WO2015010390A1 - 一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用 - Google Patents

一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用 Download PDF

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WO2015010390A1
WO2015010390A1 PCT/CN2013/086835 CN2013086835W WO2015010390A1 WO 2015010390 A1 WO2015010390 A1 WO 2015010390A1 CN 2013086835 W CN2013086835 W CN 2013086835W WO 2015010390 A1 WO2015010390 A1 WO 2015010390A1
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methacrylate
main chain
acrylate
monomer
methyl
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PCT/CN2013/086835
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French (fr)
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张广照
马春风
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华南理工大学
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Priority to US14/907,437 priority Critical patent/US9701794B2/en
Publication of WO2015010390A1 publication Critical patent/WO2015010390A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and 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
    • C08F30/04—Homopolymers and 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
    • C08F30/08—Homopolymers and 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
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/1668—Vinyl-type polymers
    • 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
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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

Definitions

  • the present invention relates to a silicon oxime ester resin, and more particularly to a method and application for preparing a main chain cleavable polyacrylic silicone phthalate resin; the application is mainly in the technical field of marine antifouling materials.
  • Marine biofouling refers to the attachment of marine microorganisms, plants and animals to the surface of ships and sea facilities, and the growth of biological scale, which is harmful to the exploration, development and utilization of marine transportation and marine resources. In the field of national defense, it has also been plagued by marine biofouling for a long time. For example, marine biofouling will accelerate the corrosion of the ship's bottom steel plate, reduce the service life of the weapon, and cause corrosion damage that requires manual and periodic maintenance.
  • the object of the present invention is to provide a main chain cleavable polyacrylic silane ester resin having a polyester chain segment in its main chain and a silane ester in a side chain, and a preparation method thereof.
  • Another object of the present invention is to provide an application of a main chain cleavable polyacrylic silane ester resin which can satisfy static antifouling in the preparation of marine antifouling coatings.
  • the main chain cleavable polyacrylic silicone phthalate resin provided by the invention is obtained by copolymerizing a cyclic monomer, a vinyl monomer and a vinyl silicon oxime monomer under a compound arching agent, and the structure thereof is A random copolymer composed of a polyester segment and a vinyl siloxane segment.
  • the invention introduces a main chain polyester segment into a conventional self-polishing resin, so that the main chain polyester can be generated under the action of sea water, in addition to the side chain silicic acid which can be hydrolyzed by the action of seawater. Broken chain to meet the needs of static antifouling applications.
  • the main chain cleavable polyacrylic silicic acid resin of the present invention comprises a main chain cleavage type polysilicyl silicate resin and a main chain cleavage type polymethacrylic acid silicate resin.
  • a method for preparing a main chain cleavable polyacrylic silane ester resin mixing a cyclic monomer, a vinyl monomer, and a vinyl silane ester monomer in a solvent, and then adding a total mass percentage of the monomer to 0.01 ⁇ 5% composite bowing agent, prepared under the condition of 25 50 ⁇ , argon or nitrogen protection; in mass percentage, the monomer composition is: cyclic monomer 5 ⁇ 95%, vinyl monomer 0 ⁇ 90% and vinyl silicon oxime ester 5 ⁇ 95%; the solvent is one of tetrahydrofuran, dimethylformamide, dimethylacetamide, butyl acetate, toluene, xylene, acetone and n-butanol or a variety of; the cyclic monomer is lactide, glycolide, caprolactone, 2. ⁇ methyl ⁇ , valerolactone, 2-methylene 1,3-dioxepane, ethylene
  • the vinyl monomer is acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid Octyl ester, dodecafluoroheptyl methacrylate, propylene, amine, methacrylamide, methylol acrylamide, isopropyl acrylamide, ethylene glycol methacrylate, hydroxyethyl acrylate, hydroxy methacrylate Ethyl ester, glycidyl methacrylate, styrene, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, vinylpyrrolidone, tetravinylpyridine, acryloyloxyethyl Methylbenzylammonium chloride, methacryloyloxyethyl
  • the vinyl silane ester monomer is trimethyl silane acrylate, triethyl silane acrylate, triisopropyl silane acrylate, triphenyl silane acrylate, propylene: tributyl silicate, Tri-n-octylsilyl acrylate, trimethylsilyl methacrylate, triethyl silane methacrylate, triisopropyl silane methacrylate, triphenyl silane methacrylate, methacrylic acid
  • the composite initiator is composed of two or more of a low molecular alcohol, a low molecular amine, a thiol, a phosphazene, a phosphazene salt, a phosphine oxide, an azobisisobutyronitrile, and a benzoyl peroxide. mixture.
