CN105085771B - A kind of water-based acrylic resin and preparation method thereof - Google Patents
A kind of water-based acrylic resin and preparation method thereof Download PDFInfo
- Publication number
- CN105085771B CN105085771B CN201510418885.1A CN201510418885A CN105085771B CN 105085771 B CN105085771 B CN 105085771B CN 201510418885 A CN201510418885 A CN 201510418885A CN 105085771 B CN105085771 B CN 105085771B
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- initiator
- chain transfer
- monomer mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 64
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title description 12
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 239000003999 initiator Substances 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012986 chain transfer agent Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 28
- 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 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 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
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 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
- 238000009835 boiling Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 23
- -1 acrylic ester Chemical class 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 230000010148 water-pollination Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- 229920000058 polyacrylate Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- OATFZMZHCHJBGR-UHFFFAOYSA-N ethenoxyperoxysilane Chemical compound C(=C)OOO[SiH3] OATFZMZHCHJBGR-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of method and the water-based acrylic resin as obtained in methods described for preparing water-based acrylic resin, the method uses green solvent, chain-transferring agent is dissolved in solvent first, it is added thereto to comprising acrylic ester monomer mixture I, the mixture A of initiator and chain-transferring agent, it is initiated by making polymerisation at a lower temperature, again reaction speed is controlled to initiator and chain-transferring agent is added in system, again to mixture B of the addition comprising acrylic monomer mixtures II in system, make obtained water soluble acrylic acid that there is core shell structure, both there is hydrophily while there is also hydrophobicity, there is good hardness with its obtained paint film, adhesive force, shock resistance, the performances such as water resistance.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to a method for preparing water-based acrylic resin and the water-based acrylic resin prepared by the method.
Background
At present, solvent-type acrylic resin products play an important role in China, but the solvent-type acrylic resin is not friendly to the environment and human health due to high VOC value, so that the solvent-type acrylic resin is in danger of exiting the market. In addition, the environmental protection consciousness of people is continuously improved, and a large number of environmental protection products come out, and are paid attention by the whole society. Among them, water-based acrylic resins are more preferred. For example, chemical mega bayer, basf, dupont, etc. in germany put a lot of effort on the development of aqueous acrylic acid.
The water-based acrylic resin takes water as a solvent, is nontoxic and tasteless, and has the characteristics of low cost, no environmental pollution and the like. In addition, the preparation of the water-based acrylic coating is simpler and more convenient, the water-based acrylic coating can be flexibly designed according to actual conditions, and one or more of the following additives are added into the water-based acrylic resin according to actual requirements: thickening agent, defoaming agent, drier, mildew-proof bactericide, corrosion inhibitor and the like.
Although the waterborne acrylic resin has the advantages of no pollution, no toxicity, no irritation, better gloss, good chemical resistance, high stability, safe production, low price and the like, the waterborne acrylic resin also has the defect of being not eliminated, and the defects are mainly reflected in that the waterborne acrylic resin is hot-sticky and cold-brittle after film forming and drying, poor in anti-tack property, poor in heat resistance, not long in water resistance, poor in impact resistance and the like, so that the application field of the waterborne acrylic resin is limited. Therefore, in order to overcome the above-mentioned disadvantages of the aqueous acrylic resin, it is necessary to modify the aqueous acrylic resin.
In the prior art, a physical blending method is mostly adopted, and a silane coupling agent is directly blended with the water-based acrylic resin. Although the modification method is simple and convenient, the emulsion after blending has poor stability, is easy to generate two-phase separation, and has no chemical bond combination with the acrylic resin polymer and the base material, so that the performance of the acrylic resin cannot be effectively improved.
In addition, in some prior arts, a silane coupling agent containing an unsaturated bond is introduced into the backbone of an aqueous acrylic resin by a chemical modification method to obtain a copolymer, thereby improving the performance of the acrylic resin. Although the method improves the performance of the water-based acrylic resin to a certain extent, the obtained water-based acrylic resin has poor film forming property, poor glossiness, poor stability and low solid content, and in addition, the emulsion has high viscosity and is not easy to emulsify in the synthesis process.
Therefore, in order to overcome the above-mentioned disadvantages of the aqueous acrylic resin, it is necessary to modify the aqueous acrylic resin.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: slowly dripping a mixture A containing an acrylate monomer mixture I, an initiator and a chain transfer agent into a solvent system in which the chain transfer agent is dissolved, supplementing the initiator and the chain transfer agent, slowly dripping a mixture B containing an acrylic monomer mixture II, the initiator and the chain transfer agent into the system, supplementing the initiator and the chain transfer agent, finally adjusting the pH value of the system, and adding water to prepare the water-based acrylic resin.
The object of the present invention is to provide the following:
in a first aspect, the present invention provides a process for the preparation of an aqueous propionic resin, characterised in that it comprises the steps of:
(1) adding a solvent and a chain transfer agent to a vessel, optionally stirring and heating;
(2) adding a mixture A containing an acrylate monomer mixture I, a silane coupling agent and an initiator into the system obtained in the step 1;
(3) adding an initiator and a chain transfer agent into the system obtained in the step 2, reacting, and optionally carrying out at the constant temperature;
(4) adding a mixture B containing an acrylic monomer mixture II, a silane coupling agent and an initiator into the system obtained in the step 3;
(5) adding an initiator and a chain transfer agent into the system obtained in the step 4, reacting, and optionally carrying out at the constant temperature;
(6) and (5) adjusting the pH value of the system obtained in the step (5), adding water, and stirring to obtain the water-based acrylic resin.
In a second aspect, the invention also provides a water-based acrylic resin prepared by the method, wherein the water-based acrylic resin contains a solvent added in the preparation process.
