CN105085769B - Aqueous acrylic resin and preparation method thereof - Google Patents
Aqueous acrylic resin and preparation method thereof Download PDFInfo
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- CN105085769B CN105085769B CN201510080888.9A CN201510080888A CN105085769B CN 105085769 B CN105085769 B CN 105085769B CN 201510080888 A CN201510080888 A CN 201510080888A CN 105085769 B CN105085769 B CN 105085769B
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 71
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003999 initiator Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims description 102
- -1 acrylic ester Chemical class 0.000 claims description 78
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 30
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 30
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 30
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 30
- 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 29
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 22
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical class CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 27
- 239000003973 paint Substances 0.000 abstract description 26
- 230000000977 initiatory effect Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- 125000002252 acyl group Chemical group 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000035939 shock Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 241000165940 Houjia Species 0.000 description 7
- 150000007530 organic bases Chemical class 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011248 coating agent Substances 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
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 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
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 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
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a preparation method of an aqueous acrylic acid and aqueous acrylic resin obtained by the method. The method initiates a polymerization reaction by using an initiator with high initiation temperature; the obtained acrylic resin polymer without removal of solvent in the reaction system can be supplemented with water directly to obtain the aqueous acrylic paint; and for usage, the paint does not need the addition of a curing agent. Compared with the paint film obtained by the prior art, the paint film obtained by the method has similar or even better hardness, adhesion, impact resistance, water resistance and particle size properties.
Description
Technical field
The invention belongs to polymeric material field, more particularly to a kind of water soluble acrylic acid and preparation method thereof.
Background technology
At present, solvent type acrylic resin product occupies an important position in China, but solvent type acrylic resin
It is extremely unfriendly to environmental and human health impacts because of its VOC values height, so as to be faced with the danger withdrawn from the market.In addition the ring of people
Protect consciousness constantly improving, substantial amounts of environmentally friendly machine mutually goes out then, receives the attention of the whole society, wherein, aqueous acrylamide
Acid resin then more gets the favour of people, and for example, chemical giant's Bayer, BASF, Du Pont of Germany etc. are for water soluble acrylic acid
Innovation Input great effort.
Water-borne acrylic resin be with water as solvent, it is nonpoisonous and tasteless, with low cost, the features such as free from environmental pollution；In addition,
The preparation of water-borne acrylic coatings is even more simple and convenient, can be according to actual conditions flexible design, according to actual demand aqueous third
One or more following auxiliary agents are added in olefin(e) acid resin：Thickener, defoamer, drier, antimildew disinfectant, corrosion inhibiter etc..
Although water-borne acrylic resin has, pollution-free, non-toxic, nonirritant, gloss is preferable, chemical resistance is good, stable
Property high and production safety, it is cheap the advantages of, but its own also has not eliminable shortcoming, is mainly manifested in resin
Film forming be dried after hot sticky cold crisp, anti-after tack is poor, heat resistance is not good, resistance to water not for a long time, impact resilience it is poor etc., so as to limit
The application of water-borne acrylic resin is restricted.
Therefore, in order to overcome the disadvantages mentioned above of water-borne acrylic resin, need to be modified water-borne acrylic resin.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Using the high initiation of initiation temperature
Water-borne acrylic resin obtained in agent, even if obtained water soluble acrylic acid is added without when in use curing agent, the acrylic acid for obtaining
Resin paint film has close performance with acrylic resin paint film obtained in curing agent is routinely added to, so as to complete the present invention.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention provides a kind of method for preparing water-borne acrylic resin, it is characterised in that the method includes
Following steps：
(1) solvent is heated up, in the solvent after intensification be added dropwise include acrylic ester monomer mixture I, initiator and
The mixture A of chain-transferring agent, insulation；
(2) being added dropwise in the system obtained to step 1 includes acrylic ester monomer mixtures II, initiator, chain-transferring agent
With the mixture B of acrylic compounds；
(3) initiator and chain-transferring agent are added in the system obtained to step 2, is incubated；
(4) alkali is added after lowering the temperature, water is added, is stirred, obtain water-borne acrylic resin.
Second aspect, the present invention also provides one kind water-borne acrylic resin by obtained in said method.
The third aspect, the present invention also provides water-borne acrylic resin or second party by obtained in the method for above-mentioned first aspect
The using method of the water-borne acrylic resin that face provides, it is characterised in that the water-borne acrylic resin is added without when in use
Curing agent.
Fourth aspect, the present invention also provides water-borne acrylic resin or second party by obtained in the method for above-mentioned first aspect
Purposes of the water-borne acrylic resin that face provides as binder.