  • the mass ratio of the total amount of monomers to the solvent is (5CT200): 100.
  • the low molecular amine is at least one of aliphatic amines having 2 to 10 carbon atoms.
  • the low molecular alcohol is at least one of aliphatic alcohols having 2 to 10 carbon atoms.
  • a main chain cleavable polyacrylic silane ester resin is obtained by the above production method.
  • main chain cleavage type polyacrylic silane ester resin in preparing marine antifouling paint: 10 parts by weight of the main chain cleavage type polyacrylic silicone phthalate resin, 20 parts by weight ⁇ 60 parts of cuprous oxide, 3 ⁇ 15 parts of organic antifouling agent, 10 ⁇ 40 parts of pigment and filler, 0 ⁇ 5 parts of auxiliary agent and 5 ⁇ 20 parts of organic solvent are mixed and stirred uniformly to obtain marine antifouling coating;
  • the organic antifouling agent is copper pyrithione, zinc pyrithione, pyridine triphenyl borane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, mitre One or more of imididine, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-:trifluoromethyl-pyrrole and:trichlorophenylphenylmaleimide ;
  • the pigment filler is one or more of zinc oxide, iron oxide red, calcium carbonate and barium sulfate;
  • the auxiliary agent is one or more of chlorinated paraffin, rosin, dioctyl phthalate, castor oil, bentonite, poly sulphamine wax, and fumed silica.
  • the organic solvent is one or more of xylene, n-butanol, methyl isobutyl ketone, butanone, diacetone alcohol, and vinyl acetate.
  • the present invention has the following advantages and benefits:
  • a main chain cleavage type self-polishing resin having a polyester chain in a main chain and a silane ester in a side chain is prepared by a copolymerization reaction of a cyclic monomer and a vinyl silane ester monomer.
  • the obtained resin can also be broken under the action of seawater, thereby solving the dependence of the traditional self-polishing material on the speed.
  • Static water can also renew a new surface by hydrolysis, which effectively regulates the release of the antifouling agent at a constant rate, ensuring the retention of the active material on the surface of the ship's coating, and is well suited to ships with low speeds, submarines and offshore oil recovery.
  • Anti-fouling requirements for platform facilities :
  • the material provided by the invention can be hydrolyzed in the seawater by the main side chain, and can be uniformly and thoroughly hydrolyzed and polished, so that the surface of the coating is smooth during the sailing, and the surface roughness is reduced, and the sailing resistance is reduced, Excellent resistance to drag reduction of materials;
  • the present invention can also add a vinyl monomer in the copolymerization to regulate the mechanical properties and adhesion of the material, and improve the solubility of the material in a conventional solvent of a marine coating, and has excellent mechanical properties and adhesion. .
  • the resin of the invention has good solubility in conventional solvent of marine coating, simple synthesis process and low cost, and is suitable for industrial production.
  • the material has good application prospect in the field of preparing marine antifouling coating.
  • 1 is an infrared spectrum of poly(caprolactone-trimethylsilyl methacrylate) obtained in Example 1;
  • Example 2 is a nuclear magnetic spectrum of poly(caprolactone-methacrylic acid: trimethylsilylester) obtained in Example 1;
  • Example 3 is a degradation map of poly(caprolactone-trimethylsilyl methacrylate) obtained in Example 1.
  • the present invention will be further described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto.
  • Four peaks (corresponding to the CH 2 absorption peak of caprolactone) appeared at -4.17 ppm, further indicating that poly(caprolactone-trimethylsilyl methacrylate) was synthesized.
  • the main chain contained a polyester segment which degraded under the action of the enzyme as ffl. Whether the main chain of the polymer can be broken is characterized by a quartz crystal microbalance. As shown in Figure 3.