In a third aspect, the present invention also provides a method for using the aqueous acrylic resin according to the second aspect, wherein a curing agent is not added to the aqueous acrylic resin during use.
Drawings
FIG. 1 shows the results of particle size testing of samples prepared in example 1;
FIG. 2 is a graph showing a particle size distribution of a sample obtained in example 1;
FIG. 3 shows the results of particle size testing of samples prepared in example 2;
FIG. 4 is a graph showing a particle size distribution of a sample obtained in example 2;
FIG. 5 shows the results of particle size testing of samples made in example 3;
FIG. 6 is a graph showing a particle size distribution of a sample obtained in example 3;
FIG. 7 shows a photograph of the morphology of a water droplet on a paint film obtained from the sample obtained in example 1;
FIG. 8 is a photograph showing the morphology of water droplets on a paint film obtained from the sample obtained in example 2;
FIG. 9 is a photograph showing the morphology of water droplets on a paint film obtained from the sample obtained in example 3.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
According to a first aspect of the present invention, there is provided a process for the preparation of an aqueous propionic resin, characterised in that it comprises the steps of:
step 1, adding a solvent and a chain transfer agent to a vessel, optionally stirring and raising the temperature.
In the present invention, the solvent is an organic solvent, preferably an organic solvent having a boiling point higher than 85 ℃ and low volatility, and among the above organic solvents, particularly preferred is a low toxicity type organic solvent selected from the group consisting of alcohol solvents, ester solvents, ketone solvents, hydrocarbon solvents, aromatic solvents, and ether solvents, preferably isopropanol, butanol, ethylene glycol butyl ether, ethyl acetate, cyclohexanone, nitroethane, cyclohexane, trichloroethylene, heptane, octane, nitromethane, acetonitrile, propionitrile, toluene, p-xylene, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether, more preferably ethylene glycol butyl ether, toluene, heptane, butanol, ethylene glycol monomethyl ether, octane, ethyl acetate, ethylene glycol monoethyl ether, and p-xylene, and more preferably ethylene glycol butyl ether.
The above solvent enables the reaction temperature to be maintained at 60 to 95 ℃, preferably 70 to 90 ℃, and the initiation temperature of the initiator used in the reaction is in the vicinity of the temperature range, even within the temperature range, so that the raw material can be polymerized at the temperature, and has an appropriate initiation rate and polymerization rate so that the polymerization can be performed at the initiation temperature of the initiator, preferably, the polymerization can be performed in a reflux state at a stable temperature.
The present inventors have found that when an aliphatic thiol type chain transfer agent is used, the molecular weight distribution of the resulting aqueous acrylic resin is narrow and the properties are stable, and therefore, in the present invention, the chain transfer agent is selected from one or more aliphatic thiols, and particularly, the chain transfer agent is preferably one or more of dodecyl mercaptan and octadecyl mercaptan, more preferably one or more of n-dodecyl mercaptan, t-dodecyl mercaptan and n-octadecyl mercaptan, and further preferably n-dodecyl mercaptan.
In the invention, the chain transfer agent is firstly dissolved in the solvent and fully mixed under the stirring condition, so that the chain transfer agent in the system is excessive compared with other raw materials added in the subsequent step, macromolecules generated by the acrylate monomer mixture I dripped into the system can quickly form micromolecule crosslinking, the molecular weight distribution of the prepared acrylic polymer is narrower, and the polymerization reaction for preparing acrylic acid is more full.
In the present invention, the temperature of the system in which the chain transfer agent is dissolved is optionally raised, so that other raw materials added in the subsequent step can be directly placed in an environment suitable for the polymerization reaction to rapidly proceed when being added into the reaction system.
In the invention, the reaction is firstly carried out under the condition of low temperature, generally 60-95 ℃, preferably 70-90 ℃, so that the heating in water bath can be realized; and the product performance deterioration caused by overhigh temperature is avoided; in addition, the production is carried out under the temperature condition, the safety is high, the operation is easy, no pollution is caused, and the water-based acrylate with good performances in all aspects can be obtained in a stable, safe and environment-friendly mode.
When the temperature of the system dissolved with the chain transfer agent is higher than 95 ℃, the molecular crosslinking density of the prepared water-based acrylic acid is too high, the water solubility is poor, the color is changed into a scorched yellow color, and even a gel reaction occurs; when the temperature of the system dissolved with the chain transfer agent is lower than 60 ℃, the temperature is increased too slowly, the reproducibility of the product performance is poor, and the performances such as water resistance, adhesive force and the like are also poor.
In step 1 of the present invention, the solvent is 100 to 200 parts by weight, preferably 120 to 180 parts by weight, such as 150 parts by weight.
In step 1 of the present invention, the chain transfer agent is 2 to 8 parts by weight, preferably 3 to 6 parts by weight, such as 4 parts by weight.
And 2, adding a mixture A containing an acrylate monomer mixture I, a silane coupling agent and an initiator into the system obtained in the step 1.
In the invention, the acrylate monomer mixture I comprises the following components in parts by weight,
40-80 parts by weight of methyl methacrylate
40-80 parts by weight of butyl acrylate
20 to 50 parts by weight of hydroxyethyl methacrylate,
preferably, the first and second liquid crystal materials are,
50-70 parts by weight of methyl methacrylate
50-70 parts by weight of butyl acrylate
30 to 40 parts by weight of hydroxyethyl methacrylate,
more preferably, the first and second liquid crystal materials are,
58 parts by weight of methyl methacrylate
Butyl acrylate 53 parts by weight
35 parts by weight of hydroxyethyl methacrylate.