Description of the drawings
Fig. 1 illustrates that embodiment 2 is obtained water-borne acrylic resin and makes after paint film, thereon water droplet form photo；
Fig. 2 illustrates that embodiment 3 is obtained water-borne acrylic resin and makes after paint film, thereon water droplet form photo；
Fig. 3 illustrates that embodiment 6 is obtained water-borne acrylic resin and makes after paint film, thereon water droplet form photo；
Fig. 4 illustrates that embodiment 7 is obtained water-borne acrylic resin and makes after paint film, thereon water droplet form photo；
Fig. 5 illustrates that embodiment 8 is obtained water-borne acrylic resin and makes after paint film, thereon water droplet form photo.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
For clear, clear and definite.
The detailed description below present invention.
According to the first aspect of the invention, there is provided a kind of method for preparing water-borne acrylic resin, it is characterised in that the party
Method is comprised the following steps：
Step 1, solvent is heated up, and being added dropwise in the solvent after intensification includes acrylic ester monomer mixture I, initiator
With the mixture A of chain-transferring agent, insulation.
The acrylic ester monomer mixture I includes the component of volumes below proportioning,
The parts by volume of methyl methacrylate 15～20
The parts by volume of butyl acrylate 15～20
The parts by volume of hydroxyethyl methacrylate 10～18,
Preferably,
The parts by volume of methyl methacrylate 16～19
The parts by volume of butyl acrylate 16～19
The parts by volume of hydroxyethyl methacrylate 12～16,
More preferably,
The parts by volume of methyl methacrylate 18
The parts by volume of butyl acrylate 18
The parts by volume of hydroxyethyl methacrylate 15.
The present invention is not specially limited to the hybrid mode of said mixture I, and the mode for preferably using ultrasound is mixed.
The inventors discovered that, water soluble acrylic acid is when in use by obtained in the initiator that initiation temperature is 90 DEG C～120 DEG C
Curing agent need not be added, after metal surface forms paint film, the hardness of paint film, adhesive force, anti-impact force, contact angle, resistance to water
Significantly increase etc. performance, therefore, the present invention selects the initiator that initiation temperature is 90 DEG C～120 DEG C, such as benzoyl peroxide (91
DEG C when half-life be t1/2=1h), cumyl peroxyneodecanoate, peroxy dicarbonate double -2 ethylhexyl esters, peroxidating two
(adjacent monomethyl benzoyl) (MBPO), TBHP (TBHP) and isopropyl benzene hydroperoxide, preferably benzoyl peroxide first
Acyl, peroxidating two (adjacent monomethyl benzoyl) (MBPO), TBHP (TBHP) and isopropyl benzene hydroperoxide, more preferably
For benzoyl peroxide.In the present invention, the chain-transferring agent is selected from one or more in aliphatic mercaptan, and especially, chain turns
Move agent and be preferably lauryl mercaptan and stearyl alcohol, more preferably n-dodecyl mercaptan, tert-dodecylmercaotan and just
One or more in Stearyl mercaptan, further, preferred n-dodecyl mercaptan.
In the present invention, mixture A includes the component of following weight/volume proportioning,
The parts by volume of acrylic ester monomer mixture I 40～60
The weight portion of initiator 1～20
The parts by volume of chain-transferring agent 2～8,
Preferably,
The parts by volume of acrylic ester monomer mixture I 45～55
The weight portion of initiator 2～18
The parts by volume of chain-transferring agent 3～7,
More preferably,
The parts by volume of acrylic ester monomer mixture I 51
The weight portion of initiator 3～15
The parts by volume of chain-transferring agent 4～5,
Wherein, 1 parts by volume/1 weight portion, equivalent to, 1mL/1g, or 1L/1kg.
The present invention selects that solvent is warming up near the initiation temperature of initiator before mixture I is added, and on the one hand accelerates
The carrying out of polymerisation, on the other hand avoids in temperature-rise period, and the raw material in system occurs side reaction, generates molecular weight
The big acrylate polymer of difference, i.e. solvent is warming up near the initiation temperature of initiator before mixture I is added, energy
The molecular weight for enough making the acrylate polymer of generation is more uniformly distributed, so as to efficiently reduce end-product water-borne acrylic resin
Viscosity, therefore, the present invention selects first solvent to be warming up to into 90 DEG C～120 DEG C, preferably 100 DEG C～118 DEG C, more preferably
114 DEG C～116 DEG C.
In the present invention, it is higher than 85 DEG C that the solvent is boiling point, while the low organic solvent of volatility, in above-mentioned organic solvent
In particularly preferred low-toxicity organic solvent, the solvent is selected from alcohols solvent, esters solvent, ketones solvent, varsol, virtue
Fragrant class solvent and ether solvent, preferably isopropanol, butanol, butyl glycol ether, ethyl acetate, cyclohexanone, nitroethane, hexamethylene
Alkane, trichloro ethylene, heptane, octane, nitromethane, acetonitrile, propionitrile, toluene, paraxylene, glycol dimethyl ether, ethylene glycol one
Methyl ether and ethylene glycol monoethyl ether, more preferably butyl glycol ether, toluene, heptane, butanol, glycol monomethyl ether, octane, acetic acid second
Ester, ethylene glycol monoethyl ether and paraxylene, more preferably butyl glycol ether, above-mentioned solvent under reflux conditions, can make reaction
Temperature is maintained at 90 DEG C～120 DEG C, meanwhile, in reaction the initiation temperature of initiator used also near the temperature range, or even
In the temperature range, so as to raw material can at high temperature carry out condensation reaction, and with appropriate velocity of initiation and polymerization
Speed, so as to polymerisation can be carried out under the initiation temperature of initiator, it is preferable that polymerisation can be in temperature stabilization
Carry out under reflux state.