  • the quartz crystal microbalance can detect the mass loss behavior of the material in situ, and the frequency change corresponds to the mass change and is inversely proportional. It can be seen that when the enzyme solution is added, the frequency rises, indicating a loss of quality. Since the silane lipid in the material cannot be hydrolyzed by the action of the enzyme, the mass loss is caused by the breakage of the main chain segment. Thus the material was proved to be backbone-breaking.
  • Marine antifouling paint The coating prepared by spraying 200g was formed on the epoxy resin board, and the shallow sea hanging board experiment (2012.4-2013.4) was carried out in Xiamen sea area according to GB/T5370-2007 "Anti-fouling paint sample shallow sea immersion test method", 12 months No marine growth, indicating that the antifouling coating prepared based on this material has a good antifouling effect, and does not depend on the speed of the ship.
  • the polymer was stirred and mixed with 20 g of cuprous oxide, 3 g of temomidazole, 12 g of zinc oxide and 5 g of xylene to prepare a marine antifouling paint.
  • the film was formed on the epoxy resin plate by brushing, and the shallow sea hanging plate experiment was carried out in Xiamen sea area (2012.4-2013.4), and no marine life was grown for 12 months.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

一种主链断裂型聚丙烯酸类硅垸酯树脂的制备方法及应用，该方法是将环状单体、乙烯基单体、乙烯基硅垸酯单体按配比混和在溶剂中，然后加入单体总量质量百分比为0.01〜5%的复合引发剂，在温度为25〜150°C，氩气或氮气保护的条件下反应制备；以质量百分比计，单体组成为：环状单体5〜95%、乙烯基单体0〜90%和乙烯基硅垸酯5〜95%；所得到的树脂除了侧链硅垸酯在海水的作用下能水解之外，主链聚酯链段在海水的作用下也能发生断链，解决了传统自抛光材料对航速的依赖性，有效调控防污剂以恒定速率释放，保证了活性物质在船舶涂层表面的保持，很好的满足低航速的船舶，潜艇以及海上采油平台设施的防污要求。