The mixing method of the acrylic monomer mixture I is not particularly limited in the present invention, and any method capable of uniformly mixing the mixture in the prior art, such as mechanical stirring, magnetic stirring, ultrasonic oscillation, etc., may be used, and the ultrasonic oscillation method is preferably used for mixing.
The inventor finds that the hydrolyzable group in the silane coupling agent can enable the prepared water-based acrylic resin to form an interpenetrating network structure when the water-based acrylic resin is formed into a film, so that the fusibility of the water-based acrylic resin during film forming is improved, and the impact resistance of the film is further improved.
In addition, the silane coupling agent is added when the waterborne acrylic resin is prepared, so that the adhesion of the prepared waterborne acrylic resin on a substrate can be improved, and the inventor believes that the Si-O bond in the silane coupling agent has higher ionization tendency and higher bond energy without being bound by any theory.
In the present invention, the silane coupling agent may be represented by the following formula:
YSiX3
wherein,
y is an unsaturated alkenyl group, preferably: CH (CH)2＝CH(CH2)n-, wherein n is 1 to 8, further, CH2＝CH(CH2)n-is preferably CH2＝C(CH3)-，CH2CH-, in particular, CH is preferable2＝CH-，
X is a hydrolysable group, preferably: -Cl, -OMe, -OEt, -OC2H4OCH3、-OSiMe3and-OAc, in particular-OC is preferred2H5。
In the present invention, the silane coupling agent is preferably vinyltriethoxysilane.
In the present invention, the silane coupling agent is added in an amount of 5 to 10 parts by weight, preferably 6 to 9 parts by weight, and more preferably 7 to 8 parts by weight, based on 100 to 210 parts by weight of the acrylate monomer mixture I.
In step 2 of the present invention, the kind of the initiator is not particularly limited, and the initiator is capable of generating a radical to initiate the reaction after being heated.
The initiator is selected from one or more of the following initiators: acyl peroxides such as benzoyl peroxide, hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, azo initiators such as azobisisobutyronitrile, azobisisoheptonitrile.
In a preferred embodiment, the initiator is Azobisisobutyronitrile (AIBN).
The inventor finds that the acrylic acid polymer prepared by using AIBN as an initiator is not easy to generate the gel phenomenon, has narrow molecular weight distribution and is beneficial to preparing the water-soluble acrylate polymer with higher solid content.
In step 2 of the present invention, the initiator is added in the mixture A in an amount of 1 to 5 parts by weight, preferably 2 to 4 parts by weight, such as 3 parts by weight, based on 100 to 210 parts by weight of the acrylate monomer mixture I.
In the present invention, the acrylate monomer mixture I, the silane coupling agent and the initiator are preferably mixed uniformly and then added to the system in step 1, the mixing method in the present invention is not particularly limited, and any method capable of uniformly mixing the above mixture in the prior art, such as mechanical stirring, magnetic stirring, ultrasonic oscillation, etc., preferably ultrasonic oscillation, may be used for mixing.
In a preferred embodiment of the present invention, the acrylate monomer mixture I, the silane coupling agent and the initiator are mixed uniformly, and then filtered to remove insoluble impurities, which is beneficial for the subsequent reaction.
In the present invention, the mixture a is preferably added dropwise within 1 to 5 hours, preferably within 2 to 4 hours, such as within 3 hours. When the dropping speed is too slow, the dropping time is too long and is more than 5 hours, the performance of the prepared acrylic polymer is unstable, and the reproducibility is poor; when the dropping speed is too fast and the dropping time is too short and is less than 1 hour, the prepared acrylic polymer has wide molecular weight distribution and nonuniform intermolecular crosslinking.
In step 2 of the present invention, the temperature of the reaction system is controlled to 60 to 95 ℃, preferably 70 to 90 ℃, such as 80 ℃, 85 ℃ or 90 ℃ when the mixture A is added.
The mixture A is preferably added into the system in the step 1 in a dropwise manner in the invention.
And 3, supplementing an initiator and a chain transfer agent into the system obtained in the step 2, reacting, and optionally carrying out at the constant temperature.
The present inventors have found that addition of an initiator and a chain transfer agent to the reaction system after completion of dropwise addition of the mixture A accelerates the progress of the polymerization reaction and also enables the polymerization reaction to be controlled at an appropriate rate.
In step 3 of the present invention, the selection range of the initiator is the same as that of the initiator in step 2, preferably, the same as that of the initiator in step 2.
In step 3 of the present invention, the initiator is 0.3 to 1 part by weight, preferably 0.4 to 0.8 part by weight, such as 0.6 part by weight, based on 100 to 210 parts by weight of the acrylate monomer mixture I in step 1.
In step 3 of the present invention, the chain transfer agent is selected in the same range as that of step 2, preferably in the same range as that of step 2.
In step 3 of the present invention, the chain transfer agent is used in an amount of 0.3 to 1 part by weight, preferably 0.4 to 0.8 part by weight, such as 0.6 part by weight, based on 100 to 210 parts by weight of the acrylate monomer mixture I in step 1.
In step 3 of the present invention, the initiator and the chain transfer agent are preferably dissolved in a solvent and then added to the reaction system, thereby avoiding reaction imbalance caused by excessive local concentration and also resulting in a narrow molecular weight distribution of the resulting acrylic polymer.
In step 3 of the present invention, the solvent is selected in the same range as that of step 1, preferably, in the same range as that of step 1.
In step 3 of the present invention, the solvent is 10 to 30 parts by weight, preferably 15 to 25 parts by weight, for example 20 parts by weight, based on 100 to 210 parts by weight of the acrylate monomer mixture I in step 1.
