CN112876600A - Boiling-resistant phosphorus-containing aqueous acrylic dispersion resin and preparation method and application thereof - Google Patents
Boiling-resistant phosphorus-containing aqueous acrylic dispersion resin and preparation method and application thereof Download PDFInfo
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- CN112876600A CN112876600A CN202110032585.5A CN202110032585A CN112876600A CN 112876600 A CN112876600 A CN 112876600A CN 202110032585 A CN202110032585 A CN 202110032585A CN 112876600 A CN112876600 A CN 112876600A
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- methacrylate
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- acrylic
- boiling
- acrylate
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- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000009835 boiling Methods 0.000 title claims abstract description 36
- 239000006185 dispersion Substances 0.000 title claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 23
- 239000011574 phosphorus Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 48
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006184 cosolvent Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract 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 abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims abstract description 5
- 229940119545 isobornyl methacrylate Drugs 0.000 claims abstract description 5
- 239000002966 varnish Substances 0.000 claims abstract description 5
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004593 Epoxy Substances 0.000 claims abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 239000003973 paint Substances 0.000 claims description 21
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims description 20
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- -1 caprolactone modified methacrylate Chemical class 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 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
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (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
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
Abstract
The invention provides a boiling-resistant phosphorus-containing aqueous acrylic dispersion resin which comprises the following components in parts by weight: 25-32 parts of acrylic resin monomer I, 0.2-5 parts of acrylic resin monomer II, 4-15 parts of acrylic resin monomer III, 10-20 parts of cosolvent, 0.5-2 parts of initiator, 1-5 parts of neutralizer and 35-45 parts of deionized water; the acrylic resin monomer I comprises isobornyl methacrylate, the acrylic resin monomer II comprises methacrylic acid phosphate or acrylic acid epoxy phosphate, and the acrylic resin monomer III comprises acrylic acid. According to the invention, the acrylic resin monomer II and the acrylic resin monomer III are simultaneously introduced into the polymerization product of the acrylic resin monomer I to modify the polymerization product, so that the boiling resistance of the polymer is effectively improved. The aqueous acrylic acid dispersoid resin is used for preparing aqueous amino baking varnish coating, and can obviously improve the boiling resistance, the adhesiveness to metal substrates, the mechanical property and the glossiness of a coating film of the coating.
Description
Technical Field
The invention belongs to the technical field of poaching-resistant paint materials, and particularly relates to poaching-resistant phosphorus-containing aqueous acrylic acid dispersion resin and a preparation method and application thereof.
Background
The water-based paint is one of the development directions of environment-friendly paints, takes water as a dispersion medium, and has the advantages of no toxicity, environmental protection, low VOC content and the like. Among them, the water-based acrylic amino baking paint is favored in industries such as automobiles, household electrical appliances and the like because of the characteristics of high hardness, high glossiness, good gloss and color retention, excellent medium resistance and the like.
The water-based acrylic resin is used as the main resin of the water-based acrylic amino baking paint, has good water solubility, and can be compounded with amino resin to prepare the water-based acrylic amino baking paint with excellent comprehensive performance, so that the performance of the water-based acrylic resin directly influences the performance of the paint.
However, the aqueous acrylic resin has a large amount of carboxyl side groups, which results in poor boiling resistance of aqueous coatings prepared from the aqueous acrylic resin, and limits the application of the aqueous acrylic resin in boiling-resistant paints.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a boiling-resistant phosphorus-containing aqueous acrylic dispersion resin and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin comprises the following components in parts by weight: 25-32 parts of acrylic resin monomer I, 0.2-5 parts of acrylic resin monomer II, 4-15 parts of acrylic resin monomer III, 10-20 parts of cosolvent, 0.5-2 parts of initiator, 1-5 parts of neutralizer and 35-45 parts of deionized water.
Further, the acrylic resin monomer I comprises at least one of isobornyl methacrylate, caprolactone modified methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and cyclohexyl methacrylate.
Further, the acrylic resin monomer in the second part comprises at least one of methacrylic acid phosphate and acrylic acid epoxy phosphate.
Further, the part iii acrylic resin monomer includes at least one of acrylic acid, methacrylic acid, caprolactone-modified methacrylate, isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, cyclohexyl methacrylate.
