CN105085771A - Waterborne acrylic resin and preparation method therefor - Google Patents
Waterborne acrylic resin and preparation method therefor Download PDFInfo
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- CN105085771A CN105085771A CN201510418885.1A CN201510418885A CN105085771A CN 105085771 A CN105085771 A CN 105085771A CN 201510418885 A CN201510418885 A CN 201510418885A CN 105085771 A CN105085771 A CN 105085771A
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- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 68
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 85
- 239000003999 initiator Substances 0.000 claims abstract description 62
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 acrylic ester Chemical class 0.000 claims description 33
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- 238000009413 insulation Methods 0.000 claims description 18
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 22
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000001502 supplementing effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229940074391 gallic acid Drugs 0.000 description 3
- 235000004515 gallic acid Nutrition 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002994 raw material Substances 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical group CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
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Abstract
The invention provides a method for preparing waterborne acrylic resin and the waterborne acrylic resin prepared by the method. According to the method, an environment-friendly solvent is used, firstly, a chain transfer agent is dissolved in the solvent, a mixture A containing an acrylate monomer mixture I, an initiator and the chain transfer agent is added into the solution, thus, polymerization reaction can be initiated at quite low temperatures, the rate of reaction is controlled through supplementing the initiator and the chain transfer agent into the system, then, a mixture B containing an acrylic monomer mixture II is added into the system, thus, the prepared waterborne acrylic resin has a core-shell structure and has hydrophilicity and hydrophobicity, and a paint film prepared from the waterborne acrylic resin has the properties of good hardness, adhesive power, impact resistance, water resistance and the like.
Description
Technical field
The invention belongs to Polymer Synthesizing field, in particular to a kind of method preparing water-borne acrylic resin and the water-borne acrylic resin obtained by described method.
Background technology
At present, solvent type acrylic resin product occupies an important position in China, but solvent type acrylic resin because of its VOC value high, very unfriendly to environmental and human health impacts, thus be faced with the danger of withdrawing from the market.In addition the environmental consciousness of people is in continuous improve, and a large amount of environmentally friendly machines goes out mutually then, receives the attention of the whole society.Wherein, water-borne acrylic resin then more obtains the favor of people.Such as, chemical giant's Bayer, BASF, Du Pont etc. of Germany are for the Innovation Input great effort of water soluble acrylic acid.
Water-borne acrylic resin take water as solvent, nonpoisonous and tasteless, to have cost low, the feature such as free from environmental pollution.In addition, the preparation of water-borne acrylic coatings is simple and convenient especially, according to practical situation flexible design, one or more following auxiliary agents can be added according to actual demand in water-borne acrylic resin: thickening material, defoamer, siccative, antimildew disinfectant, inhibiter etc.
Although water-borne acrylic resin have pollution-free, nontoxicity, nonirritant, gloss are better, chemical resistant properties good, stability is high and production safety, the advantage such as cheap, but it self also has not eliminable shortcoming, be mainly manifested in hot sticky cold crisp after the drying of resin film forming, anti-after tackiness is poor, thermotolerance is not good, water tolerance is permanent, impact-resistance is poor, thus the Application Areas limiting water-borne acrylic resin is restricted.Therefore, in order to overcome the above-mentioned shortcoming of water-borne acrylic resin, need to carry out modification to water-borne acrylic resin.
In the prior art, mostly adopt physical blending process, by silane coupling agent directly and water-borne acrylic resin blended.Although this method of modifying is simple and convenient, the stability of emulsion after blended is poor, easily produces two-phase laminated flow, and does not have chemical bonds between acrylic polymer and base material, and the performance of acrylic resin can not be improved.
In addition, in some prior aries, by chemic modified method, the silane coupling agent containing unsaturated link(age) is incorporated in the skeleton of water-borne acrylic resin, obtains multipolymer, thus improve the performance of acrylic resin.Although this method improves the performance of water-borne acrylic resin to a certain extent, the film-forming properties of the water-borne acrylic resin obtained is bad, low in glossiness, less stable, solid content is lower, in addition, in building-up process, easily make emulsion viscosity large, bad emulsification.
Therefore, in order to overcome the above-mentioned shortcoming of water-borne acrylic resin, need to carry out modification to water-borne acrylic resin.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: slowly drip in the solvent system being dissolved with chain-transfer agent and comprise acrylic ester monomer mixture I, the mixture A of initiator and chain-transfer agent, add initiator and chain-transfer agent, slowly drip in system again and comprise acrylic monomer mixtures II, the mixture B of initiator and chain-transfer agent, add initiator and chain-transfer agent again, last regulation system pH, water-borne acrylic resin can be obtained after adding water, obtained water-borne acrylic resin can not add solidifying agent in use, obtained acrylic resin paint film is close with the conventional acrylic resin paint film property using solidifying agent obtained, thus complete the present invention.
The object of the present invention is to provide following aspect:
First aspect, the invention provides a kind of method preparing water-based acrylic resin, it is characterized in that, the method comprises the following steps:
(1) in container, add solvent and chain-transfer agent, optionally stir and heat up;
(2) the mixture A comprising acrylic ester monomer mixture I, silane coupling agent and initiator is added in the system obtained to step 1;
(3) add initiator and chain-transfer agent in the system obtained to step 2, reaction, optionally carry out under insulation;
(4) the mixture B comprising acrylic monomer mixtures II, silane coupling agent and initiator is added in the system obtained to step 3;
(5) add initiator and chain-transfer agent in the system obtained to step 4, reaction, optionally carry out under insulation;
(6) pH of system that obtains of regulating step 5, adds water, stirs, obtain water-borne acrylic resin.