Description

本发明涉及一种硅垸酯树脂， 特别是涉及一种主链断裂型聚丙烯酸类硅垸酯树脂的制 备方法及应用； 该应用主要是海洋防污材料技术领域。 海洋生物污损是指海洋微生物、植物和动物在船¾和海中设施表面的附着，生长所形成 的生物垢， 它对海洋运输和海洋资源的勘探、 开发、 利用造成危害。 在国防领域,也长期受 到海洋生物污损的困扰，例如海洋生物污损会加速舰艇船底钢板的腐饨，降低武器装备的使 用寿命， 同时引起的腐蚀破坏需要人力进行频繁的周期性维护， 严重影响海军的战斗力并 造成巨大的经济损失。 此外， 海洋生物污损会增加舰船自重和航行的阻力， 增加燃油消耗， 严重影响舰船的作战性能。 尤其对于舰船或潜艇来说， 长期处于苛刻的海洋环境中， 船底 部分受到海洋生物的污损严重。 防污涂料是目前解决舰艇海洋生物污损最常用的方法。 但 海军军舰和一般民用船相比，具有停泊时间长，航行频率相对较低，跨海域机动性强等特点。 目前现有自抛光技术主要针对远洋船船设计，其性能的发挥对航期和航速都有一定的要求。 在静止阶段， 仅靠海水自流很难达到理想的自抛光效果。 实际上， 如何解决静止状态下长 效防污一直是一个世界性的难题， 对于舰船， 潜艇， 海上釆油平台都具有重要的战略意义。 本发明的目的是针对现有材料和技术的不足， 提供一种主链含有聚酯链段， 侧链含有 硅烷酯的主链断裂型聚丙烯酸类硅烷酯树脂及其制备方法。
本发明另一目的在于提供一种可满足静态防污的主链断裂型聚丙烯酸类硅烷酯树脂在 制备海洋防污涂料的应用。
本发明提供的一种主链断裂型聚丙烯酸类硅垸酯树脂是由环状单体、 乙烯基单体、 乙 烯基硅垸酯单体在复合弓发剂下共聚合而成， 其结构是由聚酯链段和乙烯基硅垸酯链段组 成的无规共聚物。 本发明在传统的自抛光树脂中引入主链聚酯链段， 使所涉及的材料除了 侧链硅垸酸在海水的作用下能水解之外， 主链聚酯在海水的作用下也能发生断链， 从而满 足静态防污的应用需要。 本发明中主链断裂型聚丙烯酸类硅垸酸树脂包括主链断裂型聚丙 烯酸硅垸酯树脂和主链断裂型聚甲基丙烯酸硅垸酸树脂。
本发明的目的通过以下技术方案实现： 一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法： 将环状单体、 乙烯基单体、 乙烯 基硅烷酯单体按配比混和在溶剂中， 然后加入单体总量质量百分比为 0.01~5%的复合弓发 剂， 在温度为 25 50Ό , 氩气或氮气保护的条件下反应制备； 以质量百分比计， 单体组成 为: 环状单体 5~95%、 乙烯基单体 0~90%和乙烯基硅垸酯 5~95%； 所述溶剂为四氢呋喃、 二甲基甲酰胺、 二甲基乙酰胺、 乙酸丁酯、 甲苯、 二甲苯、 丙酮和正丁醇中的一种或多种； 所述环状单体为丙交酯、 乙交酯、 己内酯、 2.·甲基 ·· £··己内酯、 2··氯 -ε··己内酯、 丁内酉旨、 戊内酯、 2-亚甲基 1,3-二氧杂环庚烷、 碳酸乙烯酯、 碳酸丙烯酸、 ：三亚甲基环碳酸酯、 2, 2-二甲基三亚甲基环碳酸酯、二甲氨基三亚甲基环碳酸酯、 2-乙基- 2-恶唑啉、 2-甲基 -2-恶唑 啉、 五元环磷酸酯、 六元环磷酸酯、 环氧乙烷、 环氧丙烷、 环氧氯丙垸和 Υ-缩水甘油醚氧 丙基三 φ氧基硅垸中的一种或多种；
