CN114621385A - High-distinctness of image waterborne acrylic resin and preparation method thereof - Google Patents
High-distinctness of image waterborne acrylic resin and preparation method thereof Download PDFInfo
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- CN114621385A CN114621385A CN202011458652.1A CN202011458652A CN114621385A CN 114621385 A CN114621385 A CN 114621385A CN 202011458652 A CN202011458652 A CN 202011458652A CN 114621385 A CN114621385 A CN 114621385A
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 48
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- 238000004945 emulsification Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000001502 supplementing effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 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 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- RZRRGGYPPDLRTI-UHFFFAOYSA-N propylperoxybenzene Chemical compound CCCOOC1=CC=CC=C1 RZRRGGYPPDLRTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000003973 paint Substances 0.000 abstract description 10
- 238000010992 reflux Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000005586 carbonic acid group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a high-distinctness water-based acrylic resin, which comprises raw materials of an acrylic monomer, a styrene monomer, an initiator, a chain transfer agent, a solvent and a mixed solution of glycidyl versatate and vinyl versatate with the mass ratio of 2.5: 1. The preparation method comprises the following steps: adding 80% of solvent into a reaction kettle, and heating and preserving heat; mixing an acrylic monomer, a styrene monomer, a chain transfer agent and 90% of an initiator, and dripping into a reaction kettle; then, dripping mixed solution consisting of glycidyl versatate and ethylene versatate and preserving heat; and supplementing the rest solvent and the initiator, preserving heat, then cooling to 90-95 ℃, dripping an amine neutralizer solution, dispersing at a high speed, slowly dripping deionized water at 90-95 ℃ for reverse phase emulsification to obtain the water-based acrylic resin. The water-based acrylic resin can improve the resin gloss, reduce the resin viscosity and improve the flexibility, impact resistance and water resistance of a paint film.
Description
Technical Field
The invention belongs to the field of resin materials, and particularly relates to a high-distinctness of image water-based acrylic resin and a preparation method thereof.
Background
The water-based acrylic resin has the characteristics of good light resistance, weather resistance, light color, chemical reagent resistance, good construction performance, low VOC and the like, and is widely applied to the aspects of building emulsion paint and water-based industrial coating. However, in high-end fields such as rail transit, the defects of insufficient gloss, heavy fog shadow, insufficient distinctness of image, poor water resistance and the like of the water-based acrylic paint are also exposed.
For example, publication No. CN103342783A discloses a high gloss water-based acrylic resin which has high gloss, high hardness, high distinctness of image, high fullness and other characteristics, but the water-resistant effect is not satisfactory; publication No. CN106188384A discloses a method for preparing acrylic resin, which has qualified properties such as water resistance, but the distinctness of image cannot meet the requirements. Therefore, it is necessary to research a water-based acrylic resin with high distinctness of image to meet the requirements of high-end applications in rail transit.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology and provide the water-based acrylic resin with water resistance, high fullness, high gloss and good distinctness of image and the preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the water-based acrylic resin with high distinctness of image is mainly prepared from raw materials, namely an acrylic monomer, a styrene monomer, an initiator, a chain transfer agent and a solvent, wherein the raw materials also comprise a mixed solution of glycidyl versatate and ethylene versatate with the mass ratio of 2.5: 1.
The tertiary carbonic acid glycidyl ester and the tertiary carbonic acid ethylene ester are active substances, the tertiary carbonic acid ethylene ester can be copolymerized with acrylic monomers, the tertiary carbonic acid glycidyl ester can be subjected to ring-opening reaction with the acrylic monomers and can also be used as an active solvent to participate in the curing reaction of a paint film at the later stage, the resin viscosity can be reduced by steric hindrance and shielding effect of a large group on a tertiary carbon atom in the active substances, and meanwhile, the wet film viscosity can be reduced in the curing process of the paint film, so that the leveling effect of the paint film is facilitated, and the surface effects of the paint film such as the gloss, the distinctness of image and the like are improved.
The above aqueous acrylic resin preferably further comprises an amine neutralizer.