In step 3 of the invention, after the initiator and the chain transfer agent are added, the reaction is preferably carried out at 60-90 ℃ with heat preservation, and the reaction time is preferably 0.5-2 hours, such as 1 hour.
And 4, adding a mixture B containing the acrylic monomer mixture II, the silane coupling agent and the initiator into the system obtained in the step 3.
The inventor finds that the addition of the mixture B into the system prepared in the step 3 enhances the hydrophilicity of the prepared water-based acrylic resin, so that the prepared water-based acrylic resin can stably exist in an aqueous solution and has good water resistance, and the inventor believes that the acrylic monomer mixture II in the mixture B added in the step 4 takes the polymer prepared in the step 3 as an inner core and is coated and polymerized on the surface of the inner core to form the water-based acrylic resin with a double-layer structure, wherein free carboxyl groups do not exist on the surface of the acrylate polymer prepared in the step 3 and are represented as hydrophobic properties, an acrylic compound is introduced into the mixture B added in the step 4, and the free hydroxyl groups are not active sites of polymerization reaction, so that the water-based acrylic resin prepared after the step 4 has free carboxyl groups on the surface, thereby increasing the hydrophilicity of the water-based acrylic resin, furthermore, the water-based acrylic resin prepared through the steps 3 and 4 has good hydrophilicity, namely, enhanced water solubility, and good water resistance.
In step 4 of the present invention, the acrylic monomer mixture II comprises the following components in parts by weight,
preferably, the first and second liquid crystal materials are,
more preferably, the first and second liquid crystal materials are,
in step 4 of the present invention, the range of choice of the silane coupling agent is the same as the range of choice of the silane coupling agent in step 2, preferably, the same as the range of choice of the silane coupling agent in step 2.
In step 4 of the present invention, the silane coupling agent is used in an amount of 158 to 285 parts by weight, preferably 9 to 13 parts by weight, for example 11 parts by weight, based on 158 to 285 parts by weight of the acrylic monomer mixture II.
In step 4 of the present invention, the selection range of the initiator is the same as that of the initiator in step 2, preferably, the same as that of the initiator in step 2.
In step 4 of the present invention, the amount of the initiator is 158 to 285 parts by weight, preferably 4 to 6 parts by weight, for example 5 parts by weight, based on 158 to 285 parts by weight of the acrylic monomer mixture II.
In a preferred embodiment of the present invention, the acrylic monomer mixture II, the silane coupling agent and the initiator are uniformly mixed and then added to the system in step 4, the mixing method is not particularly limited in the present invention, and any method capable of uniformly mixing the above mixture in the prior art, such as mechanical stirring, magnetic stirring, ultrasonic oscillation, and the like, preferably ultrasonic oscillation, can be used for mixing.
In a preferred embodiment of the present invention, the acrylic monomer mixture II, the silane coupling agent and the initiator are mixed uniformly, and then filtered to remove insoluble impurities, which is beneficial for the subsequent reaction.
In the present invention, the mixture B is preferably added dropwise within 1 to 5 hours, preferably within 2 to 4 hours, such as within 3.5 hours. When the dropping speed is too slow, the dropping time is too long and is more than 5 hours, the performance of the prepared acrylic polymer is unstable, and the reproducibility is poor; when the dropping speed is too fast and the dropping time is too short and is less than 1 hour, the prepared acrylic polymer has wide molecular weight distribution and nonuniform intermolecular crosslinking.
In step 4 of the present invention, when the mixture B is added, the temperature of the reaction system is controlled to be 60 to 95 ℃, preferably 70 to 90 ℃, such as 80 ℃, 85 ℃ or 90 ℃, and more preferably to be the same as the reaction temperature in step 3.
The mixture B is preferably added into the system in the step 3 in a dropwise manner in the invention.
And 5, adding an initiator and a chain transfer agent into the system obtained in the step 4, reacting, and optionally carrying out at the constant temperature.
The present inventors have found that addition of an initiator and a chain transfer agent to the reaction system after completion of dropwise addition of the mixture B accelerates the progress of the polymerization reaction and also enables the polymerization reaction to be controlled at an appropriate rate.
In step 5 of the present invention, the selection range of the initiator is the same as that of the initiator in step 2, preferably, the same as that of the initiator in step 2.
In step 5 of the present invention, the amount of the initiator is 0.5 to 2 parts by weight, preferably 0.8 to 1.5 parts by weight, for example, 1.2 parts by weight, based on 158 to 285 parts by weight of the acrylic monomer mixture II in step 4.
In step 5 of the present invention, the chain transfer agent is selected in the same range as that of step 2, preferably in the same range as that of step 2.
In step 5 of the present invention, the chain transfer agent is used in an amount of 0.3 to 1 part by weight, preferably 0.4 to 0.8 part by weight, for example, 0.6 part by weight, based on 158 to 285 parts by weight of the acrylic monomer mixture II in step 4.
In step 5 of the present invention, the initiator and the chain transfer agent are preferably dissolved in a solvent and then added to the reaction system, thereby avoiding reaction imbalance caused by excessive local concentration and also resulting in a narrow molecular weight distribution of the resulting acrylic polymer.
In step 5 of the present invention, the solvent is selected in the same range as that of step 1, preferably, in the same range as that of step 1.
In step 5 of the present invention, the solvent is used in an amount of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, for example 30 parts by weight, based on 158 to 285 parts by weight of the acrylate monomer mixture II in step 4.
In step 5 of the present invention, after the mixture B is added, the reaction is preferably performed under a condition of a temperature preservation of 60 ℃ to 90 ℃, and the reaction time is preferably 0.5 to 2 hours, such as 1 hour.