According to the invention, the acrylic resin monomer II and the acrylic resin monomer III are introduced into the polymerization product of the acrylic resin monomer I, and the polymerization product is modified to prepare the water-based acrylic dispersion resin with boiling resistance, good adhesion, high hardness, impact resistance and high gloss.
Through experimental research, the inventor finds that compared with the method of singly introducing the acrylic resin monomer with the III part, the method of simultaneously introducing the acrylic resin monomer with the II part and the acrylic resin monomer with the III part can better increase the boiling resistance, the adhesive force to a metal substrate, the glossiness and the mechanical property of the aqueous acrylic dispersion resin.
Preferably, the cosolvent comprises at least one of methyl 3-methoxypropionate and butyl propylene glycol ether. The cosolvent is an environment-friendly solvent, has good dissolving capacity and is compatible with water.
Preferably, the cosolvent consists of methyl 3-methoxypropionate and propylene glycol butyl ether, and the mass ratio of methyl 3-methoxypropionate: and (3) 1 is propylene glycol butyl ether (1-2). The inventor finds that when methyl 3-methoxypropionate and propylene glycol butyl ether are compounded and used according to the proportion, the prepared acrylic dispersion resin resisting boiling water has better water dispersibility.
Preferably, the cosolvent consists of methyl 3-methoxypropionate and propylene glycol butyl ether, and the mass ratio of methyl 3-methoxypropionate: propylene glycol butyl ether is 1.5: 1. The inventor has found through experimental study that when methyl 3-methoxypropionate and propylene glycol butyl ether are compounded and used in the above proportion, the water dispersibility of the prepared boiling water resistant acrylic dispersion resin is best.
Preferably, the initiator comprises at least one of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate and dicumyl peroxide.
Preferably, the neutralizing agent comprises at least one of triethylamine, dimethylethanolamine, and ammonia.
In another aspect, the invention also provides a preparation method of the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin, which comprises the following steps:
(1) adding a cosolvent into a container, heating to 140-145 ℃, then adding acrylic resin monomer I and an initiator with the dosage of 45-55%, and carrying out heat preservation reaction for 15-30 min;
(2) mixing the acrylic resin monomer II and the acrylic resin monomer III to obtain a mixed monomer, adding the mixed monomer and an initiator with the use amount of 15-20% into the reaction system in the step (1), carrying out heat preservation reaction for 60-80 min, adding the rest of the initiator, and carrying out heat preservation reaction for 2-2.5 h;
(3) and (3) cooling the reaction system obtained in the step (2) to 90 +/-2 ℃, adding a neutralizing agent, cooling to 80 +/-2 ℃ after the neutralization reaction is finished, then adding deionized water, and uniformly dispersing to obtain the boiling-resistant phosphorus-containing aqueous acrylic acid dispersoid resin.
Preferably, the acrylic resin monomer I is added in a dropwise manner, and the dropwise addition takes more than 3 hours.
Preferably, the mixed monomer is added in a dropwise manner, and the dropwise addition takes more than 1 hour.
In another aspect, the invention also provides the application of the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin in an aqueous coating.
Preferably, the water-based paint is water-based acrylic amino baking paint.
Preferably, the content of the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin in the aqueous acrylic amino baking paint is 70-75 parts.
On the other hand, the invention also provides a water-based acrylic amino baking varnish, which comprises the following components in parts by weight: 70-75 parts of boiling-resistant phosphorus-containing aqueous acrylic dispersion resin, 15-20 parts of aqueous amino resin, 3-5 parts of an auxiliary agent and 4-10 parts of deionized water.
Preferably, the auxiliary agent comprises at least one of a ByK-190 wetting dispersant, a ByK-022 defoaming agent, a Digao Tego-410 flatting agent, propylene glycol methyl ether and a neutralizing agent.