Second aspect, the present invention also provides a kind of water-borne acrylic resin obtained by aforesaid method, wherein containing the solvent added in preparation process.
The third aspect, the present invention also provides the using method of water-borne acrylic resin described in above-mentioned second aspect, it is characterized in that, described water-borne acrylic resin does not add solidifying agent in use.
Accompanying drawing explanation
Fig. 1 illustrates that embodiment 1 obtains the testing graininess result of sample;
Fig. 2 illustrates that embodiment 1 obtains the grain size distribution of sample;
Fig. 3 illustrates that embodiment 2 obtains the testing graininess result of sample;
Fig. 4 illustrates that embodiment 2 obtains the grain size distribution of sample;
Fig. 5 illustrates that embodiment 3 obtains the testing graininess result of sample;
Fig. 6 illustrates that embodiment 3 obtains the grain size distribution of sample;
Fig. 7 illustrates and obtains after sample obtains paint film by embodiment 1, water droplet form photo on it;
Fig. 8 illustrates and obtains after sample obtains paint film by embodiment 2, water droplet form photo on it;
Fig. 9 illustrates and obtains after sample obtains paint film by embodiment 3, water droplet form photo on it.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will illustrate along with these and become more clear, clear and definite.
Below in detail the present invention is described in detail.
According to a first aspect of the invention, provide a kind of method preparing water-based acrylic resin, it is characterized in that, the method comprises the following steps:
Step 1, adds solvent and chain-transfer agent in container, optionally stirs and heats up.
In the present invention, described solvent is organic solvent, be preferably boiling point higher than 85 DEG C, the organic solvent that volatility is low simultaneously, the organic solvent of particularly preferably low-toxicity in above-mentioned organic solvent, described solvent is selected from alcoholic solvent, esters solvent, ketones solvent, varsol, aromatic solvents and ether solvent, be preferably Virahol, butanols, butyl glycol ether, ethyl acetate, pimelinketone, nitroethane, hexanaphthene, trieline, heptane, octane, Nitromethane 99Min., acetonitrile, propionitrile, toluene, p-Xylol, glycol dimethyl ether, methyl glycol and glycol monoethyl ether, be more preferably butyl glycol ether, toluene, heptane, butanols, methyl glycol, octane, ethyl acetate, glycol monoethyl ether and p-Xylol, be more preferably butyl glycol ether.
Above-mentioned solvent can make temperature of reaction remain on 60 DEG C ~ 95 DEG C, be preferably 70 ~ 90 DEG C, simultaneously, in reaction, the kick off temperature of initiator used is also near this temperature range, and even in this temperature range, thus raw material can carry out polyreaction at said temperatures, and there is suitable velocity of initiation and polymerization velocity, thus polyreaction can be carried out under the kick off temperature of initiator, preferably, polyreaction can be carried out under the reflux state of temperature-stable.
The present inventor finds, when using aliphatics mercaptan type chain transfer agent, the narrow molecular weight distribution of obtained water-borne acrylic resin, stable performance, therefore, in the present invention, described chain-transfer agent be selected from aliphatics mercaptan one or more, especially, chain-transfer agent is preferably lauryl mercaptan and Stearyl mercaptan, be more preferably in n-dodecyl mercaptan, tertiary lauryl mercaptan and Octadecane base mercaptan one or more, further, be preferably n-dodecyl mercaptan.
In the present invention, first chain-transfer agent is dissolved in solvent, fully mix under agitation, it is excessive in a large number relative to other raw material added in subsequent step to make system Chain transfer agent, the macromole that the acrylic ester monomer mixture I of instillation system can be made to generate forms small molecules fast and is cross-linked, make the acrylate copolymer molecular weight distribution that obtains narrower, also make to prepare acrylic acid polyreaction more abundant.
In the present invention, optionally the system being dissolved with chain-transfer agent is heated up, making other raw material added in subsequent step when being added into reaction system, directly can be placed in the environment of applicable polymerization reaction take place, reaction is carried out fast.
In the present invention, first react at cold condition, generally at 60 ~ 95 DEG C, preferably react under 70 ~ 90 DEG C of conditions, like this, heating in water bath just can realize; And avoid too high due to temperature and cause product performance deterioration; In addition, produce under described temperature condition, security is high, and easy handling is pollution-free, can obtain the good water-and acrylate of various aspects of performance in the mode of stable, safety, environmental protection.
When the system temperature being dissolved with chain-transfer agent is higher than 95 DEG C, the molecule crosslinked density of obtained water soluble acrylic acid is excessive, poorly water-soluble, and color becomes coke yellow, even gel reaction occurs; When the system temperature being dissolved with chain-transfer agent is lower than 60 DEG C, heated up slow, product property poor reproducibility, the performance such as water tolerance and sticking power is also poor.
In step 1 of the present invention, described solvent is 100 ~ 200 weight parts, is preferably 120 ~ 180 weight parts, as 150 weight parts.
In step 1 of the present invention, described chain-transfer agent is 2 ~ 8 weight parts, is preferably 3 ~ 6 weight parts, as 4 weight parts.
Step 2, adds the mixture A comprising acrylic ester monomer mixture I, silane coupling agent and initiator in the system that step 1 obtains.
In the present invention, described acrylic ester monomer mixture I comprises the component of following weight proportion,
Methyl methacrylate 40 ~ 80 weight part
Butyl acrylate 40 ~ 80 weight part
Hydroxyethyl methylacrylate 20 ~ 50 weight part,
Be preferably,
Methyl methacrylate 50 ~ 70 weight part
Butyl acrylate 50 ~ 70 weight part
Hydroxyethyl methylacrylate 30 ~ 40 weight part,
Be more preferably,
Methyl methacrylate 58 weight part
Butyl acrylate 53 weight part
Hydroxyethyl methylacrylate 35 weight part.