And 6, adjusting the pH value of the system obtained in the step 5, and treating to obtain the water-based acrylic resin.
The inventor finds that after organic base is added into a reaction system to adjust the pH value of the system, free carboxyl on the surface of an acrylic polymer can react with the organic base to form salt, so that the acrylic polymer stably exists in the form of salt, and a finished product of the water-based acrylic resin is high in glossiness and flatness after film forming, so that the resin is high in glossiness after film forming, and meanwhile, the hydrophilicity of the acrylic polymer is increased.
In the present invention, the organic base is a small molecule organic base, and the small molecule organic base is an amine compound, such as one or more of diethylamine, triethylamine, N-dimethylethanolamine, diethanolamine, ethanolamine or ammonia water, preferably N, N-dimethylethanolamine and/or diethanolamine, and more preferably N, N-dimethylethanolamine.
Based on 158-285 parts by weight of the acrylate monomer mixture II in the step 4, the organic base is 8-15 parts by weight, preferably 10-13 parts by weight, such as 12 parts by weight. By adding the organic base, the pH value of the system is alkalescent.
In the present invention, the treatment comprises adding water and/or stirring.
Water is added into the system after the organic base is added, and the water-based acrylic resin with excellent performance can be directly prepared by stirring without removing the solvent in the system.
The water is one or more of deionized water, distilled water, tap water and purified water, and preferably deionized water.
The amount of the water added is 500 to 800 parts by weight, preferably 600 to 700 parts by weight, for example 660 parts by weight, based on 100 to 210 parts by weight of the acrylic monomer mixture I in the step 2.
In the conventional preparation of the aqueous acrylic resin, the solvent in the preparation system is usually removed by distillation, which consumes about 1/2 of the total time for preparing the aqueous acrylic resin, not only wastes a lot of time, but also consumes a lot of energy due to the high temperature used in the distillation, so that the step of removing the solvent in the preparation system in the conventional method not only is a speed-dependent link for preparing the aqueous acrylic resin, but also causes huge energy loss and environmental pollution.
The acrylic resin prepared by the method of the invention can be directly added with water to the system to prepare the final product of the water-based acrylic resin without removing the solvent in the system, thereby not only saving a large amount of time cost and greatly improving the production efficiency, but also reducing the energy loss and saving the economic cost; meanwhile, the solvent used in the invention is an environment-friendly green solvent, which does not cause environmental pollution.
When the waterborne acrylic resin prepared by the conventional method is used, auxiliaries such as a curing agent and the like are required to be added, when the waterborne acrylic resin prepared by the method is used, auxiliaries such as a curing agent and the like are not required to be added, the performance of the prepared waterborne acrylic paint film is equivalent to that of a waterborne acrylic paint film in the prior art, and even the performances in the aspects of hardness, impact resistance, adhesion, contact angle and the like are superior to those of the waterborne acrylic paint film in the prior art.
In a preferred embodiment of the present invention, after the reaction is completed, the temperature of the system is reduced to 40 ℃ to 60 ℃, and the pH of the system is adjusted, and the temperature reduction method and/or temperature reduction conditions are not particularly limited in the present invention, and the cooling may be natural cooling or artificial forced cooling.
According to the water-based acrylic resin and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
(1) the method has the advantages that the reaction is carried out in a green organic solvent, no excess solvent needs to be removed, and the product can be obtained by directly adding water for emulsification after the polymerization reaction is finished, so that a large amount of preparation time is saved, energy is saved, no environmental pollution is caused, and the method is green and environment-friendly;
(2) the method adopts a free radical polymerization multilayer composite technology, and the preparation conditions are controllable;
(3) the acrylic polymer prepared by the method at least has two-layer structures of a hydrophobic inner core and a hydrophilic surface coating, so that the prepared water-based acrylic resin has good hydrophilicity and good water resistance;
(4) the prepared water-based acrylic resin has narrow molecular weight distribution and stable performance;
(5) the prepared waterborne acrylic resin does not need to be added with any curing agent when in use.
Examples
Example 1
(1) Adding 150g of butyl cellosolve and 4g of n-dodecyl mercaptan into a 2000mL four-neck flask provided with a stirrer, a reflux condenser and a separating funnel, starting the stirrer, and controlling the water bath temperature to be 80 ℃;
(2) the mixture A (57.8 g of methyl methacrylate, 52.6g of butyl acrylate, 34.6g of hydroxyethyl methacrylate, 7.26g of vinyltrioxysilane and 3g of azobisisobutyronitrile) was added dropwise over about 3 hours, and the mixture was subjected to ultrasonic dispersion and filtration;
(3) adding 0.6g of azodiisobutyronitrile, 0.5g of n-dodecyl mercaptan and 20g of butyl cellosolve (directly added after ultrasonic dispersion) into the system obtained in the step 2, carrying out heat preservation reaction for 1h at the temperature of 80 ℃,
(4) dropwise adding the mixture B (86.8 g of methyl methacrylate, 12g of methacrylic acid, 79g of butyl acrylate, 52g of hydroxyethyl methacrylate, 11.5g of vinyl trioxysilane and 5g of azobisisobutyronitrile) into the system obtained in the step 3, filtering after ultrasonic dispersion, completing dropwise addition within 3.5 hours,
(5) and (3) adding 1.2g of azodiisobutyronitrile, 0.6g of n-dodecyl mercaptan and 30g of butyl cellosolve (directly added after ultrasonic dispersion) into the system obtained in the step (4), and continuing to perform heat preservation reaction for 1 hour at the temperature of 80 ℃.
(6) And (3) adding 12g of dimethylethanolamine into the system obtained in the step (5), stirring for about 10 minutes to adjust the pH, adding 600g of distilled water, and emulsifying for 0.5 hour to obtain the water-based acrylic resin.