The above aqueous acrylic resin is preferably prepared from the following raw materials in parts by weight:
acrylic acid monomer: 84-145 parts of a water-soluble polymer,
styrene monomers: 8 to 15 parts of (A) a water-soluble polymer,
the mixed solution of the tertiary carbonic acid glycidyl ester and the tertiary carbonic acid ethylene ester comprises the following components: 1 to 8 parts of (A) a water-soluble polymer,
initiator: 1.5 to 5.6 parts by weight,
chain transfer agent: 0.3 to 2.25 parts of,
amine neutralizer: 1.6 to 5.5 parts by weight,
solvent: 41-71 parts of a water-soluble polymer,
deionized water: 100 to 120 parts.
In the above aqueous acrylic resin, the solvent is preferably one or more selected from ethanol, ethyl acetate, isopropanol, propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol butyl ether, and diethylene glycol butyl ether.
In the above aqueous acrylic resin, preferably, the amine neutralizer is one or more of triethanolamine, N-methyldiethanolamine, and N, N-dimethylethanolamine.
The above aqueous acrylic resin, preferably, the initiator is selected from one or more of azobisisobutyronitrile, dicumyl peroxide and phenylpropyl peroxide; the chain transfer agent is selected from one or more of dodecyl mercaptan and 2-mercaptoethanol.
The above aqueous acrylic resin, preferably, the acrylic monomer comprises one or more of acrylic acid, methyl methacrylate, hydroxy acrylate, butyl acrylate and isooctyl acrylate; the styrenic monomer is selected from styrene.
As a general inventive concept, the present invention also provides a method for preparing the above aqueous acrylic resin, comprising the steps of:
(1) adding 80% of solvent into a reaction kettle, heating to 120-150 ℃, and preserving heat for 25-35 min;
(2) mixing and uniformly dispersing an acrylic monomer, a styrene monomer, a chain transfer agent and 90% of an initiator, and then dripping the uniformly dispersed mixture into the reaction kettle in the step (1);
(3) dripping mixed solution consisting of glycidyl versatate and ethylene versatate into the reaction kettle and preserving heat;
(4) supplementing the residual solvent and the initiator, preserving heat for 1-3 h, then cooling to 90-95 ℃, dropping an amine neutralizer solution (adjusting the pH to about 8.5), dispersing at a high speed, and slowly dropping deionized water at 90-95 ℃ for reverse emulsification for 2-3h to obtain a water-soluble water-based acrylic resin dispersoid; the amine neutralizer solvent is a mixed solution of an amine neutralizer and an environment-friendly solvent, wherein the environment-friendly solvent comprises one or more of ethanol, propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol butyl ether and diethylene glycol butyl ether.
In the preparation method, preferably, in the step (2), the mixture is dropwise added within 4-5 hours;
in the step (4), the amine neutralizer solution is dripped within 10-15 min; the temperature of the reverse phase emulsification is 90-95 ℃, and the rotating speed of the high-speed dispersion of the reverse phase emulsification is 3000-5000 r/min.
In the above preparation method, preferably, in the step (3), the time for adding the mixed solution of glycidyl versatate and ethylene versatate is within 5min after the completion of the step (2); and (3) dropwise adding the mixed solution consisting of the glycidyl versatate and the ethylene versatate within 15-20 min, and then preserving the heat for 30 min.
In the preparation method, preferably, in the step (4), the dispersion resin is subjected to inverse emulsification at 90-95 ℃ under the high-speed condition of 3000-.
Compared with the prior art, the invention has the advantages that:
(1) the water-based acrylic resin disclosed by the invention adopts the mixed solution composed of the tertiary carbonic acid glycidyl ester and the tertiary carbonic acid ethylene ester, the ester group hydrolysis stability is provided by the tertiary carbonic acid glycidyl ester and the tertiary carbonic acid ethylene ester branched fatty acid alpha steric hindrance structure, meanwhile, the weather resistance of the resin is improved by the aliphatic character of the tertiary carbonic acid group, and the suspended tertiary carbonic acid group can also reduce the viscosity, increase the pigment wettability and the internal plasticization; and due to the shielding effect of the alkyl group on the alpha-carbon atom of the ethylene versatate and the non-polarity of the alkyl group, the ethylene versatate has excellent hydrophobicity and ultraviolet resistance, and can improve the gloss of resin, reduce the viscosity of the resin, and improve the flexibility, impact resistance and water resistance of a paint film.