The hybrid mode of the present invention to aforesaid propylene esters of gallic acid monomer mixture I is not particularly limited to, the mode that in prior art, said mixture can mix by any one can be used, as mechanical stirring, magnetic agitation, the modes such as sonic oscillation, preferably use the mode of sonic oscillation to mix.
The present inventor finds, the hydrolysable group existed in silane coupling agent, can make the water-borne acrylic resin obtained when film forming, forms one and passes network structure mutually, not only improve the amalgamation of water-borne acrylic resin when film forming, and further improve the shock resistance of film.
In addition, silane coupling agent is added when preparing water-borne acrylic resin, can improve obtained water-borne acrylic resin at suprabasil sticking power, not be bound by any theory, the present inventor thiss is presumably because that in silane coupling agent, Si-O key has higher ionization trend and very high bond energy.
In the present invention, described silane coupling agent can by shown in following formula:
YSiX
3
Wherein,
Y is unsaturated thiazolinyl, is preferably: CH
2=CH (CH
2)
n-, wherein, n is 1 ~ 8, further, and CH
2=CH (CH
2)
n-be preferably CH
2=C (CH
3)-, CH
2=CH-, especially, preferred CH
2=CH-,
X is hydrolysable group, is preferably :-Cl ,-OMe ,-OEt ,-OC
2h
4oCH
3,-OSiMe
3and-OAc, especially, preferably-OC
2h
5.
In the present invention, silane coupling agent preferred vinyl triethoxyl silane.
In the present invention, be 100 ~ 210 weight parts based on acrylic ester monomer mixture I, the addition of silane coupling agent is 5 ~ 10 weight parts, is preferably 6 ~ 9 weight parts, is more preferably 7 ~ 8 weight parts.
In step 2 of the present invention, the not special restriction of kind of initiator, after initiator is heated, can produce radical initiation reaction.
Described initiator is selected from one or more of following initiator: acyl class superoxide is as benzoyl peroxide, hydroperoxide are as tertbutyl peroxide, dialkyl peroxide is as di-t-butyl peroxide, and azo-initiator is as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
In a preferred embodiment, initiator is Diisopropyl azodicarboxylate (AIBN).
The present inventor finds, AIBN is that acrylate copolymer prepared by initiator not easily gelatin phenomenon occurs, and molecular weight distribution is narrower, is conducive to the water-soluble acrylic ester polymkeric substance preparing higher solids content.
In step 2 of the present invention, be 100 ~ 210 weight parts based on acrylic ester monomer mixture I, the addition of the initiator in mixture A is 1 ~ 5 weight part, is preferably 2 ~ 4 weight parts, as 3 weight parts.
In the present invention, add again in the system of step 1 after preferably aforesaid propylene esters of gallic acid monomer mixture I, silane coupling agent and initiator being mixed, the present invention is not particularly limited to hybrid mode, the mode that in prior art, said mixture can mix by any one can be used, as mechanical stirring, magnetic agitation, the modes such as sonic oscillation, preferably use the mode of sonic oscillation to mix.
One of the present invention preferred embodiment in, by aforesaid propylene esters of gallic acid monomer mixture I, silane coupling agent and initiator after mixing, carry out filtration treatment, remove wherein insoluble impurities, be beneficial to the follow-up of reaction and carry out, the present invention is not particularly limited to the mode of filtering, the mode of any one solid-liquid separation in prior art can be used, as natural filtration, filtration under diminished pressure etc., preferably use filtration under diminished pressure.
In the present invention, described mixture A, preferably in 1 ~ 5 hour, in being preferably 2 ~ 4 hours, dropwised in 3 hours.When rate of addition is excessively slow, time for adding is long, is greater than 5 constantly little, the unstable properties of obtained acrylate copolymer, poor reproducibility; When rate of addition is too fast, time for adding is too short, is less than 1 constantly little, and obtained acrylate copolymer molecular weight distribution is wide, and intermolecular cross-linking obtains uneven.
In step 2 of the present invention, when adding mixture A, the temperature controlling reaction system is 60 DEG C ~ 95 DEG C, preferably 70 DEG C ~ 90 DEG C, as 80 DEG C, and 85 DEG C or 90 DEG C.
The present invention preferably adopts the mode of dropping to add mixture A in the system of step 1.
Step 3, adds initiator and chain-transfer agent in the system that step 2 obtains, reaction, optionally carries out under insulation.
The present inventor finds, after being dropwised by mixture A, then in reaction system, adds the carrying out that initiator and chain-transfer agent can accelerate polyreaction, and can control polyreaction and carry out under suitable speed.
In step 3 of the present invention, the range of choice of described initiator is identical with the range of choice of initiator described in step 2, preferably, identical with initiator described in step 2.
In step 3 of the present invention, be 100 ~ 210 weight parts based on acrylic ester monomer mixture I in step 1, described initiator is 0.3 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, as 0.6 weight part.
In step 3 of the present invention, the range of choice of described chain-transfer agent is identical with the range of choice of chain-transfer agent described in step 2, preferably, identical with chain-transfer agent described in step 2.
In step 3 of the present invention, be 100 ~ 210 weight parts based on acrylic ester monomer mixture I in step 1, described chain-transfer agent is 0.3 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, as 0.6 weight part.
In step 3 of the present invention, preferably initiator and chain-transfer agent are dissolved in solvent and add in reaction system again, thus it is unbalanced to avoid the reaction caused because partial concn is excessive, also make the acrylate copolymer narrow molecular weight distribution generated.