所述乙烯基单体为丙烯酸， 甲基丙烯酸， 甲基丙烯酸甲酯， 甲基丙烯酸乙酯， 甲基丙 烯酸丁酯， 甲基丙烯酸辛酯， 丙烯酸甲酯， 丙烯酸乙酯， 丙烯酸丁酯， 丙烯酸辛酯， 甲基 丙烯酸十二氟庚酯， 丙烯》胺， 甲基丙烯酰胺， 羟甲基丙烯酰胺， 异丙基丙烯酰胺， 甲基 丙烯酸乙二醇酯， 丙烯酸羟乙酯， 甲基丙烯酸羟乙酯， 甲基丙烯酸缩水甘油醚， 苯乙烯， 甲基丙烯酸二甲氨基乙酯， 甲基丙烯酸二乙氨基乙酯， 乙烯基 Ρ比咯烷酮， 四乙烯基 啶， 丙烯酰氧乙基二甲基苄基氯化铵， 甲基丙烯酰氧基乙基苄基二甲基氯化铵， 甲基丙烯酰氧 乙基 甲基氯化铵， 聚磺酸甜菜碱甲基丙烯酸甲酯和聚羧酸甜菜碱甲基丙烯酸甲酯中的一 种或多种；
所述乙烯基硅烷酯单体为丙烯酸三 ^基硅烷酯、 丙烯酸三乙基硅垸酯、 丙烯酸三异丙 基硅垸酯、 丙烯酸三苯基硅烷酯、 丙: ϋ酸三丁基硅烷酯、 丙烯酸三正辛基硅垸酯、 甲基丙 烯酸三甲基硅烷酯、 甲基丙烯酸三乙基硅烷酯、 甲基丙烯酸三异丙基硅烷酯、 甲基丙烯酸 三苯基硅烷酯、 甲基丙烯酸三丁基硅烷酯、 甲基 R烯酸三正辛基硅烷酯中的一种或任意几 种以任意比例组成的混合物；
所述复合引发剂为低分子醇， 低分子胺， 硫醇， 磷腈、 磷腈盐、 氧化磷腈、 偶氮二异 丁腈、 过氧化苯甲酰中的两种或者两种以上组成的混合物。
优选地，所述单体总量与溶剂的质量比为 (5CT200): 100。所述低分子胺为含碳原子 2~10 的脂肪族胺中的至少一种。 所述低分子醇为含碳原子 2~10的脂肪族醇中的至少一种。
一种主链断裂型聚丙烯酸类硅烷酯树脂， 由上述制备方法制得。
所述主链断裂型聚丙烯酸类硅烷酯树脂在制备海洋防污涂料中的应用： 以重量份数计'， 将 10~60份的所述主链断裂型聚丙烯酸类硅垸酯树脂、 20~60份的氧化亚铜、 3~15份的有 机防污剂、 10~40份的颜填料、 0~5份的助剂和 5~20份的有机溶剂混合搅拌均匀， 制得海 洋防污涂料； 所述有机防污剂为吡啶硫酮铜、吡啶硫酮锌、吡啶三苯基硼烷、 4,5-二氯代 -2-正辛基 -4- 异噻唑琳 -3-酮、 米托咪啶、 2- (对-氯苯基 )-3-氰基 4溴基- 5-：三氟甲基-吡咯和 ：三氯苯基 苯基马来酰亚胺中的一种或多种；
所述颜填料为氧化锌、 氧化铁红、 碳酸钙和硫酸钡中的一种或多种；
所述助剂为氯化石蜡、 松香、 邻苯二甲酸二辛酯、 蓖麻油、 膨润土、 聚醜胺蜡和气相二 氧化硅中的一种或多种。
所述有机溶剂为二甲苯、 正丁醇、 甲基异丁基酮、 丁酮、 二丙酮醇和醋酸乙烯酯中的一 种或多种。
与现有技术相比， 本发明具有以下优点和有益效果：
( 1)本发明通过环状单体和乙烯基硅烷酯单体的共聚合反应， 制备了主链含有聚酯链 段， 侧链含有硅烷酯的主链断裂型自抛光树脂 ^料。 所得到的树脂除了侧链硅烷酯在海水 的作用下能水解之外， 主链聚酯链段在海水的作用下也能发生断链， 从而解决了传统自抛 光材料对航速的依赖性， 在静态海水中也能通过水解作用更新出新的表面， 从而有效调控 防污剂以恒定速率释放， 保证了活性物质在船舶涂层表面的保持， 很好的满足低航速的船 舶， 潜艇以及海上采油平台设施的防污要求：
( 2) 本发明提供的材料由于主侧链在海水中均可发生水解， 能均匀和彻底水解抛光， 使得船 ¾在航行期间涂层表面光滑， ^而降低表面粗糙度， 减少航行阻力， 赋予材料优异 的减阻性能；
( 3 )本发明还可以在共聚合中加入乙烯基单体以调控材料的力学性能和粘附力， 同^ 改善材料在船舶涂料常规溶剂中的溶解性， 具有优异的力学性能和粘^力。
( 4)本发明树脂在船舶涂料常规溶剂中的溶解性好， 合成工艺简单， 成本较低， 适合 工业化生产， 该材料在制备海洋防污涂层领域具有很好的应用前景。 图 1为实施例 1所得聚 (己内酯-甲基丙烯酸三甲基硅烷酯)的红外图谱；
