CN109868026A - A kind of Silicone-Modified Acrylate Resin and preparation method thereof and the hydrophobic weather-proof acrylic resin modified coating of sustained release - Google Patents
A kind of Silicone-Modified Acrylate Resin and preparation method thereof and the hydrophobic weather-proof acrylic resin modified coating of sustained release Download PDFInfo
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- CN109868026A CN109868026A CN201910126028.2A CN201910126028A CN109868026A CN 109868026 A CN109868026 A CN 109868026A CN 201910126028 A CN201910126028 A CN 201910126028A CN 109868026 A CN109868026 A CN 109868026A
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- acrylate
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- silicone
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 51
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 13
- 238000013268 sustained release Methods 0.000 title claims abstract description 13
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 230000005494 condensation Effects 0.000 claims abstract description 9
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- -1 ethoxy radical siloxane Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000002421 anti-septic effect Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000548 poly(silane) polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- CPBHJGWJMLDUNB-UHFFFAOYSA-N ethenoxysilane Chemical compound [SiH3]OC=C CPBHJGWJMLDUNB-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention discloses a kind of Silicone-Modified Acrylate Resins and preparation method thereof and the hydrophobic weather-proof acrylic resin modified coating of sustained release.Organosiloxane hydrolytic condensation is obtained into organosilan oligomer, organosilan oligomer first prepolymerization is subjected to part acrylic acid resin polymerization single polymerization monomer, then polymerize with remaining part acrylic resin polymerized monomer, obtains organosilicon modified crylic acid resin;Silicone-Modified Acrylate Resin, isocyanate curing agent, filler, solvent and auxiliary agent etc. are compounded, the integrative protection material for being provided simultaneously with good hydrophobicity, heat-resisting quantity, weatherability and antiseptic property can be obtained.
Description
Technical field
The present invention relates to a kind of Silicone-Modified Acrylate Resins and preparation method thereof, further relate to one kind and are changed with organosilicon
Property acrylic resin be matrix resin hydrophobic weather-proof sustained release coating, belong to paint field.
Background technique
Coating as common important chemical products, be widely used in building, aviation, naval vessel, automobile, etc. almost each row
Each industry plays the function affects such as decorative appearance and weather-proof, anti-corrosion.With the development of engineering technology, particular job environment is more next
More common, the coating used under harsh environment has become important research content.And the base that resin is formed as organic coating
Plinth part, research and development can have become research in recent years weight as the resin with high temperature resistant, multipurpose, the protective materials haveing excellent performance
Point direction.
Acrylic resin then have color is shallow, transparency is high, good corrosion resistance, infrared region absorb small and monomer it is numerous,
The advantages such as cheap, but the shortcoming of its resistant of high or low temperature, water resistance and gas permeability is limited and is further applied.And organosilicon
Resin has both the characteristics of standby inorganic and organic compound, is a kind of high molecular material for possessing dual property.Organic silicon monomer and
Its polymer Si-O bond energy is higher, and key rotation is easy, and assigns its lower surface tension and glass transition temperature, and have good
The excellent performances such as well water-fast, heatproof, weatherability, but since polarity is low, the adhesive force on general substrate is poor, price
Also more expensive.Organosilicon is used to modified polyacrylic acid resin to be expected to obtain the composite material for having both the two advantage, improves material
The performance of material expands use scope.Currently, studying about organosilicon modified crylic acid resin, it is generally divided into mechanical blending and change
It learns and is modified.Mechanical blending method is easy to operate, but organosilicon all has larger difference, tool in structure and polarity with acrylate
The present surface free energy of body surface differs larger, poor compatibility, and organosilicon is easy to surface migration after blending, and the organosilicon of preparation changes
Being also easy to produce for acrylate polymer of property mutually separates, it is difficult to obtain the organosilicon acrylic resin of stable uniform.Chemical modification is to pass through chemistry
Reaction forms the polymer of both polarized differences of chemical bonds, silicone molecules chain is introduced into acrylate molecule.