In the present invention, the parts by volume for selecting solvent is 40～60 parts, preferably 45～55 parts, more preferably 50 parts.
Present invention preferably employs the mode being added dropwise adds mixture A in solvent.
The present invention is selected after mixture A is dripped, and makes reaction system be incubated 1～5 hour, preferably 2～3 hours, is protected
Temperature temperature be 100 DEG C～130 DEG C, preferably 110 DEG C～125 DEG C, more preferably 120 DEG C so that polymerisation is fully complete
Entirely, the molecular weight of obtained acrylate polymer is more homogeneous.
Step 2, being added dropwise in the system obtained to step 1 includes acrylic ester monomer mixtures II, initiator, chain tra nsfer
Agent and the mixture B of acrylic compounds.
In the present invention, acrylic ester monomer mixtures II described in step 2 includes the component of volumes below ratio,
The parts by volume of methyl methacrylate 15～20
The parts by volume of butyl acrylate 15～20
The parts by volume of hydroxyethyl methacrylate 10～18,
Preferably,
The parts by volume of methyl methacrylate 16～19
The parts by volume of butyl acrylate 16～19
The parts by volume of hydroxyethyl methacrylate 12～16,
More preferably,
The parts by volume of methyl methacrylate 18
The parts by volume of butyl acrylate 18
The parts by volume of hydroxyethyl methacrylate 12.5.
The scope that the initiator is selected is identical with the scope that initiator described in step 1 is selected, preferably with step 1 in
The initiator is identical.
The scope that the chain-transferring agent is selected is identical with the scope that chain-transferring agent described in step 1 is selected, preferably with step
Chain-transferring agent is identical described in rapid 1.
The acrylic compounds are the acrylic compounds with carboxyl, preferably acrylic acid and/or methyl-prop
Olefin(e) acid.
The mixture B includes the component of following weight/volume part,
Preferably,
More preferably,
Wherein, 1 parts by volume/1 weight portion, equivalent to, 1mL/1g, or 1L/1kg.
The inventors discovered that, acrylic compounds are introduced in the raw material that step 2 is added, enhance obtained aqueous
The hydrophily of acrylic resin so as to can either stable existence in aqueous, while and with good resistance to water, not by appointing
What theoretical constraint, inventors believe that, polymer obtained in the raw material with step 1 that step 2 is added as kernel, in its Surface coating
Polymerization, forms double-deck water-borne acrylic resin, wherein, there is no freedom on acrylate polymer obtained in step 1
Carboxyl, show as hydrophobicity, and acrylic compounds are introduced in the raw material that step 2 is added, and free hydroxyl is not
The avtive spot of polymerisation, therefore, the obtained water-borne acrylic resin after step 2, in its surface with free
Carboxyl, so as to, the hydrophily of water-borne acrylic resin is increased, and then, through water soluble acrylic acid obtained in step 1 and step 2
Resin had both had good hydrophily, i.e. water solubility strengthens, while and with good resistance to water.
It is amazing to be, the inventors discovered that, when step 1 feeds intake respectively with step 2 according to volumes below/weight proportion
When, obtained water-borne acrylic resin is obviously improved in the performance of the aspects such as hardness, resistance to water,
In step 1,
In step 2,
Wherein, 1 parts by volume/1 weight portion, equivalent to, 1mL/1g, or 1L/1kg.
Step 3, adds initiator and chain-transferring agent in the system obtained to step 2, insulation.
The inventors discovered that, after initiator and chain-transferring agent are added in the system obtained to step 2 so that esters of acrylic acid
Monomer is further polymerized completely, reduces the residual volume of reaction monomers, and polymerisation is more abundant thorough, and reaction efficiency is improved, together
When can adjust the viscosity of acrylic resin, therefore, the present invention selects to continue to be mended in reaction system after step 2 is added dropwise to complete
Fill dropwise addition initiator and chain-transferring agent.
The range of choice phase of the range of choice of initiator used and initiator used in step 1 and/or step 2 in step 3
Together, it is preferably identical with initiator used in step 1 and/or step 2, the range of choice of chain-transferring agent used and step 1 and/or
The range of choice of chain-transferring agent used is identical in step 2, preferably identical with chain-transferring agent used in step 1 and/or step 2.