图 2为实施例 1所得聚 (己内酯-甲基丙烯酸:三甲基硅垸酯)的核磁图谱；
图 3为实施例 1所得聚 (己内酯-甲基丙烯酸三甲基硅烷酯)的降解图谱。 为更好地理解本发明， 下面结合实施例对本发明作进一步地详细说明， 但本发明的实 施方式不限于此。 在千燥的 250 mL带有搅拌器和温度计的三口瓶中加入 50 g已内酯， 50 g甲基丙烯酸三 甲基硅烷酯、 0,1 g甲醇和 100 mL二甲苯， 加入 ΙΟΟ μί磷腈 (t- ΒυΡ4)的正已烷溶液， 在 25。C 条件下反应 6 h后， 在甲醇沉淀， 真空干燥， 得到聚 (己内酯-甲基丙烯酸三甲基硅烷酯)，其 产率为 90%。从图 1红外谱图中出现 1730 crrr1 (对应己内酯的酯基吸收峰)， ZSSO crrv 对应 己内酯的 CH2的吸收峰)以及 2950 cm"1 (对应硅垸酯的 CH3的吸收峰)， 说明成功合成目标产 物。 图 2核磁谱图中化学位移 δ=0.87 (对应硅垸酯的 CH3的吸收峰)以及 1.32-1.45ppm、 1.55-1.72ppm、 2.25-2.40ppm、 3.98-4.17ppm出现了四个峰 (对应己内酯的 CH2吸收峰), 进 一步说明合成了聚 (己内酯-甲基丙烯酸三甲基硅烷酯)。
通过凝胶渗透色谱仪检测其数均分子量为 2.0x l04 g/mol。 于本实施例 1所得产物中 主链含有聚酯链段， 其在酶的作 ffl下可发生降解作用。 通过石英晶体微天平表征该聚合物 的主链是否可断裂。 如图 3所示。 石英晶体微天平可以原位检测材料的质量损失行为， 频 率变化对应与质量变化， 且成反比。 可以看到， 当加入酶溶液后， 频率发生上升， 说明有 质量损失。 由于材料中硅烷脂在酶的作用下不能发生水解， 质量损失是有主链段发生断裂 造成的。 因而证明该材料是主链断裂型的。
将合成的 30 g聚 (己内酯-甲基丙烯酸:三甲基硅垸酯)、 40 g氧化亚铜、 5 g吡啶硫酮铜、 10 g氧化锌以及 15 g二甲苯搅拌混合， 制成海洋防污涂料。通过喷涂 200g制备的涂料在环 氧树脂板上成膜， 按照 GB/T5370-2007 《防污漆样板浅海浸泡试验方法》， 在厦门海域进行 了浅海挂板实验 (2012.4-2013.4) , 12个月无海洋生物生长， 说明基于该材料制备的防污涂 料具有很好的防污效果， 同时不依赖于航速。
实麵 2
在 250 mL封管中加入 10 g 丙交酯， 90 g丙烯酸三异丙基硅酯， 0.01 g二乙二醇和 100 mL 四氢呋喃， 液氮冷冻， 置换氮气三次后在氮气气氛下注入 70 的 t-BuP4的正己烷溶液，熔 融封管， 60。C条件下反应 2 h , 然后沉淀在 100 mL甲醇中， 真空干燥 12 h , 产率为 94%, 通过凝胶渗透色谱仪检测其数均分子量为 l,5xl04 g/mol。 将该聚合物 20 g , 与 120 g氧化 亚铜， 20 g吡啶：三苯基硼烷， 10 g氧化铁红以及 30 g甲基异丁基酮搅拌混合， 制成海洋防 污涂料。 通过刷涂的方式， 在环氧树脂板上成膜， 在厦门海域进行了浅海挂板实验 (2012.4-2013.2) , 10个月无海洋生物生长。
实施例 3
