CN117247504A - Self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and preparation method thereof - Google Patents
Self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and preparation method thereof Download PDFInfo
- Publication number
- CN117247504A CN117247504A CN202311357370.6A CN202311357370A CN117247504A CN 117247504 A CN117247504 A CN 117247504A CN 202311357370 A CN202311357370 A CN 202311357370A CN 117247504 A CN117247504 A CN 117247504A
- Authority
- CN
- China
- Prior art keywords
- parts
- acrylic resin
- aqueous acrylic
- monomer
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 65
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 65
- 238000004132 cross linking Methods 0.000 title claims abstract description 49
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000006185 dispersion Substances 0.000 claims abstract description 52
- -1 vinyl hydroxyl Chemical group 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 26
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 239000006184 cosolvent Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 14
- 239000011630 iodine Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 6
- 235000020778 linoleic acid Nutrition 0.000 claims description 6
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940114079 arachidonic acid Drugs 0.000 claims description 5
- 235000021342 arachidonic acid Nutrition 0.000 claims description 5
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-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
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- KOBJYYDWSKDEGY-UHFFFAOYSA-N 2-phenylpropan-2-yl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(C)(C)SC(=S)C1=CC=CC=C1 KOBJYYDWSKDEGY-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 39
- 238000000576 coating method Methods 0.000 abstract description 39
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000003973 paint Substances 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 12
- 239000007921 spray Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- URUCGDAHQNVLQX-UHFFFAOYSA-N C(C1=CC=CC=C1)(=S)S.C1(=CC=CC=C1)C(C)C Chemical compound C(C1=CC=CC=C1)(=S)S.C1(=CC=CC=C1)C(C)C URUCGDAHQNVLQX-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000000341 volatile oil Substances 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (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 provides a self-reinforced oxidative crosslinking aqueous acrylic resin dispersion and a preparation method thereof, wherein the dispersion is mainly used for preparing aqueous acrylic resin industrial paint, and the preparation raw materials comprise: epoxy monomer, high iodine value fatty acid, vinyl hydroxyl monomer, catalyst, styrene, initiator, chain transfer agent, vinyl hard monomer, vinyl soft monomer, hydrophilic monomer, neutralizer, cosolvent, deionized water, drier, etc. The particle size Dv (50) of the aqueous acrylic resin dispersoid is smaller than 75nm, the aqueous acrylic resin dispersoid has no precipitation and water separation phenomenon after being stored for 2 years at normal temperature, and the coating film has excellent adhesive force, high hardness and good water resistance, salt fog resistance and stain resistance. Solves the problems of poor storage stability, low film hardness, poor film water resistance, salt fog resistance and oil stain resistance of the traditional water-based acrylic industrial paint. Meanwhile, the invention has the advantages of environmental protection, simple and convenient production and preparation, and the like, and accords with the development trend of industry.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, and relates to a self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and a preparation method thereof.
Background
The acrylic resin coating has excellent weather resistance, good chemical resistance and workability, light color and moderate cost, and can be widely applied to the fields of steel structure corrosion prevention, mechanical and electrical, chemical equipment coating and the like. The acrylic acid industrial paint in the market at present still takes the oil paint as the main material, and the application of the water-based acrylic acid ester industrial paint still has a plurality of problems, such as low film hardness, poor storage stability, poor water resistance, poor solvent resistance and the like, which restrict the further popularization and application. With the increasing of national environmental protection, the water-based acrylic resin paint is a trend of developing the paint industry instead of the oily paint. Based on the above, there is a need to provide a high-performance aqueous acrylic resin for preparing industrial coating materials, which has excellent water resistance, salt spray resistance, solvent resistance, good coating hardness, storage stability, self-cleaning performance, low VOCs content and moderate cost, and is convenient for users to accept, so as to meet the market application demands.