The additional way of initiator and chain-transferring agent is not exposed to especially limit, can be by initiator and chain-transferring agent successively
In being added to reaction system, it is also possible to after initiator and chain-transferring agent are substantially dissolved in organic solvent, be added drop-wise to reactant
In system.Wherein, the range of choice of organic solvent is identical with the range of choice of solvent in step 1, preferred ether solvent, most preferably second
Glycol butyl ether.
In step 3 additional amount of initiator be step 1 in initiator used 2wt%～40wt%, preferably 3.0%～
7.5%, more preferably 3.5%～5.0%；
Step 3 Chain transfer agent additional amount be step 1 in chain-transferring agent used 2wt%～15wt%, preferably 2.5%
～6.0%, more preferably 3.0%～5.0%.
Initiator and chain-transferring agent are added after finishing, and reaction system is incubated under the initiation temperature of initiator, to promote
Carrying out completely for reaction, selects temperature retention time for 1～5 hour, more preferably 2～4 hours, such as 3 hours, and the temperature of insulation is
100 DEG C～130 DEG C, preferably 110 DEG C～125 DEG C, more preferably 120 DEG C.
Step 4, adds alkali after cooling, add water, stirring, obtains water-borne acrylic resin.
After completion of the reaction, system is made to be cooled to 80 DEG C～100 DEG C, the present invention does not do to cool-down method and/or cooling conditions
It is particularly limited to, can is natural cooling, or it is artificial to force cooling.
The inventors discovered that, adding after organic base in reaction system, the free carboxyl of polymer surfaces can be anti-with alkali
Answer forming salt so that polymer stable existence in a salt form, obtained end-product water-borne acrylic resin after film forming, paint
Film is plentiful, and flatness is good, so that glossiness is high after resin film forming, meanwhile, also increase the hydrophily of polymer.
In the present invention, the organic base is small molecule organic base, and the small molecule organic base is aminated compounds, e.g., two
Ethamine, triethylamine, N, preferably one or more in N- dimethylethanolamines, diethanol amine, monoethanolamine or ammoniacal liquor, N, N- bis-
Methylethanolamine and/or diethanol amine, more preferably N, N- dimethylethanolamines.
, with the molar amount of organic base molecule, acrylic acid mole is with propylene in step 2 raw material for the mole of organic base
The molar amount of acid molecule, the ratio of the mole of organic base and acrylic acid mole in step 2 raw material for organic base mole
Amount:Acrylic acid mole=(80～100) in step 2 raw material:100, preferably (90～98):100, such as 95:100.Pass through
Alkali is added above so that the pH of system is alkalescent.
Add water in the system added after organic base, stir, the water-borne acrylic resin of function admirable can be directly obtained,
Without the solvent in removing system.
The water is one or more in deionized water, distilled water, running water and pure water, preferred deionized water.
With the gross weight meter of finished product water soluble acrylic acid as 100 weight portions, wherein, the water of addition is 50～70 weight portions,
Preferably 55～65 weight portions, such as 60 weight portions.
When routinely water-borne acrylic resin is prepared, the solvent in preparation system is generally removed by the way of distillation, needed
The time to be consumed about prepares the 1/2 of water-borne acrylic resin total time, and this not only wastes the plenty of time, and due to distillation
Temperature used is higher, accordingly, it would be desirable to consume mass energy, so, solvent this step in preparation system is removed in conventional method
Suddenly it is not only and prepares the certainly fast link of water-borne acrylic resin speed, but also the massive losses of the energy and the dirt of environment can be caused
Dye.
And acrylic resin prepared in accordance with the method for the present invention, it is not necessary to the solvent in removing system, and directly to body
Add water in system and can be prepared by end-product water-borne acrylic resin, not only save substantial amounts of time cost, the life being greatly enhanced
Product efficiency, and the loss of the energy is reduced, save financial cost；Meanwhile, solvent used is environmental friendliness in the present invention
The green solvent of type, it does not result in environmental pollution.
Water-borne acrylic resin obtained in conventional method when in use, needs to add the auxiliary agents such as curing agent, and according to this
Water-borne acrylic resin obtained in bright method need not add when in use the auxiliary agents such as curing agent, obtained water soluble acrylic acid paint
The performance of film is suitable with the performance of water soluble acrylic acid paint film of the prior art, or even in hardness, shock resistance, adhesive force and contact
The performance of the aspects such as angle is better than water soluble acrylic acid paint film of the prior art.
According to the second aspect of the invention, there is provided one kind water-borne acrylic resin by obtained in said method, its feature exists
In method of the water-borne acrylic resin by described in above-mentioned first aspect is obtained.
Even if being added without curing agent when in use according to the water-borne acrylic resin that the present invention is obtained, the acrylic acid tree for obtaining
Fat paint film has close performance with acrylic resin paint film obtained in curing agent is routinely added to, and these performances are mainly manifested in firmly
The aspects such as degree, adhesive force, shock resistance, contact angle, resistance to water and granularity, referring specifically to experimental example.