在 500 mL—三口瓶中加入 180 g 碳酸乙烯酯， 10 g 丙烯酸三正丁基硅酯， 10g甲基丙烯 酸甲酸， 甲醇 0.02 g , 液氮冷冻， 置换氮气―三次后在氮气气氛下迅速注入 70 的 t-BuP4 的正己烷溶液， 150 条件下反应 12 h。 反应结束后沉淀在甲醇中， 过滤， 真空千燥， 产率 为 90%， 通过凝胶渗透色谱仪检测其数均分子量为 2。4><10 /^0|。 将该聚合物 30 g， 与 40 g氧化亚铜， 7 g 4,5-二氯代 -2-正辛基 -4-异噻唑啉- 3-酮， 7 g氧化锌， 6 g碳酸钙， 3g膨润土， 以及 7 g丁酮搅拌混合， 制成海洋防污涂料。通过剧涂的方式， 在环氧树脂板上成膜， 在厦 门海域进行了浅海挂板实验 (2012.4-2013.4), 12个月无海洋生物生长。 在 250 mL _三 Π瓶中加入 80 g 2-亚甲基 -1 ,3-二氧杂环庚垸, 20 g甲基丙烯酸甲酯， 20g 丙 烯酸 正丁基硅酯， 0.5 g偶氮二异丁腈和 100 mL甲苯溶液， 50°C反应 12 h。反应结束后用 正己垸沉淀， 过滤， 真空千燥 12 h , 产率为 90%, 通过凝胶渗透色谱仪检测其数均分子量 为 1.3xl04 g/mo!。 将该聚合物 60 g, 与 20 g氧化亚铜， 3 g米托咪啶， 12 g氧化锌以及 5 g 二甲苯搅拌混合， 制成海洋防污涂料。 通过刷涂的方式， 在环氧树脂板上成膜， 在厦门海 域进行了浅海挂板实验 (2012.4- 2013.4), 12个.月无海洋生物生长。 在 100 mL三口瓶中加入 50 g 2-甲基- ε-己内酯， 25 g甲基丙烯酸甲酯， 25g 甲基丙烯酸 三异丙基硅酯， 0.1 g过氧化苯甲酰和 100 mL二甲苯溶液， 70°C反应 24 h。反应结束后用水 沉淀，过滤，真空干燥 12 h ,产率为 80%,通过凝胶渗透色谱仪检测其数均分子量为 2.3xl04 g/mol。 将该聚合物 10 g, 与 30 g氧化亚铜， 5 g 2,4,6-— Ξ:氯苯基 苯基马来酰亚胺， 30 g 氧化锌， 5g氧化铁红， 5g聚酰胺蜡以及 15 g二甲苯搅拌混合， 制成海洋防污涂料。通过喷 涂的方式， 在环氧树脂板上成膜， 在厦门海域进行了浅海挂板实验 (2012.4.·2013.6) , 14个 月无海洋生物生长。 在 250 mL三口瓶中加入 40g 2-氯 -ε-己内酯， 60 g甲基丙烯酸三甲基硅垸， O.l g乙醇以 及 100 mL甲苯溶液， 液氮冷冻， 置换氮气三次后在氮气气氛下注入 7 μί的 t- BuP4的正己 垸溶液， 25 °C反应 12 h , 在甲醇沉淀， 过滤， 真空干燥， 产率 90%， 通过凝胶渗透色谱仪 检测其数均分子量为 5,5xl04 g/mol。将该聚合物 30 g, 与 30 g氧化亚铜， 10 g吡啶硫酮锌， 7 g硫酸钡， 3g 膨润土以及 20g正丁醇搅拌混合， 制成海洋防污涂料。 通过刷涂的方式， 在环氧树脂板上成膜， 在厦门海域进行了浅海挂板实验 (2012.4-2013.4), 12个月无海洋生 物生长。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制， 其他的任何未背离本发明的精神实质与原理下所作的改变、 修饰、 替代、 组合、 简化， 均 应为等效的置换方式， 都包含在本发明的保护范围之内。

Claims

1、 一种主链断裂型聚丙烯酸类硅垸酯树脂的制备方法， 其特征在于， 将环状单体、乙 烯基单体、 乙烯基硅垸酯单体按配比混和在溶剂中， 然后加入单体总量质量百分比为 0。01~5%的复合引发剂， 在温度为 25~150°C , 氩气或氮气保护的条件下反应制备； 以质量 百分比计， 单体组成为： 环状单体 5~95%、 乙烯基单体 0~90%和乙烯基硅烷酯 5~95%： 所 述溶剂为四氢呋喃、 二甲基甲酰胺、 二甲基乙酰胺、 乙酸丁酯、 甲苯、 二甲苯、 丙酮和正 了酉享 Φ &勺——禾中 4?禾中；