In step 3 of the present invention, the range of choice of described solvent is identical with the range of choice of solvent described in step 1, preferably, same with solvent phase described in step 1.
In step 3 of the present invention, be 100 ~ 210 weight parts based on acrylic ester monomer mixture I in step 1, described solvent is 10 ~ 30 weight parts, is preferably 15 ~ 25 weight parts, as 20 weight parts.
In step 3 of the present invention, after adding initiator and chain-transfer agent, preferably insulation reaction under 60 DEG C ~ 90 DEG C conditions, the time of preferred insulation reaction was 0.5 ~ 2 hour, as 1 hour.
Step 4, adds the mixture B comprising acrylic monomer mixtures II, silane coupling agent and initiator in the system that step 3 obtains.
The present inventor finds, mixture B is added in the system that step 3 is obtained, enhance the wetting ability of obtained water-borne acrylic resin, make it can either stable existence in aqueous, there is again good water tolerance simultaneously, be not bound by any theory, the present inventor thinks, acrylic monomer mixtures II in the mixture B that step 4 adds with the obtained polymkeric substance of step 3 for kernel, be polymerized at its Surface coating, form double-deck water-borne acrylic resin, wherein, there is not carboxyl freely in the acrylic ester polymer surface that step 3 obtains, show as hydrophobicity, and introduce acrylic compounds in the mixture B that step 4 adds, and hydroxyl is not the avtive spot of polyreaction freely, therefore, water-borne acrylic resin obtained after step 4, there is carboxyl in its surface freely, thus, add the wetting ability of water-borne acrylic resin, and then, the water-borne acrylic resin obtained through step 3 and step 4 had both had good wetting ability, namely, water-soluble enhancing, there is again good water tolerance simultaneously.
In step 4 of the present invention, described acrylic monomer mixtures II comprises the component of following weight proportion,
Be preferably,
Be more preferably,
In step 4 of the present invention, the range of choice of described silane coupling agent is identical with the range of choice of silane coupling agent described in step 2, preferably, identical with silane coupling agent described in step 2.
In step 4 of the present invention, be 158 ~ 285 weight parts based on acrylic monomer mixtures II, silane coupling agent is 8 ~ 15 weight parts, is preferably 9 ~ 13 weight parts, as 11 weight parts.
In step 4 of the present invention, the range of choice of described initiator is identical with the range of choice of initiator described in step 2, preferably, identical with initiator described in step 2.
In step 4 of the present invention, be 158 ~ 285 weight parts based on acrylic monomer mixtures II, initiator is 3 ~ 8 weight parts, is preferably 4 ~ 6 weight parts, as 5 weight parts.
In a kind of preferred implementation of the present invention, add again in the system of step 4 after aforesaid propylene acrylic monomer mixtures II, silane coupling agent and initiator are mixed, the present invention is not particularly limited to hybrid mode, the mode that in prior art, said mixture can mix by any one can be used, as mechanical stirring, magnetic agitation, the modes such as sonic oscillation, preferably use the mode of sonic oscillation to mix.
One of the present invention preferred embodiment in, by aforesaid propylene acrylic monomer mixtures II, silane coupling agent and initiator after mixing, carry out filtration treatment, remove wherein insoluble impurities, be beneficial to the follow-up of reaction and carry out, the present invention is not particularly limited to the mode of filtering, the mode of any one solid-liquid separation in prior art can be used, as natural filtration, filtration under diminished pressure etc., preferably use filtration under diminished pressure.
In the present invention, described mixture B, preferably in 1 ~ 5 hour, in being preferably 2 ~ 4 hours, dropwised in 3.5 hours.When rate of addition is excessively slow, time for adding is long, is greater than 5 constantly little, the unstable properties of obtained acrylate copolymer, poor reproducibility; When rate of addition is too fast, time for adding is too short, is less than 1 constantly little, and obtained acrylate copolymer molecular weight distribution is wide, and intermolecular cross-linking obtains uneven.
In step 4 of the present invention, when adding mixture B, the temperature controlling reaction system is 60 DEG C ~ 95 DEG C, preferably 70 DEG C ~ 90 DEG C, as 80 DEG C, 85 DEG C or 90 DEG C, more preferably identical with temperature of reaction in step 3.
The present invention preferably adopts the mode of dropping to add mixture B in the system of step 3.
Step 5, adds initiator, chain-transfer agent in the system that step 4 obtains, reaction, optionally carries out under insulation.
The present inventor finds, after being dropwised by mixture B, then in reaction system, adds the carrying out that initiator and chain-transfer agent can accelerate polyreaction, and can control polyreaction and carry out under suitable speed.
In step 5 of the present invention, the range of choice of described initiator is identical with the range of choice of initiator described in step 2, preferably, identical with initiator described in step 2.
In step 5 of the present invention, be 158 ~ 285 weight parts based on acrylic monomer mixtures II in step 4, described initiator is 0.5 ~ 2 weight part, is preferably 0.8 ~ 1.5 weight part, as 1.2 weight parts.
In step 5 of the present invention, the range of choice of described chain-transfer agent is identical with the range of choice of chain-transfer agent described in step 2, preferably, identical with chain-transfer agent described in step 2.
In step 5 of the present invention, be 158 ~ 285 weight parts based on acrylic monomer mixtures II in step 4, described chain-transfer agent is 0.3 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, as 0.6 weight part.
In step 5 of the present invention, preferably initiator and chain-transfer agent are dissolved in solvent and add in reaction system again, thus it is unbalanced to avoid the reaction caused because partial concn is excessive, also make the acrylate copolymer narrow molecular weight distribution generated.