Disclosure of Invention
Aiming at the technical problems of low coating hardness, poor adhesive force, water resistance, salt spray resistance, solvent resistance, poor storage stability, insufficient self-cleaning property and the like of the aqueous acrylic resin dispersion or emulsion in the application process of the coating, the invention provides the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion and the preparation method thereof, and the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion has the advantages of excellent storage stability, excellent adhesive force, high coating hardness, good water resistance, salt spray resistance, solvent resistance, low VOCs content, good self-cleaning property, moderate cost and the like.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid is prepared from the following raw materials in parts by weight:
epoxy monomer: 361-783 parts;
oleic acid with high iodine value: 104-342 parts;
vinyl hydroxyl monomer: 45-165 parts;
catalyst: 22-40 parts of a lubricant;
styrene: 525-990 parts;
and (3) an initiator: 41-148 parts;
chain transfer agent: 95-349 parts;
vinyl hard monomer: 350-810 parts;
vinyl soft monomer: 315-765 parts;
hydrophilic monomer: 70-175 parts;
neutralizing agent: 115-272 parts;
cosolvent: 835-1930 parts;
deionized water: 1708-6209 parts;
drier: 22-70 parts of a lubricant;
the solids content of the dispersion is 35% -45%.
Preferably, the epoxy monomer is E-20 epoxy resin and fluoro-glycidyl ether, and the fluoro-glycidyl ether is one or two of 2, 2-bisphenol hexafluoropropane diglycidyl ether and octafluorobiphenyl diglycidyl ether.
Preferably, the high iodine value oleic acid is one or two of linoleic acid, linoleic acid and arachidonic acid; the vinyl hydroxyl monomer is one or two of hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxyethyl acrylate.
Preferably, the catalyst is tetrabutylammonium bromide; the initiator is one or two of azodiisobutyronitrile and azodiisoheptonitrile; the chain transfer agent is one or two of (1-phenyl) ethyl dithiobenzoate and cumyl dithiobenzoate.
Preferably, the vinyl hard monomer is one or more of methyl methacrylate, acrylonitrile, methyl acrylate, tert-butyl methacrylate and norbornene methacrylate; the vinyl soft monomer is selected from one or more of n-butyl acrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate.
Preferably, the hydrophilic monomer is one or two of methacrylic acid, acrylic acid and butenoic acid; the neutralizing agent is one or two of N, N-dimethylethanolamine and triethylamine.
Preferably, the cosolvent is selected from one or two of propylene glycol methyl ether, propylene glycol butyl ether and dipropylene glycol methyl ether.
Preferably, the drier is the type Bochester 1101.
Preferably, the preparation method of the self-reinforced oxidative crosslinking type aqueous acrylic resin dispersion comprises the following steps:
(1) Adding an epoxy monomer, a vinyl hydroxyl monomer and a catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 115-160 ℃, stirring at a speed of 110-240 r/min, reacting for 2-4 hours, then adding high-iodine value oleic acid, continuously reacting for 2-4 hours, cooling to room temperature when the acid value is reduced to below 5mgKOH/g, then adding a vinyl hard monomer, a vinyl soft monomer, a hydrophilic monomer and 50-60% of cosolvent, uniformly mixing to obtain a mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 60-80 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 130-200 r/min, and the prepolymer B is obtained after constant temperature reaction for 3-4 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to be 60-80 ℃ for 2-5 hours, and continuing to react for 1.5-3 hours after the dropwise adding is finished; then heating to 90-100 ℃, continuing to react for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 300-500 r/min, and reacting for 20-30 min; then slowly adding deionized water, dispersing and stirring for 1 hour, and finally adding a drier, and continuously stirring for 30 minutes to obtain the self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid.
Preferably, the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion prepared according to the method has the styrene segment of regular homopolymerization and the acrylic ester segment of random copolymerization; the dispersion particle diameter Dv (50) is less than 75nm.
The invention has the beneficial effects that:
1. the self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and the downstream aqueous acrylic resin coating product thereof prepared by the invention have excellent water resistance, salt fog resistance and solvent resistance, good storage stability, coating hardness and self-cleaning property, and low VOCs content, meet the national energy-saving and emission-reducing standard, and are green and environment-friendly.
2. The conventional film-forming substances for the aqueous acrylic resin coating are mostly aqueous acrylic emulsion, which contains a large amount of emulsifying agents, the emulsifying agents still remain in the coating layer in the film-forming process of the coating, so that the water resistance and salt spray resistance of the coating film are reduced, and the coating prepared from the emulsion has poor storage stability and is extremely easy to break and deteriorate. The invention designs the molecular structure of the water-based acrylic resin, adds acrylic acid or methacrylic acid monomer containing carboxyl in the resin preparation process, introduces hydrophilic carboxyl on the resin molecular chain, achieves the effect of resin water dispersion through salification, and finally prepares the self-emulsifiable oxidative crosslinking water-based acrylic resin dispersoid.