所述环状单体为丙交酯、 乙交酯、 己内酯、 2-甲基 - ε-己内酯、 2-氯 -ε-己内酯、 丁内酯、 戊内酯、 2-亚甲基 -1,3-二氧杂环庚烷、 碳酸乙烯酯、 碳酸丙烯酯、 Ξ:亚甲基环碳酸酯、 2, 2-二甲基：三亚甲基环碳酸酯、二甲氨基 Ξ:亚甲基环碳酸酯、 2 -乙基 -2-恶唑啉、 2-甲基- 2-恶唑 啉、 五元环磷酸酯、 六元环磷酸酯、 环氧乙烷、 环氧丙烷、 环氧氯丙烷和 γ··縮水甘油醚氧 丙基:三甲氧基硅垸中的一种或多种；
所述乙烯基单体为丙铩酸， 甲基丙烯酸， 甲基丙烯酸甲酯， 甲基丙烯酸乙酯， 甲基丙 烯酸丁酯， 甲基丙烯酸辛酯， 丙烯酸甲酯， 丙烯酸乙酯， 丙烯酸丁酯， 丙烯酸辛酯， 甲基 丙烯酸十二氟庚酯， 丙烯酰胺， 甲基丙烯酰胺， 羟甲基丙铩酰胺， 异丙基丙烯酰胺， 甲基 丙烯酸乙二醇酯， 丙烯酸羟乙酯， 甲基丙烯酸羟乙酯， 甲基丙烯酸缩水甘油醚， 苯乙烯， 甲基丙烯酸二甲氨基乙酯， 甲基丙烯酸二乙氨基乙酯， 乙烯基吡咯烷酮， 四乙烯基吡啶， 丙烯酰氧乙基二甲基苄基氯化铵， 甲基丙烯酰氧基乙基苄基二甲基氯化铵， 甲基 R烯酰氧 乙基≡甲基氯化铵， 聚磺酸甜菜碱甲基丙烯酸甲酯和聚羧酸甜菜碱甲基丙烯酸甲酯中的 种或多种；
所述乙烯基硅烷酯单体为丙烯酸三甲基硅烷酯、 丙烯酸三乙基硅垸酯、 丙烯酸 Ξ:异丙 基硅烷酯、 丙烯酸：三苯基硅垸酸、 丙烯酸：三丁基硅烷酯、 丙烯酸：三正辛基硅垸酯、 甲基丙 烯酸三甲基硅垸酯、 甲基丙烯酸三乙基硅垸酯、 甲基丙烯酸三异丙基硅烷酯、 甲基丙烯酸 三苯基硅垸酯、 甲基丙烯酸三丁基硅垸酯、 甲基丙烯酸三正辛基硅垸酯中的一种或任意几 种以任意比例组成的混合物；
所述复合引发剂为低分子醇， 低分子胺， 硫醇， 磷腈、 磷腈盐、 氧化磷腈、 偶氮二异 丁腈、 过氧化苯甲酰中的两种或者两种以上组成的混合物。
2、根据权利要求 1所述的主链断裂型聚 R烯酸类硅烷酯树脂的制备方法，其特征在于， 所述单体总量与溶剂的质量比为 (50~200): 100。
3、根据权利要求 1所述的主链断裂型聚丙烯酸类硅烷酯树脂的制备方法，其特征在于， 所述低分子胺为含碳原子 2 0的脂肪族胺中的至少一种。
4、根据权利要求 1所述的主链断裂型聚 R烯酸类硅烷酯树脂的制备方法，其特征在于， 所述低分子醇为含碳原子 2 0的脂肪族醇中的至少一种。
5、 一种主链断裂型聚丙烯酸类硅垸酯树脂， 其特征在于， 其由权利要求 1-4任一项所 述制备方法制得。
6、 权利要求 5所述主链断裂型聚丙烯酸类硅烷酯树脂在制备海洋防污涂料中的应用， 其特征在于， 以重量份数计， 将 10~60份的所述主链断裂型聚丙烯酸类硅烷酯树脂、 20-60 份的氧化亚铜、 3~15份的有机防污剂、 10~40份的颜填料、 0~5份的助剂和 5~20份的有机 溶剂混合搅拌均匀， 制得海洋防污涂料；
所述有机防污剂为吡啶硫酮铜、吡啶硫酮锌、吡啶三苯基硼垸、 4,5-二氯代 -2-正辛基 -4- 异噻唑辭- 3-酮、 米托咪啶、 2- (对-氯苯基 )-3-氰基 -4-溴基- 5-三氟 ^基-吡喀和 2,4,6-三氯苯基 -Ν-苯基马来酰亚胺中的一种或多种；
所述颜填料为氧化锌、 氧化铁红、 碳酸钙和硫酸钡中的一种或多种；
所述助剂为氯化石蜡、 松香、 邻苯二甲酸二辛酯、 蓖麻油、 膨润土、 聚酰胺蜡和气相二 氧化硅中的一种或多种。
所述有机溶剂为二甲苯、 正丁醇、 甲基异丁基酮、 丁酮、 二 R酮醇和醋酸乙烯酯中的 一种或多种。
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