In step 5 of the present invention, the range of choice of described solvent is identical with the range of choice of solvent described in step 1, preferably, same with solvent phase described in step 1.
In step 5 of the present invention, be 158 ~ 285 weight parts based on acrylic ester monomer mixtures II in step 4, described solvent is 10 ~ 50 weight parts, is preferably 20 ~ 40 weight parts, as 30 weight parts.
In step 5 of the present invention, after adding mixture B, preferably insulation reaction under 60 DEG C ~ 90 DEG C conditions, the time of preferred insulation reaction was 0.5 ~ 2 hour, as 1 hour.
Step 6, the pH of the system that regulating step 5 obtains, after treatment, obtains water-borne acrylic resin.
The present inventor finds, add organic bases regulation system pH in reaction system after, acrylate copolymer surface freely carboxyl can be reacted with described organic bases and formed salt, thus making acrylate copolymer stable existence in a salt form, obtained end product water-borne acrylic resin is after film forming, and paint film is plentiful, planeness is good, thus glossiness is high after making resin film forming, meanwhile, the wetting ability of acrylate copolymer is too increased.
In the present invention, described organic bases is small molecules organic bases, described small molecules organic bases is aminated compounds, as, one or more in diethylamine, triethylamine, N, N-dimethylethanolamine, diethanolamine, thanomin or ammoniacal liquor, be preferably N, N-dimethylethanolamine and/or diethanolamine, be more preferably N, N-dimethylethanolamine.
Be 158 ~ 285 weight parts based on acrylic ester monomer mixtures II in step 4, described organic bases is 8 ~ 15 weight parts, is preferably 10 ~ 13 weight parts, as 12 weight parts.By adding organic bases above, the pH of system is made to be weakly alkaline.
In the present invention, described process comprises and adds water and/or stir.
Adding water to adding in the system after organic bases, stirring, directly can obtain the water-borne acrylic resin of excellent property, and not need the solvent in removing system.
Described water is one or more in deionized water, distilled water, tap water and pure water, preferred deionized water.
Be 100 ~ 210 parts by weight with Acrylic Acid Monomer mixture I in step 2, the add-on of described water is 500 ~ 800 weight parts, is preferably 600 ~ 700 weight parts, as 660 weight parts.
When routine prepares water-borne acrylic resin, the mode of usual employing distillation removes the solvent in preparation system, need the time consumed to be about and prepare 1/2 of water-borne acrylic resin total time, this not only wastes the plenty of time, and it is higher owing to distilling temperature used, therefore, need to consume mass energy, so, this step of solvent removed in ordinary method in preparation system is not only the certainly fast link preparing water-borne acrylic resin speed, but also can cause the massive losses of the energy and the pollution of environment.
And the acrylic resin of prepared in accordance with the method for the present invention, do not need the solvent in removing system, and end product water-borne acrylic resin can be obtained directly to adding water in system, not only save a large amount of time costs, the production efficiency greatly improved, and reduce the loss of the energy, save Financial cost; Meanwhile, solvent used in the present invention is environmentally friendly green solvent, and it can not cause environmental pollution.
The water-borne acrylic resin that ordinary method obtains in use, need to add the auxiliary agents such as solidifying agent, and the water-borne acrylic resin obtained according to the inventive method does not need to add the auxiliary agents such as solidifying agent in use, the performance of obtained water soluble acrylic acid paint film is suitable with the performance of water soluble acrylic acid paint film of the prior art, and the performance even in hardness, shock resistance, sticking power and contact angle etc. is better than water soluble acrylic acid paint film of the prior art.
In the present invention one preferred embodiment, after completion of the reaction, system is made to be cooled to 40 DEG C ~ 60 DEG C, then the pH of regulation system, the present invention is not particularly limited to cool-down method and/or cooling conditions, can be naturally cooling, also can for artificially forcing cooling.
According to water-borne acrylic resin provided by the invention and preparation method thereof, there is following beneficial effect:
(1) described method is reacted in green organic solvent, does not need to remove unnecessary solvent, directly adds emulsifying water and namely obtains product, save a large amount of preparation time, save energy, non-environmental-pollution, environmental protection after polyreaction;
(2) the method adopts radical polymerization MULTILAYER COMPOSITE technology, and preparation condition is controlled;
(3) acrylate copolymer that described method is obtained at least has hydrophobic cores and hydrophilic surface coating double-layer structure, thus obtained water-borne acrylic resin had both had good wetting ability, has again good water tolerance simultaneously;
(4) obtained water-borne acrylic resin narrow molecular weight distribution, stable performance;
(5) obtained water-borne acrylic resin does not need to add any solidifying agent in use.
Embodiment
embodiment 1
(1) in the 2000mL four-hole boiling flask that agitator, reflux exchanger and separating funnel are housed, add 150g butyl glycol ether, 4g n-dodecyl mereaptan, starting agitator bath temperature control temperature is 80 DEG C;
(2) mixture A (methyl methacrylate 57.8g, butyl acrylate 52.6g, hydroxyethyl methacrylate second fat 34.6g, vinyl three TMOS 7.26g, Diisopropyl azodicarboxylate 3g, filter after ultrasonic disperse) is dripped with about 3h;
(3) 0.6g Diisopropyl azodicarboxylate, 0.5g n-dodecyl mereaptan, 20g butyl glycol ether (directly adding after ultrasonic disperse) is added, insulation reaction 1h at 80 DEG C in the system obtained to step 2,
(4) mixture B (methyl methacrylate 86.8g, methacrylic acid 12g, butyl acrylate 79g, hydroxyethyl methacrylate second fat 52g, vinyl three TMOS 11.5g, Diisopropyl azodicarboxylate 5g is dripped in the system obtained to step 3, filter after ultrasonic disperse), about 3.5h drips off
(5) add 1.2g Diisopropyl azodicarboxylate, 0.6g n-dodecyl mereaptan, 30g butyl glycol ether (directly adding after ultrasonic disperse) in the system obtained to step 4, at 80 DEG C, continue insulation reaction 1h.
