Method for preparing main chain scission-type polysilyl (meth)acrylate resin and application thereof

Patent metadata

Field	Value
Publication number	US-2016185913-A1
Application number	US-201314907437-A
Country	US
Kind code	A1
Filing date	Nov 11, 2013
Priority date	Jul 24, 2013
Publication date	Jun 30, 2016
Grant date	—

Abstract

A method for preparing a main chain scission-type polysilyl (meth)acrylate resin and application thereof. The method comprises: a cyclic monomer, vinyl monomer and vinyl silyl ester monomer are mixed in a solvent at a formulation ratio, then added a composite initiator in a mass percentage of 0.01-5% based on the total amount of the monomers, and reacted at a temperature of 25-150° C., and under the protection of argon or nitrogen gas, so as to prepare the main chain scission-type polysilyl (meth)acrylate resin, wherein the monomers are consisted of 5-95% by mass of cyclic monomer, 0-90% by mass of vinyl monomer and 5-95% by mass of vinyl silyl ester monomer. The resulting resin can not only be hydrolyzed on the side chain silyl ester segment under the effect of the sea water, but also occur chain scission on the main chain polyester segment under the effect of the seawater, so as to solve the dependency of the traditional self-polishing material on the sailing speed, effectively control the release of the antifouling agent at a constant rate, ensure the active substance preserved on the coating surface of the ships, and properly meet the antifouling requirements on the low sailing speed ships, submarines and off-shore oil platform facilities.

First claim

1 . A method for preparing a main chain scission-type polysilyl (meth)acrylate resin, wherein a cyclic monomer, vinyl monomer, and vinyl silyl ester monomer are mixed in a solvent at a formulation ratio, then added a composite initiator in a mass percentage of 0.01 to 5% based on the total amount of the monomers, and reacted at a temperature of 25 to 150° C., and under the protection of argon or nitrogen gas, so as to prepare the main chain scission-type polysilyl (meth)acrylate resin; wherein the monomers are consisted of 5 to 95% by mass of cyclic monomer, 0 to 90% by mass of vinyl monomer, and 5-95% by mass of vinyl silyl ester monomer; the solvent is one or more of tetrahydrofuran, dimethyl formamide, dimethyl acetamide, butyl acetate, toluene, xylene, acetone and n-butanol;
the cyclic monomer is one or more of lactide, glycolide, caprolactone, 2-methyl-ε-caprolactone, 2-chloro-ε-caprolactone, butyrolactone, valerolactone, 2-methylene-1,3-dioxepane, ethylene carbonate, propylene carbonate, tri-methylene cyclic carbonate, 2,2-dimethyl trimethylene cyclic carbonate, dimethylaminotrimethylene cyclic carbonate, 2-ethyl-2-oxazoline, 2-methyl-2-oxazoline, five-membered ring phosphate, six-membered ring phosphate, epoxy ethane, epoxy propane, epoxy chloropropane and γ-glycidyloxypropyltrimethoxy siliane;
the vinyl monomer is one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecafluoroheptyl methacrylate, acrylamide, methacrylamide, methylol acrylamide, isopropyl acrylamide, ethylene glycol methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, styrene, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, vinylpyrrolidone, tetravinylpyridine, acryloyloxyethyldimethylbenzyl ammonium chloride, methacryloyloxyethylbenzyldimethyl ammonium chloride, methacryloyloxyethyltrimethyl ammonium chloride, polysulfobetainemethyl methacrylate and polycarboxybetainemethyl methacrylate;
the vinyl silyl ester monomer is one or a mixture in any ratio of two or more of trimethylsilyl acrylate, triethylsilyl acrylate, isopropylsilyl acrylate, triphenylsilyl acrylate, tributyl silyl acrylate, tri-n-octylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, triphenylsilyl methacrylate, tributylsilyl methacrylate, and tri-n-octylsilyl methacrylate,
the composite initiator is a mixture of two or more of low molecular weight alcohol, low molecular weight amine, thiol, phosphazene, phosphazene salt, phosphazene oxide, azobisisobutyronitrile, and benzoyl peroxide.

2 . A method for preparing a main chain scission-type polysilyl (meth)acrylate resin according to claim 1 , wherein the mass ratio between the total amount of monomers and the solvent is (50˜200): 100.

3 . A method for preparing a main chain scission-type polysilyl (meth)acrylate resin according to claim 1 , wherein the low molecular weight amine is at least one of aliphatic amines containing 2˜10 carbon atoms.

4 . A method for preparing a main chain scission-type polysilyl (meth)acrylate resin according to claim 1 , wherein the low molecular weight alcohol is at least one of aliphatic alcohols containing 2˜10 carbon atoms.

5 . A main chain scission-type polysilyl (meth)acrylate resin, prepared by a method according to claim 1 .

6 . Use of a main chain scission-type polysilyl (meth)acrylate resin of claim 5 in preparing a marine antifouling coating, wherein 10 to 60 parts by weight of the main chain scission-type polysilyl (meth)acrylate resin, 20 to 60 parts by weight of cuprous oxide, 3 to 15 parts by weight of organic antifouling agent, 10 to 40 parts by weight of pigment filler, 0 to 5 parts by weight of auxiliary agent and 5 to 20 parts by weight of organic solvent are mixed and stirred to uniform, so as to produce a marine antifouling coating;
wherein the organic fouling agent is one or more of copper pyrithione, zinc pyrithione, pyridyltriphenyl borane, 4,5-dichloro-2-n-octyl-4-isothiazolinyl-3-one, medetomidine, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, and 2,4,6-trichlorophenyl-N-phenyl maleimide;
the pigment filler is one or more of zinc oxide, red iron oxide, calcium carbonate and barium sulfate;
the auxiliary agent is one or more of chlorinated paraffin, rosin, dioctyl phthalate, castor oil, bentonite, polyamide wax and fumed silica;
the organic solvent is one or more of xylene, n-butanol, methyl isobutyl ketone, butanone, diacetone alcohol and vinyl acetate.

Assignees

• Univ South China Tech

Inventors

• Zhang Guangzhao
• Ma Chunfeng

Classifications

• C09D5/1668

  Vinyl-type polymers · CPC title

• C08G65/2615

  the other compounds containing carboxylic acid, ester or anhydride groups · CPC title

• C09D171/00

  Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain (based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06); Coating compositions based on derivatives of such polymers · CPC title

• C09D143/04

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C09D133/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title