3. Meanwhile, the invention adopts a living radical polymerization method, and designs a styrene hard segment ordered and acrylic ester segment unordered structure by regulating and controlling the addition sequence of monomers. In the film forming process, the styrene hard segment has weaker polarity and high glass transition temperature, the styrene structure segment can spontaneously aggregate to form styrene microspheres, the acrylic ester structure forms a continuous phase, and the styrene microspheres dispersed in the acrylic ester soft segment form physical crosslinking points in the coating film. The initial hardness and the later hardness of the coating are effectively improved while the mechanical property of the coating is improved.
4. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid prepared by the invention contains an oleic acid structure with high iodine value in an acrylic ester soft segment, contains a large amount of diallyl alpha hydrogen, and is subjected to oxidative crosslinking under the action of a drier, so that the crosslinking density of the coating is further improved, and the comprehensive properties of the coating, such as hardness, water resistance, salt fog resistance and the like are improved.
5. Meanwhile, the fluorine-containing monomer is introduced, so that the surface energy of the later-stage coating is reduced, the hydrophobicity and oleophobicity of the coating are improved, and the self-cleaning property of the coating is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the results of infrared spectrum test of a sample coating film prepared in example 1 of the present invention.
FIG. 2 is a graph showing GPC test results of samples prepared in example 1 of the present invention.
FIG. 3 is a graph showing the results of thermal weight loss test of the coating film of the sample prepared in example 1 of the present invention.
FIG. 4 is a graph showing the results of particle size measurement of a sample prepared in example 1 of the present invention.
FIG. 5 is a graph showing the results of particle size measurement of a sample prepared in example 3 of the present invention.
FIG. 6 is a graph showing the results of particle size measurement of a sample prepared in example 5 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersion is prepared from the following components in parts by weight:
e-20 epoxy resin: 206 parts of octafluorobiphenyl diglycidyl ether: 155 parts;
arachidonic acid: 169 parts;
hydroxyethyl acrylate: 64 parts;
tetrabutylammonium bromide: 22 parts;
styrene: 525 parts;
azobisisobutyronitrile: 46 parts;
cumene dithiobenzoate: 103 parts;
methyl methacrylate: 292 parts of methyl acrylate: 58 parts;
n-butyl acrylate: 315 parts;
methacrylic acid: 44 parts of acrylic acid: 27 parts;
triethylamine: 115 parts;
635 parts of propylene glycol methyl ether; propylene glycol butyl ether: 286 parts;
deionized water: 1708 parts;
the borsch boc1101 drier: 22 parts.
The preparation process of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid comprises the following steps:
(1) Adding epoxy resin E-20, fluoroglycidyl ether, vinyl hydroxyl monomer and catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 115 ℃, stirring at a speed of 240 r/min, reacting for 4 hours, then adding high-iodine value oleic acid, continuously reacting for 4 hours, cooling to room temperature when the acid value is reduced to 2.4mgKOH/g, then adding vinyl hard monomer, vinyl soft monomer, hydrophilic monomer and 55% cosolvent, uniformly mixing to obtain mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 80 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 130 r/min, and the prepolymer B is obtained after constant-temperature reaction for 4 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to be 60 ℃, dropwise adding for 4.6 hours, continuously reacting for 2 hours after dropwise adding is finished, then heating to 90 ℃, continuously reacting for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 500 r/min, and reacting for 30 minutes; then slowly adding deionized water, dispersing and stirring for 1 hour, finally adding a drier, and continuously stirring for 20 minutes to obtain the aqueous acrylic resin dispersion with 45% of solid content for styrene segment homopolymerization and acrylic ester segment random copolymerization.