Polysilane is mainly introduced acrylate by grafting mode by chemic modified method, can inhibit organosilicon point to a certain extent
Migration of the son to surface, so as to improve the two compatibility, but since polysilane chain and polyacrylic acid chain are in structure and polarity
It differs greatly with acrylate, poor compatibility, however it remains phenomenon of phase separation.In addition existing organic-silane-modified acrylic ester
Hydrophobicity, heat-resisting quantity, weatherability etc. be improved, but antiseptic property is bad.
Summary of the invention
For silicone modified polyacrylate in the prior art, first mesh of the invention
Be be to provide it is a kind of using while comprising unsaturated double-bond and hydrolyzable condensation group functional monomer come with organosilicon
Alkane oligomer and acrylic monomer carry out copolymerization and obtain stable structure, uniform, organosilan and polyacrylate compatibility it is good,
It is not easy the method for organosilicon modified crylic acid resin mutually separated, this method is easy to operate, at low cost, is conducive to industrial metaplasia
It produces.
Second object of the present invention is to be to provide that a kind of organosilan is good with polyacrylate compatibility, is not easy phase point
From organosilicon modified crylic acid resin, which is provided simultaneously with good hydrophobicity, heat-resisting quantity, weatherability and anti-corrosive properties
Can, it is suitable for hydrophobic weather-proof sustained release integrative protection material.
Third object of the present invention is to be to provide a kind of coating hydrophobicity, heat-resisting quantity, weatherability and antiseptic property
Good hydrophobic weather-proof sustained release integrative protection coating.
In order to achieve the above technical purposes, the present invention provides a kind of preparation sides of Silicone-Modified Acrylate Resin
Method, this method are that organosiloxane hydrolytic condensation is obtained organosilan oligomer, by organosilan oligomer elder generation and part third
Olefin(e) acid resin polymerization single polymerization monomer carries out prepolymerization, then is polymerize with remaining part acrylic resin polymerized monomer, and organosilicon is obtained
It is acrylic resin modified;Acrylic resin polymerized monomer includes soft monomer, hard monomer and function monomer;The hard monomer includes third
E pioic acid methyl ester, methyl methacrylate, ethyl methacrylate, n-BMA, tert-butyl acrylate, styrene,
At least one of acrylonitrile, acrylic acid;The soft monomer includes ethyl acrylate, n-butyl acrylate, lauryl acrylate, third
At least one of olefin(e) acid -2- ethylhexyl, lauryl methacrylate, n octyl methacrylate;The function monomer includes
2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid -2- hydroxy methacrylate, methacrylic acid -2- hydroxyl third
At least one of ester.
The key of technical solution of the present invention is to use 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, first
The special function monomer such as base 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy propyl ester participate in organosilan oligomer and
The copolymerization of acrylic ester monomer.These function monomers not only include that double bond functional group also includes hydroxyl ester group, both can with have
Condensation is hydrolyzed in machine silane, and can carry out free radical polymerization with acrylate monomer, is dispersed in poly- third by random copolymerization
In olefin(e) acid resin, and condensation cross-linking can be carried out with organosilan oligomer, so that good coupled action is played, so as to improve having
The compatibility of machine silicon and polyacrylate can obtain stable organosilicon modified crylic acid resin.
Preferred scheme, the organosiloxane include methltriethoxysilone, dimethyl diethoxysilane, second
At least one of alkenyl triethoxysilane, phenyltriethoxy silane oxygen alkane.
Organosiloxane by R/Si value is 1.2~1.4 by preferred scheme, Ph/R value be 0.2~0.6 after mixing,
Acid solution is added dropwise, 3~6h is reacted at a temperature of 70~80 DEG C, obtains organosilan oligomer.Wherein, R is straight with silicon atom
Connected alkyl groups are connect, Ph is the phenyl number being connected directly with silicon atom.R/Si value can estimate the curing rate of resin, line
Type structure and flexibility etc., Ph/Si value assign organic siliconresin different characteristics.The preferred R/Si value of the present invention be 1.2~1.4,
Ph/R value is 0.2~0.6, to obtain the organic siliconresin of excellent properties.