(2) The water-based acrylic resin disclosed by the invention adopts the mixed solution composed of the glycidyl versatate and the vinyl versatate, wherein the reactivity ratio of the vinyl versatate and acrylic acid is close, the reaction activity is high, the conversion efficiency is high, the glossiness of the acrylic resin is obviously improved, the effect of reducing the viscosity of the resin is obviously achieved by the multi-branched large groups on the tertiary carbon atoms, the leveling effect is improved, and the glossiness is further improved.
(3) In the preparation process, the amine neutralizer is added before the resin is reversed, the pH value is adjusted to about 8.5 to improve the reversed phase effect, the distribution coefficient in the oil phase is reduced by gradually converting acrylic acid into salt, and meanwhile, excessive amine hydrate reacts with hydroxyl or forms associated molecules with hydrogen bonds, so that the water solubility is improved.
(4) The preparation process of the invention carries out inverse emulsification on the dispersed resin under the high-speed conditions of 90-95 ℃ and 3000-.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a high-distinctness of image waterborne acrylic resin which is mainly prepared from the following raw materials in parts by weight:
acrylic monomers (4 parts of acrylic acid, 35 parts of methyl methacrylate, 16 parts of hydroxyl acrylate, 23 parts of butyl acrylate and 11 parts of isooctyl acrylate): 89 parts of (a) to (b),
styrene monomer (styrene): 12 parts of (a) to (b),
initiator (azobisisobutyronitrile): 4.7 parts of (a) a solvent,
chain transfer agent (dodecyl mercaptan): 1.2 parts of (A) a solvent,
amine neutralizer (N, N-dimethylethanolamine): 2.8 parts of (by weight),
mixed solvent (2.5 parts of tertiary carbonic acid glycidyl ester and 1 part of tertiary carbonic acid ethylene ester): 3.5 parts of (A) a reaction product,
solvent (propylene glycol butyl ether 25 parts, propylene glycol methyl ether acetate 25 parts): 50 parts of the raw materials.
The preparation method of the high distinctness of image waterborne acrylic resin of the embodiment comprises the following steps:
(1) adding 80% of solvent into a reaction kettle, stirring, introducing nitrogen, heating and refluxing, controlling the temperature at 138 ℃, and keeping the temperature for 30 min;
(2) fully mixing and dissolving 4 parts of acrylic acid, 35 parts of methyl methacrylate, 16 parts of hydroxyl acrylate, 23 parts of butyl acrylate, 11 parts of isooctyl acrylate, 12 parts of styrene, 4.23 parts of azobisisobutyronitrile and 1.2 parts of dodecyl mercaptan, dropwise adding into the reaction kettle in the step (1) at a constant speed, and finishing dropwise adding for 4 hours;
(3) dropwise adding a mixed solution consisting of 2.5 parts of glycidyl versatate and 1 part of ethylene versatate into the reaction kettle, keeping the temperature for 30min after 15min of dropwise adding;
(4) adding the balance of azodiisobutyronitrile and the balance of solvent into a reaction kettle, fully mixing and dissolving, preserving heat for 2 hours, stopping heating, introducing cooling water, and reducing the temperature to maintain the temperature in the reaction kettle to be 90 ℃;
(5) and (2) under the condition of keeping the temperature at 90 ℃, dripping a mixed solution consisting of 2.8 parts of N, N-dimethylethanolamine and 1.5 parts of propylene glycol methyl ether into the reaction kettle, after dripping for 10min (the pH is about 8.5), accelerating the stirring speed to 4500r/min, uniformly and continuously dripping 120 parts of deionized water, after dripping for 2h, discharging, and filtering to obtain the water-based acrylic resin.
Example 2:
the invention relates to a high-distinctness of image waterborne acrylic resin which is mainly prepared from the following raw materials in parts by weight:
acrylic monomers (20 parts of propylene glycol methyl ether acetate, 4.5 parts of acrylic acid, 40 parts of methyl methacrylate, 13 parts of hydroxyl acrylate, 22 parts of butyl acrylate and 12 parts of isooctyl acrylate): 111.5 parts of (A) and (B),
styrene monomer (styrene): 10 parts of (a) to (b),
initiator (azobisisobutyronitrile): 4.7 parts of (a) a solvent,
chain transfer agent (dodecyl mercaptan): 1.5 parts of (A) a reaction product,
amine neutralizer (N, N-dimethylethanolamine): 3.0 parts of (C), by weight,
mixed solution (5 parts of tertiary carbonic acid glycidyl ester and 2 parts of tertiary carbonic acid ethylene ester): 7 parts of (a) a mixture of (b),
solvent (propylene glycol butyl ether 31 parts, propylene glycol methyl ether acetate 25 parts): and 56 parts.