For the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion prepared in example 1, water removal and drying were performed, and the results of the infrared spectroscopic test (FT-IR) are shown in FIG. 1, in which 2927 and cm are obtained -1 At C-H telescopic vibration absorption peak 1728 and 1728 cm -1 Where c=o stretchThe vibration absorption peak was contracted, 1505cm in the figure -1 The absorption peak at the position is a C=C framework telescopic vibration absorption peak on the benzene ring of the epoxy resin, which indicates that the epoxy resin used in the invention contains bisphenol A epoxy resin, and indicates that the styrene is successfully polymerized on the molecular chain of the acrylic resin; 1218cm in the figure -1 And 1140cm -1 The C-F bond stretches and stretches to absorb the peak, which shows that the fluorine-containing monomer is successfully introduced into the molecular chain of the resin. GPC measurement of the prepared oxidative crosslinking aqueous acrylic resin dispersion revealed that the prepared resin Mn=6203, mw=8994, polydispersity of 1.45, and narrow dispersity, was in accordance with the characteristics of radical living polymerization, as shown in FIG. 2. The thermal weight loss of the coating film is detected, and the result is shown in fig. 3, and the thermal decomposition temperature of the prepared resin coating film is 380 ℃ and the resin coating film has good thermal stability. The dispersion particle size was measured by a laser particle sizer and the results are shown in FIG. 4, which shows that the prepared dispersion has a uniform particle size distribution, a Dv (90) of 134nm and a Dv (50) of 73nm.
Example 2
The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersion is prepared from the following components in parts by weight:
e-20 epoxy resin: 443 parts of octafluorobiphenyl diglycidyl ether: 340 parts;
linoleic acid: 342 parts;
hydroxypropyl acrylate: 157 parts;
tetrabutylammonium bromide: 39 parts;
styrene: 970 parts;
azobisisobutyronitrile: 146 parts;
cumene dithiobenzoate: 349 parts;
acrylonitrile: 110 parts of methyl methacrylate: 545 parts of t-butyl methacrylate: 155 parts;
311 parts of n-butyl acrylate and isooctyl acrylate: 417 parts;
butenoic acid: 175 parts;
144 parts of triethylamine, N, N-dimethylethanolamine: 116 parts;
propylene glycol methyl ether: 1930 parts;
deionized water: 4822 parts;
the borsch boc1101 drier: 71 parts.
The preparation process of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid comprises the following steps:
(1) E-20 epoxy resin, fluoroglycidyl ether, vinyl hydroxyl monomer and catalyst are added into a reactor filled with inert gas and having an initial temperature of 80 ℃, then the temperature is raised to 155 ℃, the stirring speed is 240 r/min, the reaction time is 2.2 hours, then oleic acid with high iodine value is added, the reaction is continued for 2 hours, the acid value is reduced to 3.6mgKOH/g, the temperature is reduced to room temperature, then vinyl hard monomer, vinyl soft monomer, hydrophilic monomer and 50% cosolvent are added, the mixture A is obtained after uniform mixing, and the mixture A is discharged for standby;
(2) Another new reactor is taken, the initial temperature is set at 80 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 200 r/min, and the prepolymer B is obtained after constant-temperature reaction for 3 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to 80 ℃, controlling the dropwise adding time to 5 hours, and continuing to react for 1.5 hours after the dropwise adding is finished; then heating to 90 ℃, continuing to react for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 340 r/min, and reacting for 25 minutes; then adding deionized water slowly, dispersing and stirring for 1 hour, finally adding a drier, and continuously stirring for 30 minutes to obtain the aqueous acrylic resin dispersoid with 40% of solid content of styrene segment homo-polymerization and acrylic ester segment random copolymerization.
Example 3
The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid is prepared from the following components in parts by weight:
e-20 epoxy resin: 312 parts of 2, 2-bisphenol hexafluoropropane diglycidyl ether: 155 parts of octafluorobiphenyl diglycidyl ether: 105 parts;
arachidonic acid: 110 parts of linoleic acid: 113 parts;
hydroxypropyl acrylate: 114 parts;
tetrabutylammonium bromide: 35 parts;
styrene: 762 parts;
azodiisoheptonitrile: 96 parts;
(1-phenyl) ethyl dithiobenzoate: 210 parts;
methyl methacrylate: 620 parts;
n-butyl methacrylate: 632 parts;
acrylic acid: 136 parts;
n, N-dimethylethanolamine: 136 parts;
propylene glycol methyl ether: 1010 parts of dipropylene glycol methyl ether: 450 parts;
deionized water: 4854 parts;
the borsch boc1101 drier: 52 parts.