(6) add 12g dimethylethanolamine in the system obtained in step 5, stir about regulates pH in 10 minutes, adds 600g distilled water emulsification 0.5h, obtained water-borne acrylic resin.
embodiment 2
(1) in the 2000mL four-hole boiling flask that agitator, reflux exchanger and separating funnel are housed, add 180g butyl glycol ether, the positive stearylmercaptan of 6g, starting agitator bath temperature control temperature is 85 DEG C;
(2) mixture A (methyl methacrylate 80g, butyl acrylate 70g, hydroxyethyl methacrylate second fat 40g, vinyl three TMOS 6g, Diisopropyl azodicarboxylate 5g, filter after ultrasonic disperse) is dripped with about 2h;
(3) 0.3g Diisopropyl azodicarboxylate, the positive stearylmercaptan of 0.8g, 10g butyl glycol ether (directly adding after ultrasonic disperse) is added, insulation reaction 1h at 85 DEG C in the system obtained to step 2,
(4) mixture B (methyl methacrylate 100g, methacrylic acid 15g, butyl acrylate 60g, hydroxyethyl methacrylate second fat 70g, vinyl three TMOS 8g, Diisopropyl azodicarboxylate 8g is dripped in the system obtained to step 3, filter after ultrasonic disperse), about 2h drips off
(5) add 0.5g Diisopropyl azodicarboxylate, the positive stearylmercaptan of 0.8g, 50g butyl glycol ether (directly adding after ultrasonic disperse) in the system obtained to step 4, at 85 DEG C, continue insulation reaction 0.5h.
(6) add 15g dimethylethanolamine in the system obtained in step 5, stir about regulates pH in 10 minutes, adds 600g distilled water emulsification 0.5h, obtained water-borne acrylic resin.
embodiment 3
(1) in the 2000mL four-hole boiling flask that agitator, reflux exchanger and separating funnel are housed, add 120g butyl glycol ether, 3g n-dodecyl mereaptan, starting agitator bath temperature control temperature is 90 DEG C;
(2) mixture A (methyl methacrylate 70g, butyl acrylate 80g, hydroxyethyl methacrylate second fat 30g, vinyl three TMOS 9g, Diisopropyl azodicarboxylate 1g, filter after ultrasonic disperse) is dripped with about 5h;
(3) 0.8g Diisopropyl azodicarboxylate, 0.4g n-dodecyl mereaptan, 30g butyl glycol ether (directly adding after ultrasonic disperse) is added, insulation reaction 1h at 90 DEG C in the system obtained to step 2,
(4) mixture B (methyl methacrylate 60g, methacrylic acid 8g, butyl acrylate 100g, hydroxyethyl methacrylate second fat 30g, vinyl three TMOS 15g, Diisopropyl azodicarboxylate 3g is dripped in the system obtained to step 3, filter after ultrasonic disperse), about 5h drips off
(5) add 2g Diisopropyl azodicarboxylate, 0.3g n-dodecyl mereaptan, 10g butyl glycol ether (directly adding after ultrasonic disperse) in the system obtained to step 4, at 90 DEG C, continue insulation reaction 2h.
(6) add 10g dimethylethanolamine in the system obtained in step 5, stir about regulates pH in 10 minutes, adds 600g distilled water emulsification 0.5h, obtained water-borne acrylic resin.
Comparative example
comparative example 1 (using methyl alcohol as solvent)
This comparative example method therefor is similar to embodiment 1, and difference is only to substitute butyl glycol ether as solvent with methyl alcohol.
It increases step 5 before step 6 after step 5 ' for the methyl alcohol in removing system, step 5 ' be specially:
System step 5 obtained under vacuum, is heated to 60 DEG C and revolves steaming, removing solvent methanol wherein, 24 hours consuming time.
Experimental example
(1) paint film is prepared:
By the sample that embodiment 1 ~ 3 and comparative example 1 ~ 3 obtain, be directly coated in metal sheet surface, natural surface drying.
(2) mensuration of product solid content
Get one piece of masking foil and claim its weight, be designated as a, after testing sample is spread upon masking foil surface uniformly, weigh its weight, be designated as b, the masking foil after coated sample being placed on temperature is dry 30 minutes at 120 DEG C, claim its weight, be designated as m, then the solid content n of sample calculates according to following formula:
n＝(m-a)/(b-a)。
(3) mensuration of paint film adhesion
Draw # font with paint film lattice drawing instrument and draw lattice, with adhesive tape be adjacent to rear pull fast to draw to observe draw the change at lattice place, if not having pull-away to be namely defined as 0 grade, to come off on a small quantity is 1 grade, coming off in a large number is 2 grades.
(4) mensuration of paint film shock resistance
Du Pont's shock resistance instrument is adopted to measure, at the counterweight of upper ends certainweight, place a pair punching groove below and impact pestle, tinplate is placed on the centre of groove and pestle, and counterweight pounds the impact pestle immediately below hitting to measure the shock resistance of paint film at certain height freely falling body.Here just adopt the weight of counterweight and highly demarcate the size of shock resistance.