The mass ratio of preferred scheme, organosilan oligomer and soft monomer, hard monomer and function monomer is 15~30:20
~50:40~70:5~25.The optimal organosilicon-modified acrylic tree of comprehensive performance can be obtained in preferred proportional region
Rouge.
Preferred scheme, by the acrylic resin polymerized monomer of organosilan oligomer and 30~50% mass 75~85
DEG C carry out polymerization reaction 1~2 hour after, then in 1.5~2h by remaining part acrylic resin polymerized monomer drop evenly to
In reaction system, 0.5~1.5h of insulation reaction is to get organosilicon modified crylic acid resin.In the course of the polymerization process, using routine
The addition of initiator, initiator mixes addition with acrylic resin polymerized monomer.
The present invention also provides a kind of Silicone-Modified Acrylate Resins, are obtained by above-mentioned preparation method.
The present invention also provides a kind of hydrophobic weather-proof acrylic resin modified coating of sustained release comprising above-mentioned organic-silicon-modified
Acrylate, isocyanate curing agent, filler, solvent and auxiliary agent.
Preferred scheme, the filler are silane-modified nanoparticle;The silane-modified nanoparticle includes that silane changes
At least one of property nano silica, silane-modified nano-titanium dioxide, silane-modified nano zine oxide.The present invention uses silicon
Alkane modified Nano particle is silane-modified by carrying out to common nanoparticle surface as filler, and two-phase can be effectively reduced
Interfacial effect reduces and reunites, and improves inorganic nano-particle in the stability of organic resin.Silane-modified nanoparticle of the invention
Preparation method: inorganic nano-particle is dispersed to ethyl alcohol, water that pH is 4~5, in glacial acetic acid mixed solution, at 70~90 DEG C
At a temperature of, it is stirred to react 8~16h, obtains silane-modified nanoparticle.The partial size of nanoparticle is generally 10~100nm.
Preferred scheme, a kind of hydrophobic weather-proof acrylic resin modified coating of sustained release comprising following content of component: have
75~100 parts of resin of machine fluorine-silicon modified acrylic ester;10~20 parts of isocyanate curing agent;1~10 part of filler;Solvent 30~50
Part;2~8 parts of auxiliary agent.
Preferred scheme, isocyanate curing agent are selected from De Shimo all N75, De Shimo all N3390, BASF HI100ap
At least one of.
Preferred scheme, solvent in butyl acetate, ethyl acetate, toluene, dimethylbenzene, propylene glycol methyl ether acetate extremely
Few one kind.
Preferred scheme, the auxiliary agent can be at least one in BYK series levelling agent, defoaming agent, wetting agent, dispersing agents
Kind.Auxiliary agent is the common auxiliary agent of paint field, such as: the auxiliary agent for the effects of playing levelling, defoaming, pigment wetting, viscosity-adjusting agent.
The preparation method of the hydrophobic weather-proof acrylic resin modified coating of sustained release of one kind of the invention, comprising the following steps:
1) organosiloxane hydrolytic condensation is obtained into organosilan oligomer;
2) part acrylic acid resin polymerization single polymerization monomer and organosilan oligomer are subjected to prepolymerization, with remaining part propylene
Acid resin polymerized monomer is polymerize, and organosilicon modified crylic acid resin is obtained;
3) Silane coupling reagent KH-570 is added dropwise in nanoparticle dispersion liquid and is reacted, obtain silane-modified nanoparticle;
4) it is uniformly mixed with silane-modified nanoparticle by polysilane is acrylic resin modified, obtains organic-silicon-modified propylene
Acid ester resin and nano-particle compound;
5) by Silicone-Modified Acrylate Resin and nano-particle compound and isocyanate curing agent, solvent and auxiliary agent
Mixing to get.