According to the third aspect of the invention we, there is provided the water-borne acrylic resin or by obtained in the method for above-mentioned first aspect
The using method of the water-borne acrylic resin that two aspects are provided, it is characterised in that the water-borne acrylic resin is when in use not
Add curing agent.
According to the fourth aspect of the invention, there is provided the water-borne acrylic resin or by obtained in the method for above-mentioned first aspect
Purposes of the water-borne acrylic resin that two aspects are provided as binder.
Water soluble acrylic acid provided according to the present invention and preparation method thereof, has the advantages that：
(1) higher reaction temperature has been used, 110-120 DEG C, decomposition rate in the temperature range has been simultaneously used in suitable
Initiator；
(2) methods described is reacted in green organic solvent, it is not necessary to remove unnecessary solvent, and polymerisation is finished
Directly add water emulsification to obtain final product product afterwards, save a large amount of preparation times, energy saving；
(3) the method adopts radical polymerization MULTILAYER COMPOSITE technology；
(4) acrylate copolymer obtained in methods described at least has hydrophobic cores and hydrophilic surface coating two-layer
Structure, so as to obtained water-borne acrylic resin had both had good hydrophily, while and with good resistance to water；
(5), in the case where any curing agent is not used, the hardness of resulting paint film can for water-borne acrylic resin obtained in
To reach 3H, adhesive force can reach 0 grade, and resistance to water can reach more than 24h, and shock resistance can reach Du Pont's shock resistance
Instrument maximum detectable limit.
Embodiment
Embodiment 1
(1) 50mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 116 DEG C is heated to；Measure respectively
18mL methyl methacrylates are taken, 18mL butyl acrylates, 15mL hydroxyethyl methacrylates weigh 2.95g benzoyl peroxide first
Acyl, 4.0mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is fallen
Enter dropping funel, mixture A is added dropwise in four-hole bottle with dropping funel, uniformly drip off within 3 hours；In 120 DEG C of guarantors after completion of dropping
Temperature 1 hour；
(2) 36mL methyl methacrylates are measured respectively, 36mL butyl acrylates, 25mL hydroxyethyl methacrylates,
10mL acrylic acid, weighs 2.7mL n- dodecyl mereaptans, and 2.00g benzoyl peroxides are well mixed in beaker and obtain mixture B,
Mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 10mL butyl glycol ethers are measured, 0.1g benzoyl peroxides are added thereto to
With 0.1mL n- dodecyl mereaptans, at the uniform velocity it is added dropwise 0.5～1 hour until completely dissolved；2 hours are incubated at 120 DEG C.
(4) the ethylene glycol fourth methyl ether solution containing 132mmol diethanol amine is added dropwise after being cooled to 90 DEG C, is subsequently adding
The water of 130mL is quickly stirred half an hour, water-borne acrylic resin is obtained, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 2
(1) 150mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 114 DEG C is heated to；Measure respectively
54mL methyl methacrylates are taken, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 14.07g benzoyl peroxide first
Acyl, 15mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 8mL n- dodecyl mereaptans, and 24.22g benzoyl peroxides are well mixed in beaker and obtain mixture B, will
Mixture B is poured in dropping funel, and mixture B is at the uniform velocity added dropwise in four-hole bottle, and drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL butyl glycol ethers are measured, 1.09g benzoyl peroxide first is added thereto to
Acyl and 0.6mL n- dodecyl mereaptans, are at the uniform velocity added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 600mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 3
(1) 150mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 116 DEG C is heated to；Measure respectively
54mL methyl methacrylates are taken, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 15.04g benzoyl peroxide first
Acyl, 13mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 8.78mL n- dodecyl mereaptans, and 9.00g benzoyl peroxides are well mixed in beaker and obtain mixture B,
Mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL butyl glycol ethers are measured, 0.5g benzoyl peroxides are added thereto to
With 0.4mL n- dodecyl mereaptans, at the uniform velocity it is added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 500mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 4
(1) 50mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 116 DEG C is heated to；Measure respectively
18mL methyl methacrylates are taken, 18mL butyl acrylates, 15mL hydroxyethyl methacrylates weigh 2.99g benzoyl peroxide first
Acyl, 4mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 35mL methyl methacrylates are measured respectively, 35mL butyl acrylates, 25mL hydroxyethyl methacrylates,
10mL acrylic acid, weighs 2.9mL n- dodecyl mereaptans, and 1.00g benzoyl peroxides are well mixed in beaker and obtain mixture B,
Mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 10mL butyl glycol ethers are measured, 0.12g benzoyl peroxide first is added thereto to
Acyl and 0.1mL n- dodecyl mereaptans, are at the uniform velocity added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 15mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 120mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 5
(1) 150mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 114 DEG C is heated to；Measure respectively
54mL methyl methacrylates are taken, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 14.00g benzoyl peroxide first
Acyl, 12mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 18.6mL n- dodecyl mereaptans, and 23.48g benzoyl peroxides are well mixed in beaker and obtain mixture