(5) mensuration of hardness of paint film
Draw the iron plate of spraying successively with Type B BH type H type 2H type 3H type pencil 45 degree, observe the situation of the film on iron plate.
(6) mensuration of paint film water tolerance
Paint film is immersed in tap water, observe water resistance, until paint film starts whiting take out timing.
(7) the absorptive mensuration of paint film
The iron plate of having polished is weighed, is designated as A, then sample is sprayed on this iron plate, air-dry, put into 80 DEG C of baking ovens and dry four hours, take out cooling, weigh, be designated as B, finally the iron plate being coated with sample be fully immersed in water, take out after 24 hours, blot with the water of thieving paper by its surface, weigh, be designated as C, its water-intake rate N calculates according to the following formula:
N＝(C-A)/(B-A)。
(8) mensuration of water-borne acrylic resin particle diameter
The beaker of 100ml put into by the coating that takes a morsel, and adds 50ml water, and ultrasonic 5-10 minute in ultrasonic apparatus, measures the size of its particle diameter with particle instrument, and record data.
(9) mensuration of paint film contact angle
The iron plate of having polished is weighed, be designated as A, then sample is sprayed on this iron plate, air-dry, put into 80 DEG C of baking ovens to dry four hours, take out cooling, contact angle instrument (model JCY-1, sharp Chemical Company of Shenzhen three) is measured to the iron plate through above-mentioned process and measures its contact angle.
experimental example 1
This experimental example specimen in use is the obtained sample of embodiment 1 ~ 3 and comparative example 1 ~ 3 or obtains paint film with above-mentioned sample, and the method according to above-mentioned (two) ~ (nine) measures its respective performances, and result is as shown in table 1 below,
Table 1
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. prepare a method for water-based acrylic resin, it is characterized in that, the method comprises the following steps:
(1) in container, add solvent and chain-transfer agent, optionally stir and heat up;
(2) the mixture A comprising acrylic ester monomer mixture I, silane coupling agent and initiator is added in the system obtained to step 1;
(3) add initiator and chain-transfer agent in the system obtained to step 2, reaction, optionally carry out under insulation;
(4) the mixture B comprising acrylic monomer mixtures II, silane coupling agent and initiator is added in the system obtained to step 3;
(5) add initiator and chain-transfer agent in the system obtained to step 4, reaction, optionally carry out under insulation;
(6) pH of system that obtains of regulating step 5, obtains water-borne acrylic resin after treatment.
2. method according to claim 1, is characterized in that, in step 1,
Described solvent is organic solvent, and be preferably boiling point higher than 85 DEG C, the organic solvent that volatility is low simultaneously, is preferably selected from alcoholic solvent, esters solvent, ketones solvent, varsol, aromatic solvents and ether solvent; And/or
Described chain-transfer agent is aliphatics mercaptan type chain transfer agent, is preferably lauryl mercaptan and Stearyl mercaptan; And/or
Described solvent is 100 ~ 200 weight parts, is preferably 120 ~ 180 weight parts, as 150 weight parts; And/or
Described chain-transfer agent is 2 ~ 8 weight parts, is preferably 3 ~ 6 weight parts, as 4 weight parts; And/or
Be warming up to 60 DEG C ~ 95 DEG C, be preferably 70 ~ 90 DEG C.
3. method according to claim 1 and 2, is characterized in that, in step 2,
Described acrylic ester monomer mixture I comprises the component of following weight proportion,
Methyl methacrylate 40 ~ 80 weight part
Butyl acrylate 40 ~ 80 weight part
Hydroxyethyl methylacrylate 20 ~ 50 weight part; And/or
Described silane coupling agent can by shown in following formula:
YSiX
3
Wherein,
Y is unsaturated thiazolinyl, is preferably: CH
2=CH (CH
2)
n-, wherein, n is 1 ~ 8, further, and CH
2=CH (CH
2) n-is preferably CH
2=C (CH
3)-, CH
2=CH-, especially, preferred CH
2=CH-,
X is hydrolysable group, is preferably :-Cl ,-OMe ,-OEt ,-OC
2h
4oCH
3,-OSiMe
3and-OAc, especially, preferably-OC
2h
5;
Be 100 ~ 210 weight parts based on acrylic ester monomer mixture I, the addition of silane coupling agent is 5 ~ 10 weight parts, is preferably 6 ~ 9 weight parts, is more preferably 7 ~ 8 weight parts; And/or
Described initiator is selected from one or more of following initiator: acyl class superoxide is as benzoyl peroxide, hydroperoxide are as tertbutyl peroxide, dialkyl peroxide is as di-t-butyl peroxide, and azo-initiator is as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile); And/or
Be 100 ~ 210 weight parts based on acrylic ester monomer mixture I, the addition of the initiator in mixture A is 1 ~ 5 weight part, is preferably 2 ~ 4 weight parts, as 3 weight parts.
4., according to the method one of claims 1 to 3 Suo Shu, it is characterized in that, in step 2,
Described mixture A, preferably in 1 ~ 5 hour, in being preferably 2 ~ 4 hours, dropwised in 3 hours; And/or
The temperature controlling reaction system is 60 DEG C ~ 95 DEG C, preferably 70 DEG C ~ 90 DEG C, as 80 DEG C, and 85 DEG C or 90 DEG C.
5., according to the method one of Claims 1 to 4 Suo Shu, it is characterized in that, in step 3,
The range of choice of described initiator is identical with the range of choice of initiator described in step 2; And/or
Be 100 ~ 210 weight parts based on acrylic ester monomer mixture I in step 1, described initiator is 0.3 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, as 0.6 weight part; And/or
The range of choice of described chain-transfer agent is identical with the range of choice of chain-transfer agent described in step 2; And/or
Be 100 ~ 210 weight parts based on acrylic ester monomer mixture I in step 1, described chain-transfer agent is 0.3 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, as 0.6 weight part.