Example 2
(1) Adding 180g of ethylene glycol butyl ether and 6g of n-octadecanethiol into a 2000mL four-neck flask provided with a stirrer, a reflux condenser and a separating funnel, starting the stirrer, and controlling the water bath temperature to be 85 ℃;
(2) dropwise adding the mixture A (80 g of methyl methacrylate, 70g of butyl acrylate, 40g of hydroxyethyl methacrylate, 6g of vinyltrioxysilane and 5g of azobisisobutyronitrile) for about 2h, ultrasonically dispersing and filtering;
(3) adding 0.3g of azodiisobutyronitrile, 0.8g of n-octadecanethiol and 10g of butyl glycol ether (directly adding after ultrasonic dispersion) into the system obtained in the step 2, keeping the temperature at 85 ℃ for reaction for 1 hour,
(4) dropwise adding the mixture B (100 g of methyl methacrylate, 15g of methacrylic acid, 60g of butyl acrylate, 70g of hydroxyethyl methacrylate, 8g of vinyl trioxysilane and 8g of azodiisobutyronitrile) into the system obtained in the step 3, filtering after ultrasonic dispersion, completing dropwise addition within 2 hours,
(5) and (3) adding 0.5g of azodiisobutyronitrile, 0.8g of n-octadecanethiol and 50g of butyl glycol ether (directly adding after ultrasonic dispersion) into the system obtained in the step (4), and continuing to perform heat preservation reaction for 0.5h at the temperature of 85 ℃.
(6) Adding 15g of dimethylethanolamine into the system obtained in the step 5, stirring for about 10 minutes to adjust the pH, adding 600g of distilled water, and emulsifying for 0.5 hour to obtain the water-based acrylic resin.
Example 3
(1) Adding 120g of ethylene glycol butyl ether and 3g of n-dodecyl mercaptan into a 2000mL four-neck flask provided with a stirrer, a reflux condenser and a separating funnel, starting the stirrer, and controlling the water bath temperature to be 90 ℃;
(2) dropwise adding mixture A (70 g of methyl methacrylate, 80g of butyl acrylate, 30g of hydroxyethyl methacrylate, 9g of vinyltrioxysilane and 1g of azodiisobutyronitrile) for about 5h, ultrasonically dispersing and filtering;
(3) adding 0.8g of azodiisobutyronitrile, 0.4g of n-dodecyl mercaptan and 30g of butyl cellosolve (directly added after ultrasonic dispersion) into the system obtained in the step 2, carrying out heat preservation reaction for 1h at 90 ℃,
(4) dropwise adding the mixture B (60 g of methyl methacrylate, 8g of methacrylic acid, 100g of butyl acrylate, 30g of hydroxyethyl methacrylate, 15g of vinyl trioxysilane and 3g of azodiisobutyronitrile) into the system obtained in the step 3, filtering after ultrasonic dispersion, completing dropwise addition within 5 hours,
(5) and (3) adding 2g of azodiisobutyronitrile, 0.3g of n-dodecyl mercaptan and 10g of butyl cellosolve (directly added after ultrasonic dispersion) into the system obtained in the step (4), and continuing to perform heat preservation reaction for 2 hours at the temperature of 90 ℃.
(6) And (3) adding 10g of dimethylethanolamine into the system obtained in the step (5), stirring for about 10 minutes to adjust the pH, adding 600g of distilled water, and emulsifying for 0.5 hour to obtain the water-based acrylic resin.
Comparative example
Comparative example 1 (using methanol as solvent)
This comparative example is similar to example 1 except that methanol is used as the solvent instead of butyl cellosolve.
After step 5 and before step 6, step 5 'is added for removing methanol in the system, and the step 5' is specifically as follows:
heating the system obtained in the step 5 to 60 ℃ under vacuum condition, and performing rotary evaporation to remove the solvent methanol, wherein the time is 24 hours.
Examples of the experiments
Preparing a paint film:
the samples prepared in examples 1-3 and comparative examples 1-3 were directly coated on the surface of a metal plate and naturally dried.
(II) determination of product solid content
Weighing a piece of tin foil paper, recording as a, uniformly coating a sample to be detected on the surface of the tin foil paper, weighing as b, placing the tin foil paper coated with the sample at the temperature of 120 ℃ for drying for 30 minutes, weighing as m, and calculating the solid content n of the sample according to the following formula:
n＝(m-a)/(b-a)。
(III) measurement of paint film adhesion
And (3) marking a # -shaped marking by using a paint film marking instrument, quickly pulling and observing the change of the marking position after the paint film is tightly adhered by using an adhesive tape, wherein if no paint film falls off, the marking is defined as 0 grade, a small amount of the paint film falls off to be 1 grade, and a large amount of the paint film falls off to be 2 grade.
(IV) determination of the impact resistance of the paint film
The method is characterized in that a DuPont impact resistance instrument is adopted for determination, a weight with a certain weight is placed at the upper end, a pair of impact grooves and an impact pestle are placed below the weight, a tinplate is placed between the grooves and the pestle, and the impact pestle under the free falling body of the weight at a certain height is used for pounding to determine the impact resistance of a paint film. The weight and height are used to calibrate the impact resistance.
(V) measurement of paint film hardness
The iron pieces sprayed were scratched with B-type BH type H-type 2H-type 3H-type pencils 45 degrees in order to observe the condition of the film on the iron pieces.
(VI) measurement of Water resistance of paint film
The paint film was immersed in tap water and the water resistance was observed until the time when the paint film started to whiten was taken out.