B, mixture B is poured in dropping funel, and mixture B is at the uniform velocity added dropwise in four-hole bottle, and drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL butyl glycol ethers are measured, 0.5g benzoyl peroxides are added thereto to
With 0.4mL n- dodecyl mereaptans, at the uniform velocity it is added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 700mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 6
(1) 150mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 114 DEG C is heated to；Measure respectively
54mL methyl methacrylates are taken, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 8.36g benzoyl peroxide first
Acyl, 12mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 8.2mL n- dodecyl mereaptans, and 12.03g benzoyl peroxides are well mixed in beaker and obtain mixture B,
Mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL butyl glycol ethers are measured, 0.32g benzoyl peroxide first is added thereto to
Acyl and 0.7mL n- dodecyl mereaptans, are at the uniform velocity added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 700mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 7
(1) 150mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 100 DEG C is heated to；Measure respectively
54mL methyl methacrylates are taken, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 12.01g benzoyl peroxide first
Acyl, 12mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 8.5mL n- dodecyl mereaptans, and 8.64g benzoyl peroxides are well mixed in beaker and obtain mixture B,
Mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL butyl glycol ethers are measured, 0.32g benzoyl peroxide first is added thereto to
Acyl and 0.7mL n- dodecyl mereaptans, are at the uniform velocity added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 700mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Embodiment 8
(1) 150mL butyl glycol ethers are measured with graduated cylinder to pour in four-hole boiling flask, with electric jacket 90 DEG C is heated to；Measure respectively
54mL methyl methacrylates are taken, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 11.32g benzoyl peroxide first
Acyl, 12mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, and mixture A is poured into
Dropping funel, with dropping funel mixture A is added dropwise in four-hole bottle, is uniformly dripped off within 3 hours；2 are incubated after completion of dropping at 120 DEG C
Hour；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 10.9mL n- dodecyl mereaptans, and 8.01g benzoyl peroxides are well mixed in beaker and obtain mixture B,
Mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL butyl glycol ethers are measured, 0.51g benzoyl peroxide first is added thereto to
Acyl and 0.5mL n- dodecyl mereaptans, are at the uniform velocity added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is added dropwise after being cooled to 90 DEG C and contains 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Houjia
The water for entering 700mL is quickly stirred half an hour, shown in the following experimental example table 1 of its performance parameter.
Water-borne acrylic resin achieved above when in use, is added without curing agent.
Comparative example
Comparative example 1 (using the initiator of low initiation temperature)
This comparative example method therefor is identical with the method therefor of embodiment 3, differs only in initiator used for peroxidating 2-
Ethyl acid tert-pentyl ester, it is swift in response in the early stage for preparing acrylic resin, and late phase reaction speed substantially slows down, and the third of generation
The molecular weight distribution of olefin(e) acid resin is extremely uneven, and final obtained water-borne acrylic resin viscosity is big, hardness, impact resistance
The performances such as energy, adhesive force, resistance to water are remarkably decreased, referring specifically to experimental example.
Comparative example 2 (initiator of low initiation temperature+lower boiling solvent, curing agent is not added with when using)
This comparative example method therefor is identical with the method therefor of embodiment 3, differs only in initiator used for peroxidating 2-
Ethyl acid tert-pentyl ester, solvent for use is methyl alcohol, and curing agent is added without when using, its hardness, shock resistance, adhesive force, resistance to
The poor performance such as aqueous, referring specifically to experimental example.
Comparative example 3 (initiator of low initiation temperature+lower boiling solvent, curing agent is added when using)
(1) measure 150mL methyl alcohol with graduated cylinder to pour in four-hole boiling flask, with electric jacket 64 DEG C are heated to；54mL is measured respectively
Methyl methacrylate, 54mL butyl acrylates, 45mL hydroxyethyl methacrylates weigh 15.04g peroxidating 2- ethyl acids
Tert-pentyl ester, 13mL n- dodecyl mereaptans mix in beaker, ultrasonically treated, and all dissolving obtains mixture A to solid, by mixture A
Pour dropping funel into, mixture A is added dropwise in four-hole bottle with dropping funel, uniformly drip off within 3 hours；In 60 DEG C of guarantors after completion of dropping
Temperature 2 hours；
(2) 108mL methyl methacrylates are measured respectively, 108mL butyl acrylates, 75mL hydroxyethyl methacrylates,
30mL acrylic acid, weighs 8.78mL n- dodecyl mereaptans, and 9.00g peroxidating 2- ethyl acid tert-pentyl esters are well mixed in beaker
To mixture B, mixture B is poured in dropping funel, mixture B is at the uniform velocity added dropwise in four-hole bottle, drop finishes within 3 hours.
(3) initiator and chain-transferring agent are added, 30mL methyl alcohol is measured, 0.5g peroxidating 2- ethyl acid uncles are added thereto to
Pentyl ester and 0.4mL n- dodecyl mereaptans, are at the uniform velocity added dropwise 1 hour until completely dissolved；3 hours are incubated at 120 DEG C.