6., according to the method one of Claims 1 to 5 Suo Shu, it is characterized in that, in step 4,
Described acrylic monomer mixtures II comprises the component of following weight proportion,
The range of choice of described silane coupling agent is identical with the range of choice of silane coupling agent described in step 2; And/or
Be 158 ~ 285 weight parts based on acrylic monomer mixtures II, silane coupling agent is 8 ~ 15 weight parts, is preferably 9 ~ 13 weight parts, as 11 weight parts; And/or
The range of choice of described initiator is identical with the range of choice of initiator described in step 2; And/or
Be 158 ~ 285 weight parts based on acrylic monomer mixtures II, initiator is 3 ~ 8 weight parts, is preferably 4 ~ 6 weight parts, as 5 weight parts; And/or
Described mixture B, preferably in 1 ~ 5 hour, in being preferably 2 ~ 4 hours, dropwised in 3 hours; And/or
When adding mixture B, the temperature controlling reaction system is 60 DEG C ~ 95 DEG C, preferably 70 DEG C ~ 90 DEG C, as 80 DEG C, and 85 DEG C or 90 DEG C.
7., according to the method one of claim 1 ~ 6 Suo Shu, it is characterized in that, in steps of 5,
The range of choice of described initiator is identical with the range of choice of initiator described in step 2; And/or
Be 158 ~ 285 weight parts based on acrylic monomer mixtures II in step 4, described initiator is 0.5 ~ 2 weight part, is preferably 0.8 ~ 1.5 weight part, as 1.2 weight parts; And/or
The range of choice of described chain-transfer agent is identical with the range of choice of chain-transfer agent described in step 2; And/or
Be 158 ~ 285 weight parts based on acrylic monomer mixtures II in step 4, described chain-transfer agent is 0.3 ~ 1 weight part, is preferably 0.4 ~ 0.8 weight part, as 0.6 weight part; And/or
Be 158 ~ 285 weight parts based on acrylic ester monomer mixtures II in step 4, described solvent is 10 ~ 50 weight parts, is preferably 20 ~ 40 weight parts, as 30 weight parts; And/or
After adding mixture B, preferably insulation reaction under 60 DEG C ~ 90 DEG C conditions, the time of preferred insulation reaction was 0.5 ~ 2 hour, as 1 hour.
8., according to the method one of claim 1 ~ 7 Suo Shu, it is characterized in that, in step 6,
Described process comprises and adds water and/or stir,
With organic bases regulation system pH, preferably, described organic bases is small molecules organic bases, and described small molecules organic bases is aminated compounds, e.g., and one or more in diethylamine, triethylamine, N, N-dimethylethanolamine, diethanolamine, thanomin or ammoniacal liquor; And/or
Be 158 ~ 285 weight parts based on acrylic ester monomer mixtures II in step 4, described organic bases is 8 ~ 15 weight parts, is preferably 10 ~ 13 weight parts, as 12 weight parts; And/or
Be 100 ~ 210 parts by weight with Acrylic Acid Monomer mixture I in step 2, the add-on of described water is 500 ~ 800 weight parts, is preferably 600 ~ 700 weight parts, as 660 weight parts.
9. a water-borne acrylic resin obtained according to the described method of one of claim 1 ~ 8, wherein containing the solvent added in preparation process.
10. a using method for water-borne acrylic resin according to claim 9, is characterized in that, described water-borne acrylic resin does not add solidifying agent in use.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108300036A (en) * | 2017-08-29 | 2018-07-20 | 河北晨阳工贸集团有限公司 | A kind of farm implement aqueous dip-coating baking vanish and preparation method thereof |
| CN110092865A (en) * | 2019-06-13 | 2019-08-06 | 深圳市志邦科技有限公司 | A kind of hydrophobic type water-based acrylic resin, paint vehicle and its synthetic method |
| CN111217954A (en) * | 2018-11-26 | 2020-06-02 | 阜阳师范学院 | Acrylate aqueous dispersion and preparation method thereof |
| CN111217955A (en) * | 2018-11-26 | 2020-06-02 | 阜阳师范学院 | Water-based acrylic resin and preparation method thereof |
| CN112279955A (en) * | 2019-07-25 | 2021-01-29 | 阜阳师范大学 | Preparation method of water-based acrylic resin |
| CN112279956A (en) * | 2019-07-25 | 2021-01-29 | 阜阳师范大学 | Water-based acrylic resin and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108300036A (en) * | 2017-08-29 | 2018-07-20 | 河北晨阳工贸集团有限公司 | A kind of farm implement aqueous dip-coating baking vanish and preparation method thereof |
| CN111217954A (en) * | 2018-11-26 | 2020-06-02 | 阜阳师范学院 | Acrylate aqueous dispersion and preparation method thereof |
| CN111217955A (en) * | 2018-11-26 | 2020-06-02 | 阜阳师范学院 | Water-based acrylic resin and preparation method thereof |
| CN110092865A (en) * | 2019-06-13 | 2019-08-06 | 深圳市志邦科技有限公司 | A kind of hydrophobic type water-based acrylic resin, paint vehicle and its synthetic method |
| CN112279955A (en) * | 2019-07-25 | 2021-01-29 | 阜阳师范大学 | Preparation method of water-based acrylic resin |
| CN112279956A (en) * | 2019-07-25 | 2021-01-29 | 阜阳师范大学 | Water-based acrylic resin and preparation method thereof |
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