(VII) measurement of Water absorption of paint film
Weighing the polished iron sheet, recording the weight A, spraying a sample on the iron sheet, air-drying, putting the iron sheet into an oven at 80 ℃ for drying for four hours, taking out, cooling, weighing, recording the weight B, finally completely soaking the iron sheet coated with the sample in water, taking out after 24 hours, sucking water on the surface of the iron sheet by using absorbent paper, weighing, recording the weight C, and calculating the water absorption N according to the following formula:
N＝(C-A)/(B-A)。
(VIII) measurement of particle diameter of Water-based acrylic resin
Putting a small amount of the coating into a 100ml beaker, adding 50ml of water, carrying out ultrasonic treatment in an ultrasonic instrument for 5-10 minutes, measuring the particle size of the coating by using a particle size instrument, and recording data.
(nine) measurement of paint film contact Angle
Weighing the polished iron sheet, marking the weighed iron sheet as A, spraying a sample on the iron sheet, air-drying, placing the iron sheet in an oven at 80 ℃ for four hours, taking out the iron sheet for cooling, and measuring the contact angle of the iron sheet subjected to the treatment by using a contact angle measuring instrument (model JCY-1, Shenzhen Sanli chemical Co., Ltd.).
Experimental example 1
The samples used in this experimental example were those obtained in examples 1 to 3 and comparative examples 1 to 3 or paint films obtained from the above samples, and their respective properties were measured according to the methods (two) to (nine) described above, and the results are shown in Table 1 below,
TABLE 1
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A method of preparing an aqueous propionic acid resin, comprising the steps of:
(1) adding solvent and chain transfer agent into a container, stirring and heating to 60-95 ℃,
the solvent is an organic solvent with boiling point higher than 85 ℃ and low volatility,
the chain transfer agent is aliphatic thiol chain transfer agent,
the solvent is 100 to 200 parts by weight,
the chain transfer agent is 2-8 parts by weight;
(2) adding a mixture A containing an acrylate monomer mixture I, a silane coupling agent and an initiator into the system obtained in the step 1, wherein,
the acrylate monomer mixture I comprises the following components in parts by weight,
40-80 parts by weight of methyl methacrylate
40-80 parts by weight of butyl acrylate
20 to 50 parts by weight of hydroxyethyl methacrylate,
the silane coupling agent is represented by the formula:
YSiX3
wherein,
y is CH2＝CH(CH2)nWherein n is 1 to 8,
x is-Cl, -OMe, -OEt, -OC2H4OCH3、-OSiMe3and-OAc;
(3) adding an initiator and a chain transfer agent into the system obtained in the step 2, reacting, and keeping the temperature;
(4) adding a mixture B containing an acrylic monomer mixture II, a silane coupling agent and an initiator into the system obtained in the step 3, wherein,
the acrylic monomer mixture II comprises the following components in parts by weight,
(5) adding an initiator and a chain transfer agent into the system obtained in the step 4, reacting, and optionally carrying out at the constant temperature;
(6) and (5) adjusting the pH value of the system obtained in the step (5), and treating to obtain the water-based acrylic resin.
2. The method according to claim 1, wherein, in step 1,
the solvent is selected from alcohol solvents, ester solvents, ketone solvents, hydrocarbon solvents, aromatic solvents and ether solvents;
the chain transfer agent is dodecyl mercaptan and octadecyl mercaptan;
120-180 parts by weight of a solvent;
3-6 parts by weight of a chain transfer agent; and
heating to 70-90 ℃.
3. The method according to claim 1, wherein, in step 2,
the silane coupling agent is represented by the formula:
YSiX3
wherein,
y is CH2＝C(CH3)-，CH2＝CH-，
X is-OC2H5；
Based on 100-210 parts by weight of the acrylate monomer mixture I, the adding amount of the silane coupling agent is 5-10 parts by weight;
the initiator is selected from one or more of the following initiators: benzoyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile; and
based on 100-210 parts by weight of the acrylate monomer mixture I, the addition amount of the initiator in the mixture A is 1-5 parts by weight.
4. The method according to claim 1, wherein, in step 2,
the mixture A is preferably dripped within 1-5 hours;
the temperature of the reaction system is controlled to be 60-95 ℃.
5. The method according to claim 1, wherein, in step 3,
the selection range of the initiator is the same as that of the initiator in the step 2;
based on 100-210 parts by weight of the acrylate monomer mixture I in the step 2, 0.3-1 part by weight of an initiator;
the selection range of the chain transfer agent is the same as that of the chain transfer agent in the step 2; and
based on 100-210 parts by weight of the acrylate monomer mixture I in the step 2, 0.3-1 part by weight of the chain transfer agent is used.
6. The method according to claim 1, wherein, in step 4,
the selection range of the silane coupling agent is the same as that of the silane coupling agent in the step 2;
158-285 parts by weight of an acrylic monomer mixture II and 8-15 parts by weight of a silane coupling agent;
the selection range of the initiator is the same as that of the initiator in the step 2;
158-285 parts by weight of an initiator based on the acrylic monomer mixture II;
the mixture B is preferably dripped within 1-5 hours; and
when the mixture B is added, the temperature of the reaction system is controlled to be 60-95 ℃.
7. The method according to claim 1, wherein, in step 5,
the selection range of the initiator is the same as that of the initiator in the step 2;
158-285 parts by weight of the initiator based on the acrylic monomer mixture II in the step 4;
the selection range of the chain transfer agent is the same as that of the chain transfer agent in the step 2;
based on 158-285 parts by weight of the acrylic monomer mixture II in the step 4, 0.3-1 part by weight of the chain transfer agent;
based on 158-285 parts by weight of the acrylate monomer mixture II in the step 4, 10-50 parts by weight of the solvent; and
and after the mixture B is added, carrying out heat preservation reaction at the temperature of 60-90 ℃, wherein the heat preservation reaction time is 0.5-2 hours.