The preparation method of the water-based acrylic resin with high distinctness of image of the embodiment is the same as that of the embodiment 1.
Comparative example 1:
the raw materials and the preparation method of the aqueous acrylic resin of this comparative example were substantially the same as those of example 1 except that the weight part of the mixed liquid of glycidyl versatate and vinyl versatate in this comparative example was 2 parts, and the mass ratio of glycidyl versatate and vinyl versatate was 1: 1.
comparative example 2:
the thermosetting acrylic resin of the comparative example is prepared from the following raw materials in parts by weight: 15% of prepolymer, 25% of styrene, 15% of n-butyl acrylate, 10% of butyl acrylate, 0.5% of tert-butyl peroxybenzoate and 34.5% of xylene.
The preparation method of the thermosetting acrylic resin of the comparative example comprises the following steps:
(1) preparation of a prepolymer: firstly, placing 39.8 percent of dimethylbenzene by weight ratio into a reaction kettle, stirring and heating to the reflux temperature of 137 ℃, and keeping reflux for 1 hour; uniformly dropwise adding a mixed monomer consisting of 33.5% of allyl alkylphenol polyoxyethylene, 12.5% of methacrylic acid and 14.0% of ethyl methacrylate at a reflux temperature, and ensuring that the mixed monomer is completely dripped within 4-4.5 hours; after the dropwise addition is finished, continuously maintaining for 2 hours in a reflux state, and then supplementing an initiator of 0.2% tert-butyl peroxybenzoate until the reaction is complete to prepare a prepolymer;
(2) preparation of thermosetting acrylic resin: firstly, putting a xylene prepolymer with the weight ratio of 34.5 percent into a reaction kettle with 15 percent of the prepolymer, stirring and heating to the reflux temperature of 137 ℃, and keeping reflux for 1 hour; uniformly dripping a mixed monomer consisting of 25 percent of styrene, 15 percent of n-butyl acrylate and 10 percent of butyl acrylate at the reflux temperature to ensure that the mixed monomer is dripped in 4 to 4.5 hours; after the dropwise addition is finished, the mixture is kept for 2 hours under the reflux state, then 0.5% of tert-butyl peroxybenzoate initiator is supplemented until the reaction is complete, and finally the thermosetting acrylic resin is prepared, and after the resin solid content, the viscosity, the acid value and the appearance are checked, the temperature is reduced after the resin is qualified, and the filtration and the packaging are carried out.
Comparative example 3:
the benzene-free high-gloss high-solid acrylic resin of the comparative example is mainly prepared from the following raw materials: 10% of n-butyl alcohol, 12% of butyl acetate, 0.5% of thiopropionic acid, 10% of hydroxypropyl acrylate, 15% of lauryl methacrylate, 38% of isobornyl acrylate, 7% of glycidyl methacrylate, 5% of butyl methacrylate and 2.5% of azodiisobutyronitrile.
The preparation method of the benzene-free high-gloss high-solid acrylic resin of the comparative example comprises the following steps:
(1) preparing raw materials according to a proportion, adding 90 percent of the total amount of n-butyl alcohol and butyl acetate into a reaction kettle, starting nitrogen purging, and starting to heat to 110 ℃;
(2) mixing mercaptopropionic acid, hydroxypropyl acrylate, lauryl methacrylate, isobornyl acrylate, glycidyl methacrylate, butyl methacrylate and 90% of azobisisobutyronitrile according to a proportion, and dropwise adding two thirds of the mixed solution into the reaction kettle in the step (1) for 3 hours;
(3) heating to reflux state at 125 deg.c for 0.5 hr to react completely;
(4) dropwise adding the remaining one third of the mixed solution obtained in the step (2) into a reaction kettle for 1.5 hours, and continuing reflux reaction;
(5) supplementing the rest 10% of n-butyl alcohol and butyl acetate, supplementing the rest 10% of azodiisobutyronitrile, and continuously carrying out reflux reaction for 1 hour;
(6) and (5) cooling after the reflux is finished, and then filtering and packaging.