(4) it is cooled to after room temperature and is added dropwise containing 40mL N, the ethylene glycol fourth methyl ether solution of N- dimethylethanolamines, Ran Housheng
Temperature backflow removes methyl alcohol, then adds the water of 500mL quickly to stir half an hour in system.
(5) after the completion of preparing, curing agent isocyanates is added in obtained water-borne acrylic resin.
The poor performances such as its hardness, shock resistance, adhesive force, resistance to water, referring specifically to experimental example.
Experimental example
(1) paint film is prepared：
By embodiment 1～8 and sample obtained in comparative example 1～3, metal sheet surface, natural surface drying are not applied directly to.
(2) hardness is measured：
It is dried being placed in baking oven after paint film in atmosphere natural surface drying 4 hours, temperature is 80 DEG C, takes out and determined after cooling
Hardness, using determination of pencil hardness method；
(3) adhesive force：
45 after being adjacent to adhesive tape after lattice are drawn using stroke lattice instrument and quickly pulls the change drawn at observation stroke lattice, if without paint film
Come off be defined as 0 grade, come off on a small quantity for 1 grade, come off in a large number for 2 grades.
(4) impact resistance：
Determined using Du Pont's shock resistance instrument, in the counterweight of upper ends constant weight, a pair of punching grooves and punching is placed below
Pestle is hit, tinplate is placed on the centre of groove and pestle, impact pestle of the counterweight immediately below certain height freely falling body is pounded and hit
Determine the shock resistance of paint film.Here the size of shock resistance is just demarcated using the weight and height of counterweight.
(5) resistance to water：
Paint film is immersed in running water, water resistance is observed, until paint film starts whiting timing is taken out.
(6) contact angle：It is measured using contact angle instrument (model JCY-1, sharp Chemical Company of Shenzhen three),
Contact angle is as described shown in accompanying drawing.
(7) granularity：By in a little sample dispersion to deionized water, determined using laser particle analyzer.
The properties of product test result of the not same date of table 1.
| Sample | Hardness | Adhesive force | Shock resistance | Contact angle | Resistance to water | Granularity/nm |
| Embodiment 1 | 2H | 0 grade | 1800g/42cm | 78.6 | 24h | 1156.9 |
| Embodiment 2 | 2H | 1 grade | 1800g/42cm | 95.5/ Fig. 1 | 6h | 122.1 |
| Embodiment 3 | HB | 1 grade | 1800g/42cm | 85.8/ Fig. 2 | 8h | 885.2 |
| Embodiment 4 | 3H | 0 grade | 1800g/42cm | 78.92 | 24h | 1937.5 |
| Embodiment 5 | 3H | 0 grade | 1000g/50cm | 89.7 | 27h | 264.3 |
| Embodiment 6 | 5H | 0 grade | 1000g/50cm | 84.49/ Fig. 3 | 8h | 544.7 |
| Embodiment 7 | 4H | 1 grade | 1000g/42cm | 85.13/ Fig. 4 | 8h | 361.0 |
| Embodiment 8 | HB | 3 grades | 300g/30cm | 100.5/ Fig. 5 | 3h | 477.0 |
| Comparative example 1 | H | 3 grades | 300g/20cm | 80 | 2h | 803.2 |
| Comparative example 2 | 2B | 3 grades | 300g/15cm | 73 | 3h | 205.1 |
| Comparative example 3 | 2H | 0 grade | 100g/45cm | 75 | 72 | 200.5 |
The present invention has been described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Various equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention
In the range of.Protection scope of the present invention is defined by claims.
Claims (15)
1. a kind of method for preparing water-borne acrylic resin, it is characterised in that the method is comprised the following steps：
(1) solvent is warming up to into 90 DEG C～120 DEG C, in the solvent after intensification be added dropwise include acrylic ester monomer mixture I,
The mixture A of initiator and chain-transferring agent, insulation, the temperature of the insulation is 100 DEG C～130 DEG C, and the solvent is ethylene glycol
Butyl ether,
The acrylic ester monomer mixture I includes the component of volumes below proportioning,
The parts by volume of methyl methacrylate 15～20
The parts by volume of butyl acrylate 15～20
The parts by volume of hydroxyethyl methacrylate 10～18,
The mixture A includes the component of following weight/volume proportioning,
The parts by volume of acrylic ester monomer mixture I 40～60
The weight portion of initiator 1～20
The parts by volume of chain-transferring agent 2～8,
Wherein, 1 parts by volume/1 weight portion, equivalent to, 1mL/1g, or, 1L/1kg；
(2) being added dropwise in the system obtained to step 1 includes acrylic ester monomer mixtures II, initiator, chain-transferring agent and third
The mixture B of alkene acid compounds,
The acrylic ester monomer mixtures II includes the component of volumes below ratio,
The parts by volume of methyl methacrylate 15～20
The parts by volume of butyl acrylate 15～20
The parts by volume of hydroxyethyl methacrylate 10～18,
The mixture B includes the component of following weight/volume part,
Wherein, 1 parts by volume/1 weight portion, equivalent to, 1mL/1g, or 1L/1kg；
(3) initiator and chain-transferring agent are added in the system obtained to step 2, is incubated, the temperature of insulation is 100 DEG C～130 DEG C；
(4) alkali is added after lowering the temperature, water is added, is stirred, obtain water-borne acrylic resin；
Initiator described in step 1-3 is benzoyl peroxide, peroxidating two (adjacent monomethyl benzoyl), TBHP
And isopropyl benzene hydroperoxide.