On the other hand, the invention also provides a preparation method of the water-based acrylic amino baking paint, which comprises the following steps: and mixing and uniformly dispersing the boiling-resistant phosphorus-containing aqueous acrylic acid dispersoid resin, the aqueous amino resin and the auxiliary agent, then adding deionized water, filtering and discharging to obtain the aqueous acrylic acid amino baking paint.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, through optimization of a formula and a process, the acrylic resin monomer II and the acrylic resin monomer III are simultaneously introduced into the polymerization product of the acrylic resin monomer I, so that the polymerization product is modified, and the water boiling resistance of the polymer is effectively improved. When the aqueous acrylic acid dispersoid resin prepared by the invention is used for preparing aqueous amino baking varnish paint, the boiling resistance of paint film, the adhesiveness to metal substrate, the mechanical property and the glossiness can be obviously improved.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Sources of raw materials in examples and comparative examples:
the cosolvent 1 comprises the following components: methyl 3-methoxypropionate and propylene glycol butyl ether, wherein the mass ratio of the methyl 3-methoxypropionate to the propylene glycol butyl ether is 1: 1.
The cosolvent 2 comprises the following components: methyl 3-methoxypropionate and propylene glycol butyl ether, wherein the mass ratio of the methyl 3-methoxypropionate to the propylene glycol butyl ether is 1.5: 1.
The cosolvent 3 comprises the following components: methyl 3-methoxypropionate and propylene glycol butyl ether, wherein the mass ratio of the methyl 3-methoxypropionate to the propylene glycol butyl ether is 2: 1.
The cosolvent 4 is 3-methoxypropionic acid methyl ester.
Cosolvent 5 is propylene glycol butyl ether.
Examples 1 to 5
Embodiments 1 to 5 provide a boiling-resistant phosphorus-containing aqueous acrylic dispersion resin, the formulation of which is shown in table 1, and the preparation method thereof is as follows:
(1) adding a cosolvent into a container, heating to 140-145 ℃, then dripping all the acrylic resin monomer I for 3 hours, adding an initiator with the dosage of 45% -55%, and carrying out heat preservation reaction for 15-30 min until the reaction is complete;
(2) mixing the acrylic resin monomer II and the acrylic resin monomer III to obtain a mixed monomer, then dripping all the mixed monomer into the reaction system in the step (1) for 1 hour, adding an initiator with the use amount accounting for 15-20%, carrying out heat preservation reaction for 60-80 min, then adding the rest of the initiator, and carrying out heat preservation reaction for 2-2.5 hours;
(3) and (3) cooling the reaction system obtained in the step (2) to 90 +/-2 ℃, adding a neutralizing agent, cooling to 80 +/-2 ℃ after the neutralization reaction is finished, then adding deionized water, and uniformly dispersing to obtain the phosphorus-containing aqueous acrylic acid dispersoid resin.
Comparative examples 1 to 4: comparative examples 1 to 4 provide aqueous acrylic dispersion resins having the formulations shown in Table 1, and the preparation methods thereof were according to the preparation methods of examples 1 to 5.
TABLE 1
Note: in the table, "-" indicates that the component was not added.
And (3) performance testing:
firstly, the type of the cosolvent is effective for abnormal viscosity thickening in the dilution process, and in order to investigate the influence of the cosolvents 1-5 on the water dispersion performance of the resin, the following item test of table 2 is carried out. Wherein the viscosity was measured at 25 ℃ by using an NDJ-1 type rotational viscometer.
TABLE 2
From the test results in table 2, it can be seen that under the same conditions of monomers, initiators and the like, the mass fractions of the solid contents of the resins of examples 1 to 3 and comparative examples 1 to 2 are not obviously different, but the dissolving capacity of the resin of examples 1 to 3 is obviously better than that of the resin of comparative examples 1 to 2, which shows that when methyl 3-methoxypropionate and propylene glycol butyl ether are used in a compounding manner, the dissolving capacity of the resin can be obviously improved, and the resin has good water dispersibility.
Secondly, the resins prepared in the examples 2, 4 to 5 and 3 to 4 are respectively used as resin dispersions, then the aqueous acrylic amino baking paint is prepared according to the following formula, the performances of the paint films obtained by the aqueous acrylic amino baking paints are tested, and the test results are shown in the table 3.
The water-based acrylic amino baking varnish consists of the following components in parts by weight: 72 parts of resin dispersoid, 18 parts of CYMEL303 aqueous amino resin, 0.5 part of BYK-190 wetting dispersant, 0.2 part of BYK-022 defoaming agent, 0.2 part of Tego-410 flatting agent, 3 parts of propylene glycol methyl ether, 0.2 part of dimethylethanolamine and 5.9 parts of deionized water.