The results of testing the properties of the aqueous acrylic resins prepared in examples 1 to 4 of the present invention and comparative example are shown in Table 1.
TABLE 1 test results of the paint film properties of the waterborne acrylic resins of the examples
As is apparent from the results shown in Table 1, the water-based acrylic resin provided by the present invention has the advantages of low viscosity, good hardness, good water resistance, good distinctness of image, high gloss, etc., and is a water-based acrylic resin with excellent properties, which can improve gloss, reduce resin viscosity, and improve paint film flexibility, impact resistance and water resistance.
Claims (10)
1. The high-distinctness of image water-based acrylic resin is characterized by further comprising a mixed solution of glycidyl versatate and vinyl versatate with the mass ratio of 2.5: 1.
2. The aqueous acrylic resin of claim 1 wherein the starting material further comprises an amine neutralizer.
3. The aqueous acrylic resin as claimed in claim 2, wherein the amount of each raw material is, in parts by weight:
acrylic acid monomer: 84-145 parts of a water-soluble polymer,
styrene monomers: 8 to 15 parts of (A) a water-soluble polymer,
the mixed solution of the tertiary carbonic acid glycidyl ester and the tertiary carbonic acid ethylene ester comprises the following components: 1 to 8 parts of (A) a water-soluble polymer,
initiator: 1.5 to 5.6 parts by weight,
chain transfer agent: 0.3 to 2.25 parts of,
amine neutralizer: 1.6 to 5.5 parts by weight,
solvent: 41-71 parts of a water-soluble polymer,
deionized water: 100 to 120 parts.
4. The aqueous acrylic resin according to claim 3, wherein the solvent is one or more selected from the group consisting of ethanol, ethyl acetate, isopropyl alcohol, propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol butyl ether, and diethylene glycol butyl ether.
5. The aqueous acrylic resin of claim 3 wherein the amine neutralizer is one or more of triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine.
6. The aqueous acrylic resin according to claim 3, wherein the initiator is selected from one or more of azobisisobutyronitrile, dicumyl peroxide, phenylpropyl peroxide; the chain transfer agent is selected from one or more of dodecyl mercaptan and 2-mercaptoethanol.
7. The aqueous acrylic resin of any one of claims 1 to 6 wherein the acrylic monomer comprises one or more of acrylic acid, methyl methacrylate, hydroxy acrylate, butyl acrylate, isooctyl acrylate; the styrenic monomer is selected from styrene.
8. A method for preparing the aqueous acrylic resin according to any one of claims 1 to 7, comprising the steps of:
(1) adding 80% of solvent into a reaction kettle, heating to 120-150 ℃, and preserving heat for 25-35 min;
(2) mixing and uniformly dispersing an acrylic monomer, a styrene monomer, a chain transfer agent and 90% of an initiator, and then dripping the uniformly dispersed mixture into the reaction kettle in the step (1);
(3) dripping mixed solution consisting of glycidyl versatate and ethylene versatate into the reaction kettle and preserving heat;
(4) and supplementing the residual solvent and the initiator, keeping the temperature for 1-3 h, then cooling to 90-95 ℃, dripping an amine neutralizer solution, dispersing at a high speed, slowly dripping deionized water at 90-95 ℃ for reverse emulsification for 2-3h, and obtaining the water-soluble water-based acrylic resin dispersoid.
9. The preparation method according to claim 8, wherein in the step (2), the mixture is dropwise added within 4-5 hours;
in the step (4), the amine neutralizer solution is dripped within 10-15 min; the temperature of the reverse phase emulsification is 90-95 ℃, and the rotating speed of the high-speed dispersion of the reverse phase emulsification is 3000-5000 r/min.
10. The method according to claim 8, wherein in the step (3), the time for adding the mixed solution of glycidyl versatate and vinyl versatate is within 5min after the completion of the step (2); and (3) dropwise adding the mixed solution consisting of the glycidyl versatate and the ethylene versatate within 15-20 min, and then preserving the heat for 30 min.
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| CN115387118A (en) * | 2022-09-16 | 2022-11-25 | 卫星化学股份有限公司 | Organic phosphorus modified acrylic slurry and preparation method and application thereof |
| CN115387118B (en) * | 2022-09-16 | 2023-06-16 | 卫星化学股份有限公司 | Organophosphorus modified acrylic slurry and preparation method and application thereof |
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