Compared with prior art, the beneficial effect of technical solution of the present invention is:
Technical solution of the present invention utilizes in the preparation process of Silicone-Modified Acrylate Resin contains double bond function simultaneously
The function monomer of energy group and hydroxyl ester group, can not only be hydrolyzed condensation, but also can carry out with acrylate monomer with organosilan
Free radical polymerization is dispersed in polyacrylic resin by random copolymerization, and can carry out condensation friendship with organosilan oligomer
Connection improves the compatibility of organosilicon and polyacrylate to obtain stable organosilicon modified crylic acid resin.
The organic-silicon-modified polyacrylic resin that technical solution of the present invention obtains has excellent hydrophobicity, heat resistance, together
When have lower surface can, preferable pollution resistance and to metal adhesion.
The technology of the present invention Silicone-Modified Acrylate Resin and organic-silicon-modified nanoparticle and conventional solidified dose, auxiliary agent
The formulation for coating material of equal acquisitions, is provided simultaneously with excellent hydrophobicity, heat resistance, antiseptic property and mechanical performance.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of acrylic resin and organosilicon modified crylic acid resin;
Fig. 2 is the thermal multigraph of acrylic resin and organosilicon modified crylic acid resin;
Fig. 3 is the contact angle figure of acrylic resin and organosilicon modified crylic acid resin;
Fig. 4 is that coating impregnates chemical impedance spectrogram after 600h, 1800h.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Embodiment 1
1. the preparation of silicone oligomer
By monomer 19.20g phenyl triethoxysilane, 11.84g dimethyl diethoxysilane, three second of 7.62g vinyl
Oxysilane mixed solution after reactor is added, stirs and is warming up to 80 DEG C, 9.36g distilled water and 0.09g hydrochloric acid is slowly added dropwise
Mixed solution is as hydrolysis material and catalyst, after being added dropwise, then after isothermal reaction 5h, starts to be evaporated under reduced pressure, pressure control
In 0.06MPa, the small molecule generated in reaction process and water are boiled off, room temperature is cooled to, adjusted pH to neutrality with ammonium hydroxide, had
Machine silicon oligomer.
2. the preparation of organosilicon modified crylic acid resin
6.25g organosilicon performed polymer is poured into three-necked flask, is added solvent (ethyl acetate: butyl acetate=1:1)
20g.After stirring and being warming up to 70 DEG C, dropwise addition acrylic acid mix monomer (8.2g methyl methacrylate, 5.3g butyl acrylate,
0.3g acrylic acid, 7.3g styrene, 4.5g methacrylic acid-beta-hydroxy ethyl ester) and (initiation of initiator 0.25g azodiisobutyronitrile
Agent has been dissolved in mix monomer), 90min or so is added dropwise.After being warming up to 80 DEG C, then isothermal reaction 1h, discharging.
3. organic modified nano SiO2Preparation
By 5g Nano-meter SiO_22(20nm) is scattered in 300g solvent (ethyl alcohol: water=3:1), after reactor is added, high speed dispersion
0.5g γ-methacryloxypropyl trimethoxy silane is slowly added dropwise after uniformly, in 70 DEG C of water-bath back flow reaction 8h, to
It is down to room temperature, product obtains organic modified nano SiO by centrifuge separation and ethanol washing2。
4. coating
By 80 parts of organosilicon modified crylic acid resins and 4 parts of organic modified nano SiO2It is added in dispersion machine and disperses, and add
Enter 30 parts of mixed solvents (butyl acetate: toluene: propylene glycol methyl ether acetate=3:3:2) and is used as diluent, after being uniformly dispersed,
16 parts of N75 curing agent (hexamethylene diisocyanate) are added, and amount to 3 parts of BYK series wetting agent, levelling agent, defoaming
After agent, uniformly it is applied to tinplate and carries out isothermal curing.
Embodiment 2
1. the preparation of silicone oligomer
By monomer 38.4g phenyl triethoxysilane, 23.68g dimethyl diethoxysilane, three second of 15.20g vinyl
Oxysilane mixed solution after reactor is added, stirs and is warming up to 80 DEG C, 26.2g distilled water and 0.17g hydrochloric acid is slowly added dropwise
Mixed solution is as hydrolysis material and catalyst, after being added dropwise, then after isothermal reaction 6h, starts to be evaporated under reduced pressure, pressure control
In 0.06MPa, the small molecule generated in reaction process and water are boiled off, room temperature is cooled to, adjusted pH to neutrality with ammonium hydroxide, had
Machine silicon oligomer.
