; wherein the other monocarboxylic acid is in formic acid, acetic acid, propionic acid, octanoic acid or benzoic acid Any one.
  10. 如权利要求9所述一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于：所述异硬脂酸与其它一元羧酸的组合物按重量份的配制比例为异硬脂酸:其它一元羧酸＝1：0～1。A method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 9, wherein the composition of the isostearic acid and the other monocarboxylic acid is in parts by weight The formulation ratio is isostearic acid: other monocarboxylic acids = 1:0 to 1.
  11. 如权利要求4所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，步骤二中，所述合成(甲基)丙烯酸锌-硅共聚物的各原料重量份数如下：步骤一中合成的所述(甲基)丙烯酸锌单体10～20份，(甲基)丙烯酸甲硅烷酯6～25份，(甲基)丙烯酸酯20～40份，B溶剂20～40份，引发剂1～5份。A method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein in the second step, the synthesis of zinc (meth) acrylate-silicon copolymer The parts by weight of each raw material are as follows: 10 to 20 parts of the zinc (meth) acrylate monomer synthesized in the first step, 6 to 25 parts of silyl (meth) acrylate, and 20 to (meth) acrylate. 40 parts, 20 to 40 parts of B solvent, and 1 to 5 parts of initiator.
  12. 如权利要求11所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，所述(甲基)丙烯酸锌-硅共聚物的合成方法如下：向制备容器内加入B溶剂，加热制备容器至80～115℃，之后在5～10小时内，向制备容器内滴入所述(甲基)丙烯酸锌单体、(甲基)丙烯酸酯、(甲基)丙烯酸甲硅烷酯和引发剂的混合液并保持加热；得到无色透明物质，即合成出(甲基)丙烯酸锌-硅共聚物。The method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 11, wherein the method for synthesizing the zinc (meth) acrylate-silicon copolymer is as follows Adding B solvent to the preparation vessel, heating the preparation vessel to 80 to 115 ° C, and then dropping the (meth)acrylic acid zinc monomer and (meth) acrylate into the preparation container within 5 to 10 hours. A mixture of silyl (meth) acrylate and an initiator is kept heated; a colorless transparent material is obtained, that is, a zinc (meth) acrylate-silicon copolymer is synthesized.
  13. 如权利要求4所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，所述(甲基)丙烯酸甲硅烷酯结构式如下：The method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein the silyl (meth) acrylate has the following structural formula:
    Figure PCTCN2017096470-appb-100002
    Figure PCTCN2017096470-appb-100002
    上述结构式中R为H或者CH3；R1，R2，R3代表碳数为1-10的烷基、环烷基、芳基、芳烷基。 In the above formula, R is H or CH 3 ; R 1 , R 2 and R 3 represent an alkyl group having a carbon number of 1 to 10, a cycloalkyl group, an aryl group or an aralkyl group.
  14. 如权利要求13所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于：所述(甲基)丙烯酸甲硅烷酯是丙烯酸三甲基甲硅烷酯、丙烯酸三乙基甲硅烷酯、丙烯酸三异丙基甲硅烷酯、丙烯酸三丁基甲硅烷酯、甲基丙烯酸三甲基甲硅烷酯、甲基丙烯酸三乙基甲硅烷酯、甲基丙烯酸三异丙基甲硅烷酯、甲基丙烯酸三丁基甲硅烷酯的任意一种或多种的组合物。A method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 13, wherein the silyl (meth) acrylate is trimethyl methacrylate Silane ester, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, methacrylic acid A composition of any one or more of isopropyl silyl ester and tributyl silyl methacrylate.
  15. 如权利要求4所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，所述(甲基)丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、丙烯酸异辛酯中任一种或多种组合物。The method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein the (meth) acrylate is methyl methacrylate or Any one or more of ethyl acrylate, propyl methacrylate, butyl methacrylate, isooctyl acrylate.
  16. 如权利要求4所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于：所述(甲基)丙烯酸酯为羟基化的单体；所述羟基化的单体选自(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸2-羟基丁酯中的任一种。A method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein the (meth) acrylate is a hydroxylated monomer; The hydroxylated monomer is selected from any one of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate.
  17. 如权利要求4所述一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于：所述A溶剂中，烃类溶剂是甲苯、二甲苯、三甲苯中的任一种或两种的组合物，所述醇类溶剂是正丁醇、异丁醇、苯乙醇中的任一种或两种的组合物，所述酮类溶剂是甲基乙基酮、丁酮和环己酮中的任一种或两种的组合物。A method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein in the solvent A, the hydrocarbon solvent is toluene, xylene, and trimethylbenzene. A composition of any one or two of the following, wherein the alcohol solvent is a combination of any one or two of n-butanol, isobutanol, and phenylethyl alcohol, and the ketone solvent is methyl ethyl ketone. A composition of either or both of methyl ethyl ketone and cyclohexanone.
  18. 如权利要求4所述的一种自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物的制备方法，其特征在于，B溶剂中，所述芳香烃类溶剂是甲苯、二甲苯的任一种或两种的组合物，所述酮类溶剂是甲基乙基酮、丁酮、环己酮中的任一种或两种的组合物，所述酯类溶剂是醋酸丁酯、乙酸乙酯的任一种或两种的组合物；所述醚类溶剂是丙二醇甲醚，丙二醇乙醚中的一种。 The method for preparing a zinc (meth) acrylate-silicon copolymer for self-polishing antifouling paint according to claim 4, wherein in the solvent B, the aromatic hydrocarbon solvent is toluene or xylene. In any one or two of the compositions, the ketone solvent is a combination of any one or two of methyl ethyl ketone, methyl ethyl ketone, and cyclohexanone, and the ester solvent is butyl acetate. Any one or a combination of two of ethyl acetate; the ether solvent is one of propylene glycol methyl ether and propylene glycol diethyl ether.
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