8. The method according to claim 1, wherein, in step 6,
the treatment comprises adding water and/or stirring,
adjusting the pH value of the system by using organic base, wherein the organic base is one or more of diethylamine, triethylamine, N-dimethylethanolamine, diethanolamine, ethanolamine or ammonia water;
based on 158-285 parts by weight of the acrylate monomer mixture II in the step 4, 8-15 parts by weight of the organic base; and
the amount of the water added is 500-800 parts by weight based on 100-210 parts by weight of the acrylic monomer mixture I in the step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418885.1A CN105085771B (en) | 2015-07-14 | 2015-07-14 | A kind of water-based acrylic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418885.1A CN105085771B (en) | 2015-07-14 | 2015-07-14 | A kind of water-based acrylic resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085771A CN105085771A (en) | 2015-11-25 |
| CN105085771B true CN105085771B (en) | 2017-06-16 |
Family
ID=54567164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510418885.1A Active CN105085771B (en) | 2015-07-14 | 2015-07-14 | A kind of water-based acrylic resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085771B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0825203A1 (en) * | 1996-08-22 | 1998-02-25 | Elf Atochem S.A. | (Meth)Acrylic resin compositions for marine antifouling coatings |
| CN102321253A (en) * | 2011-06-15 | 2012-01-18 | 陶栋梁 | Method for preparing acrylate water-based dispersion by continuously dripping under low temperature condition |
-
2015
- 2015-07-14 CN CN201510418885.1A patent/CN105085771B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0825203A1 (en) * | 1996-08-22 | 1998-02-25 | Elf Atochem S.A. | (Meth)Acrylic resin compositions for marine antifouling coatings |
| CN102321253A (en) * | 2011-06-15 | 2012-01-18 | 陶栋梁 | Method for preparing acrylate water-based dispersion by continuously dripping under low temperature condition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105085771A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105085771B (en) | A kind of water-based acrylic resin and preparation method thereof | |
| CN106543381B (en) | A kind of hydroxyl polyacrylate aqueous dispersion and preparation method thereof | |
| CN107434842B (en) | Core-shell structure hydroxyl acrylic resin emulsion and preparation method and application thereof | |
| KR101704888B1 (en) | Coating composition for a food or beverage can | |
| CN107082841B (en) | Medium-high temperature preparation method of acrylic ester aqueous dispersion | |
| CN102643380B (en) | Acrylate emulsion used for vacuum aluminum plating and laser embossing and preparation method thereof | |
| CN110358005B (en) | Acrylic emulsion and preparation method thereof | |
| CN105330784A (en) | Method for preparing waterborne acrylic resin | |
| CN113307918B (en) | Vegetable oil-based polyacrylate nonionic emulsion and preparation method and application thereof | |
| CN109608575A (en) | A kind of hydroxyl polyacrylate second level aqueous dispersion and preparation method thereof | |
| JPH05117344A (en) | Core-shell emulsion and aqueous press varnish using the same emulsion | |
| CN108329438A (en) | High-acid-resistance water-based epoxy dispersion and preparation method thereof | |
| CN107964063B (en) | PFOA-free polymer and preparation method and application thereof | |
| Delatte et al. | Synthesis and characterization of a soybean oil‐based macromonomer | |
| YU77090A (en) | Adhesive agent with hydroxylic groups, process for obtaining and use thereof | |
| CN106467603B (en) | A kind of anionic dispersing agents and its preparation method and application | |
| CN105085770B (en) | A kind of water-based acrylic resin containing naphtha and preparation method thereof | |
| JPH0370763A (en) | Aqueous composition of acid-functional acrylsilanol polymer base | |
| CN108794703A (en) | A kind of preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function | |
| CN111285953B (en) | Acrylic emulsion and preparation method thereof | |
| CN111217955A (en) | Water-based acrylic resin and preparation method thereof | |
| CN114213608B (en) | Water-based hydroxyl acrylic acid dispersoid and preparation method and application thereof | |
| CN105482043B (en) | A kind of acrylate polymer, preparation method and its usage | |
| US3557040A (en) | Process for preparing a carbon black-synthetic resin composition | |
| CN112279968B (en) | Preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 236041 Qinghe Road, Fuyang City, Anhui Province Patentee after: Fuyang Normal University Address before: 236041 no.741, Qinghe East Road, Fuyang City, Anhui Province Patentee before: FUYANG NORMAL University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20210126 Address after: 465450 in vein Industrial Park, south of 312 National Road, Zhaihe Town, Guangshan County, Xinyang City, Henan Province Patentee after: Henan Soton New Material Co.,Ltd. Address before: 236041 Qinghe Road, Fuyang City, Anhui Province Patentee before: Fuyang Normal University |
|
| TR01 | Transfer of patent right | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 453499 No. 3, Pubei pilot industrial park, Changheng County, Xinxiang, Henan Province Patentee after: Henan Soton New Material Co.,Ltd. Address before: 465450 in vein Industrial Park, south of 312 National Road, Zhaihe Town, Guangshan County, Xinyang City, Henan Province Patentee before: Henan Soton New Material Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 453499 No. 3, Pubei pilot industrial park, Changyuan City, Xinxiang City, Henan Province Patentee after: Henan Soton New Material Co.,Ltd. Address before: 453499 No. 3, Pubei pilot industrial park, Changheng County, Xinxiang, Henan Province Patentee before: Henan Soton New Material Co.,Ltd. |