2. the preparation of organosilicon modified crylic acid resin
6g organic-silicone prepolymer is poured into three-necked flask, is added solvent (ethyl acetate: butyl acetate=1:1)
20g.After stirring and being warming up to 70 DEG C, dropwise addition acrylic acid mix monomer (7.4g methyl methacrylate, 8.4g butyl acrylate,
0.5g acrylic acid, 6.6g styrene, 4.8g methacrylic acid-beta-hydroxy ethyl ester) and initiator azodiisobutyronitrile (initiator is solubilized
In mix monomer), 90min or so is added dropwise.After being warming up to 80 DEG C, then isothermal reaction 1h, discharging.
3. organic modified nano TiO2Preparation
By 5g nano-TiO2(25nm) is scattered in 300g solvent (ethyl alcohol: water=3:1), after reactor is added, high speed dispersion
0.5g γ-methacryloxypropyl trimethoxy silane is slowly added dropwise after uniformly, in 70 DEG C of water-bath back flow reaction 8h, to
It is down to room temperature, product obtains organic modified nano TiO by centrifuge separation and ethanol washing2。
4. coating
By 80 parts of organosilicon modified crylic acid resins and 5 parts of organic modified nano TiO2It is added in dispersion machine and disperses, and add
Enter 35 parts of mixed solvents (butyl acetate: toluene: propylene glycol methyl ether acetate=3:3:2) and is used as diluent, after being uniformly dispersed,
18 parts of N75 curing agent (hexamethylene diisocyanate) are added, and amount to 4 parts of BYK series wetting agent, levelling agent, defoaming
After agent, uniformly it is applied to tinplate and carries out isothermal curing.
Embodiment 3
As 1., 2. 1 step of embodiment prepares organosilicon modified crylic acid resin and nano modification SiO2。
80 parts of resins are added in dispersion machine with 5 parts of organically-modified mix nanoparticles and are dispersed, and it is molten that 35 parts of mixing are added
16 parts of N75 are added after being uniformly dispersed as diluent in agent (butyl acetate: toluene: propylene glycol methyl ether acetate=5:3:2)
Curing agent (hexamethylene diisocyanate), and 4 parts of BYK series wetting agent is amounted to, after levelling agent, defoaming agent, uniformly apply
In tinplate and carry out isothermal curing.
The performance test results of sample obtained by 1 Examples 1 to 3 of table
The organosilicon known to attached drawing 1 successfully grafts on acrylic resin.From attached drawing 2 as can be seen that passing through organosilicon
Acrylic resin modified initial decomposition temperature, decomposition mechanism corresponding temperature improve, organosilicon modified crylic acid resin heat
Weightlessness 5% and maximum weight loss rate temperature are respectively 320 DEG C and 428 DEG C, compared to 302 DEG C of pure acrylic resin and 405 DEG C,
18 DEG C and 23 DEG C have been respectively increased, illustrate it is organic-silicon-modified after can improve acrylic resin heat resistance.Such as attached drawing 3, process is organic
The acrylic contact angle of Si modification is significantly increased compared to 67.5 ° of Unmodified propylene's acid resin, is 87.5 °.By organic
Silicon nano is modified and after being prepared as coating, and hydrophobicity and corrosion resistance are improved.As embodiment 3 prepares a series of coatings
Afterwards, contact angle has different degrees of raising compared with 87.5 ° when being not added with, and wherein Maximum Contact angle reaches 108.4 °.Contact
Angle result illustrates that organic silicon nano particle, which is added, can be such that coating hydrophobicity further improves.Coating is measured by electro-chemical test
Corrosion resistance, as shown in Fig. 4, it is known that be added to nanoparticle coating after impregnating 1800h, coating impedance is in 109 Ω cm2
More than, keep good protective performance.