2. method according to claim 1, it is characterised in that in step 1,
The acrylic ester monomer mixture I includes the component of volumes below proportioning,
The parts by volume of methyl methacrylate 16～19
The parts by volume of butyl acrylate 16～19
The parts by volume of hydroxyethyl methacrylate 12～16；And/or
Solvent is warming up to into 100 DEG C～118 DEG C；And/or
The temperature of the insulation is 110 DEG C～125 DEG C.
3. method according to claim 2, it is characterised in that in step 1,
The acrylic ester monomer mixture I includes the component of volumes below proportioning,
The parts by volume of methyl methacrylate 18
The parts by volume of butyl acrylate 18
The parts by volume of hydroxyethyl methacrylate 15；And/or
Solvent is warming up to into 114 DEG C～116 DEG C；And/or
The temperature of the insulation is 120 DEG C.
4. method according to claim 1, it is characterised in that mixture A described in step 1 includes following weight/volume
The component of proportioning,
The parts by volume of acrylic ester monomer mixture I 45～55
The weight portion of initiator 2～18
The parts by volume of chain-transferring agent 3～7.
5. method according to claim 4, it is characterised in that mixture A described in step 1 includes following weight/volume
The component of proportioning,
The parts by volume of acrylic ester monomer mixture I 51
The weight portion of initiator 3～15
The parts by volume of chain-transferring agent 4～5.
6. method according to claim 1, it is characterised in that the bag of acrylic ester monomer mixtures II described in step 2
The component of volumes below ratio is included,
The parts by volume of methyl methacrylate 16～19
The parts by volume of butyl acrylate 16～19
The parts by volume of hydroxyethyl methacrylate 12～16.
7. method according to claim 6, it is characterised in that the bag of acrylic ester monomer mixtures II described in step 2
The component of volumes below ratio is included,
The parts by volume of methyl methacrylate 18
The parts by volume of butyl acrylate 18
The parts by volume of hydroxyethyl methacrylate 12.5.
8. method according to claim 1, it is characterised in that mixture B described in step 2 includes following weight/volume
The component of part,
9. method according to claim 8, it is characterised in that mixture B described in step 2 includes following weight/volume
The component of part,
10. the method according to one of claim 1～9, it is characterised in that
Chain-transferring agent is identical or different described in step 1-3, and one or more be respectively selected from aliphatic mercaptan.
11. methods according to claim 10, it is characterised in that
Chain-transferring agent described in step 1-3 is in n-dodecyl mercaptan, tert-dodecylmercaotan and n-octadecane base mercaptan
One or more.
12. methods according to claim 11, it is characterised in that
Initiator described in step 1-3 is benzoyl peroxide, and/or
Chain-transferring agent described in step 1-3 is n-dodecyl mercaptan.
13. methods according to one of claim 1～9, it is characterised in that in step 3 be incubated temperature be 110 DEG C～
125 DEG C, and/or
Alkali described in step 4 be diethylamine, triethylamine, N, in N- dimethylethanolamines, diethanol amine, monoethanolamine or ammoniacal liquor
Plant or various.
14. methods according to claim 13, it is characterised in that the temperature being incubated in step 3 is 120 DEG C, and/or
Alkali described in step 4 is N, N- dimethylethanolamines and/or diethanol amine.
The using method of water-borne acrylic resin obtained in 15. methods according to one of claim 1～14, its feature exists
In the water-borne acrylic resin is added without when in use curing agent.
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| CN108395495A (en) * | 2018-03-29 | 2018-08-14 | 苏州博莱特新材料有限公司 | A kind of water-based acrylic resin |
| CN108456278A (en) * | 2018-03-29 | 2018-08-28 | 苏州博莱特新材料有限公司 | A kind of preparation method of water-based acrylic resin |
| CN111217954A (en) * | 2018-11-26 | 2020-06-02 | 阜阳师范学院 | Acrylate aqueous dispersion 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 |
| CN111944377A (en) * | 2020-08-24 | 2020-11-17 | 江苏华夏制漆科技有限公司 | Multifunctional water-based epoxy acrylic resin composition and preparation method thereof |
| CN112662353B (en) * | 2020-12-07 | 2022-08-05 | 浙江农林大学 | Surface wetting type phenolic resin adhesive for bamboo materials such as bamboo green, bamboo yellow and the like and synthetic method thereof |
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