Performance test standard:
the gloss was tested in accordance with GB/T9754-2007;
the hardness of the paint film is tested according to GB/T6739-2006;
impact resistance was tested according to GB/T1732-1993;
water resistance was tested according to GB/T1733-1993;
the adhesion was tested according to GB/T1720-;
boiling resistance: after boiling water test for 2h, the coating should not fall off, blister or other defects after boiling water test, allowing slight color change.
TABLE 3
As can be seen from the test results of table 3: in the paint films of the examples 2, 4-5 and 3-4, the comprehensive performance of the examples 2 and 4-5 is obviously superior to that of the comparative examples 3-4, which shows that the boiling resistance, the adhesion to a metal substrate and the mechanical property of the aqueous acrylic dispersion resin can be further improved by introducing the acrylic resin monomer II and the acrylic resin monomer III into the polymerization product of the acrylic resin monomer I.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The boiling-resistant phosphorus-containing aqueous acrylic dispersion resin is characterized by comprising the following components in parts by weight: 25-32 parts of acrylic resin monomer I, 0.2-5 parts of acrylic resin monomer II, 4-15 parts of acrylic resin monomer III, 10-20 parts of cosolvent, 0.5-2 parts of initiator, 1-5 parts of neutralizer and 35-45 parts of deionized water; the acrylic resin monomer I comprises at least one of isobornyl methacrylate, caprolactone modified methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and cyclohexyl methacrylate; the acrylic resin monomer in the second part comprises at least one of methacrylic acid phosphate and acrylic acid epoxy phosphate; the acrylic resin monomer in the III part comprises at least one of acrylic acid, methacrylic acid, caprolactone modified methacrylate, isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and cyclohexyl methacrylate.
2. The boiling resistant phosphorus containing aqueous acrylic dispersion resin of claim 1 wherein the co-solvent comprises at least one of methyl 3-methoxypropionate, and butyl propylene glycol ether.
3. The boiling-resistant phosphorus-containing aqueous acrylic dispersion resin according to claim 1, wherein the cosolvent consists of methyl 3-methoxypropionate and butyl propylene glycol ether, and the mass ratio of methyl 3-methoxypropionate: and (3) 1 is propylene glycol butyl ether (1-2).
4. The boiling-resistant phosphorus-containing aqueous acrylic dispersion resin according to claim 1, wherein the cosolvent consists of methyl 3-methoxypropionate and butyl propylene glycol ether, and the mass ratio of methyl 3-methoxypropionate: propylene glycol butyl ether is 1.5: 1.
5. The boiling resistant phosphorus-containing aqueous acrylic dispersion resin of claim 1, wherein the initiator comprises at least one of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide.
6. The boiling resistant phosphorus-containing aqueous acrylic dispersion resin of claim 1, wherein the neutralizing agent comprises at least one of triethylamine, dimethylethanolamine, and ammonia.
7. The preparation method of the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin according to any one of claims 1 to 6, comprising the steps of:
(1) adding a cosolvent into a container, heating to 140-145 ℃, then adding acrylic resin monomer I and an initiator with the dosage of 45-55%, and carrying out heat preservation reaction for 15-30 min;
(2) mixing the acrylic resin monomer II and the acrylic resin monomer III to obtain a mixed monomer, adding the mixed monomer and an initiator with the use amount of 15-20% into the reaction system in the step (1), carrying out heat preservation reaction for 60-80 min, adding the rest of the initiator, and carrying out heat preservation reaction for 2-2.5 h;
(3) and (3) cooling the reaction system obtained in the step (2) to 90 +/-2 ℃, adding a neutralizing agent, cooling to 80 +/-2 ℃ after the neutralization reaction is finished, adding deionized water, and uniformly dispersing to obtain the water-boiling-resistant acrylic acid dispersoid resin.
8. The use of the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin according to any one of claims 1 to 6 in an aqueous coating.
9. Use according to claim 8, characterized in that the aqueous coating is an aqueous acrylic amino stoving varnish.
10. The water-based acrylic amino baking paint is characterized by comprising the following components in parts by weight: the boiling-resistant phosphorus-containing aqueous acrylic dispersion resin as claimed in any one of claims 1 to 6, an aqueous amino resin, an auxiliary agent and deionized water.
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