Claims (10)
1. a kind of preparation method of Silicone-Modified Acrylate Resin, it is characterised in that: obtain organosiloxane hydrolytic condensation
To organosilan oligomer, organosilan oligomer is first subjected to prepolymerization with part acrylic acid resin polymerization single polymerization monomer, then with it is remaining
Lower part acrylic resin polymerized monomer is polymerize, and organosilicon modified crylic acid resin is obtained;
The acrylic resin polymerized monomer includes soft monomer, hard monomer and function monomer;
The hard monomer include methyl acrylate, methyl methacrylate, ethyl methacrylate, n-BMA,
At least one of tert-butyl acrylate, styrene, acrylonitrile, acrylic acid;
The soft monomer includes ethyl acrylate, n-butyl acrylate, lauryl acrylate, acrylic acid-2-ethyl caproite, methyl
At least one of lauryl acrylate, n octyl methacrylate;
The function monomer includes 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid -2- hydroxyl second
At least one of ester, methacrylic acid -2- hydroxy propyl ester.
2. a kind of preparation method of Silicone-Modified Acrylate Resin according to claim 1, it is characterised in that: described
Organosiloxane includes methltriethoxysilone, dimethyl diethoxysilane, vinyltriethoxysilane, phenyl three
At least one of ethoxy radical siloxane.
3. a kind of preparation method of Silicone-Modified Acrylate Resin according to claim 1 or 2, it is characterised in that:
By R/Si value be 1.2~1.4 by organosiloxane, Ph/R value is 0.2~0.6 after mixing, acid solution to be added dropwise, 70~
3~6h is reacted at a temperature of 80 DEG C, obtains organosilan oligomer.
4. a kind of preparation method of Silicone-Modified Acrylate Resin according to claim 1, it is characterised in that: organic
The mass ratio of silane oligomer and soft monomer, hard monomer and function monomer is 15~30:20~50:40~70:5~25.
5. a kind of preparation method of Silicone-Modified Acrylate Resin according to claim 1, it is characterised in that: will have
The acrylic resin polymerized monomer of machine silane oligomer and 30~50% mass 75~85 DEG C progress polymerization reaction 1~2 hour
Afterwards, then in 1.5~2h remaining part acrylic resin polymerized monomer is dropped evenly into reaction system, insulation reaction 0.5
~1.5h is to get organosilicon modified crylic acid resin.
6. a kind of Silicone-Modified Acrylate Resin, it is characterised in that: by any one of Claims 1 to 5 preparation method
It obtains.
7. a kind of hydrophobic weather-proof acrylic resin modified coating of sustained release, it is characterised in that: change including organosilicon described in claim 6
Property acrylate, isocyanate curing agent, filler, solvent and auxiliary agent.
8. the hydrophobic weather-proof acrylic resin modified coating of sustained release of one kind according to claim 7, it is characterised in that: described to fill out
Material is silane-modified nanoparticle;The silane-modified nanoparticle includes silane-modified nano silica, silane-modified receives
At least one of rice titanium dioxide, silane-modified nano zine oxide.
9. the hydrophobic weather-proof acrylic resin modified coating of sustained release of one kind according to claim 7 or 8, it is characterised in that: packet
Include following content of component:
75~100 parts of Silicone-Modified Acrylate Resin;
10~20 parts of isocyanate curing agent;
1~10 part of filler;
30~50 parts of solvent;
2~8 parts of auxiliary agent.
10. the hydrophobic weather-proof acrylic resin modified coating of sustained release of one kind according to claim 9, it is characterised in that: isocyanide
Acid esters curing agent is selected from least one of De Shimo all N75, De Shimo all N3390, BASF HI100ap;
Solvent is selected from least one of butyl acetate, ethyl acetate, toluene, dimethylbenzene, propylene glycol methyl ether acetate;The auxiliary agent
At least one of BYK series levelling agent, defoaming agent, wetting agent, dispersing agent can be selected from.
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