The preparation process of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid comprises the following steps:
(1) Adding E-20 epoxy resin, fluoroglycidyl ether, vinyl hydroxyl monomer and catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 140 ℃, stirring at a speed of 200 r/min, reacting for 3 hours, then adding high-iodine value oleic acid, continuing to react for 3.5 hours, cooling to room temperature when the acid value is reduced to 4.7mgKOH/g, then adding vinyl hard monomer, vinyl soft monomer, hydrophilic monomer and 55% cosolvent, uniformly mixing to obtain mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 75 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 130 revolutions per minute, and the prepolymer B is obtained after the constant-temperature reaction for 3.2 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to be 75 ℃, controlling the dropwise adding time to be 3 hours, and continuing to react for 2 hours after the dropwise adding is finished; then heating to 100 ℃, continuing to react for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 500 r/min, and reacting for 30 minutes; then adding deionized water slowly, dispersing and stirring for 1 hour, finally adding a drier, and continuously stirring for 30 minutes to obtain the aqueous acrylic resin dispersion with 35% of solid content of styrene segment homo-polymerization and acrylic ester segment random copolymerization.
For the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion prepared in example 3, the particle size of the dispersion was measured by a laser particle sizer, and the result is shown in FIG. 5, in which it can be seen that the particle size distribution of the prepared resin dispersion was uniform, dv (90) was 114nm, dv (50) was 68nm.
Example 4
The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersion is prepared from the following components in parts by weight:
e-20 epoxy resin: 228 parts of 2, 2-bisphenol hexafluoropropane diglycidyl ether: 330 parts;
linoleic acid: 207 parts;
hydroxypropyl acrylate: 65 parts of hydroxypropyl methacrylate: 92 parts;
tetrabutylammonium bromide: 30 parts;
styrene: 920 parts;
azobisisobutyronitrile: 47 parts of azodiisoheptonitrile: 47 parts;
(1-phenyl) ethyl dithiobenzoate: 163 parts;
methyl methacrylate: 440 parts of acrylonitrile: 130 parts;
isooctyl acrylate: 610 parts;
methacrylic acid: 110 parts;
triethylamine: 208 parts;
propylene glycol butyl ether: 1437 parts;
deionized water: 4035 parts;
the borsch boc1101 drier: 55 parts.
The preparation process of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid comprises the following steps:
(1) Adding epoxy resin E-20, fluoroglycidyl ether, vinyl hydroxyl monomer and catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 125 ℃, stirring at a speed of 110 r/min, reacting for 3.5 hours, adding high-iodine value oleic acid, continuing to react for 3 hours, cooling to room temperature when the acid value is reduced to 4.8mg KOH/g, then adding vinyl hard monomer, vinyl soft monomer, hydrophilic monomer and 60% cosolvent, uniformly mixing to obtain mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 80 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 140 revolutions per minute, and the prepolymer B is obtained after constant-temperature reaction for 3 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to 80 ℃, controlling the dropwise adding time to 2 hours, and continuing to react for 3 hours after the dropwise adding is finished; then heating to 90 ℃, continuing to react for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 300 r/min, and reacting for 20 minutes; then adding deionized water slowly, dispersing and stirring for 1 hour, finally adding a drier, and continuously stirring for 30 minutes to obtain the aqueous acrylic resin dispersoid with 38% of solid content of styrene segment homo-polymerization and acrylic ester segment random copolymerization.
Example 5
The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersion is prepared from the following components in parts by weight:
e-20 epoxy resin: 270 parts of octafluorobiphenyl diglycidyl ether: 152 parts;
linoleic acid: 277 parts;
hydroxypropyl acrylate: 45 parts of hydroxyethyl acrylate: 68 parts;
tetrabutylammonium bromide: 34 parts;
styrene: 740 parts;
azobisisobutyronitrile: 95 parts;
(1-phenyl) ethyl dithiobenzoate: 200 parts;
methyl methacrylate: 520, norbornene methacrylate: 100 parts;
n-butyl acrylate: 580 parts;
methacrylic acid: 140 parts;
triethylamine: 184 parts;
dipropylene glycol methyl ether: 1380 parts;
deionized water: 3680 parts;
borsch boc1101 model drier: 42 parts.
The preparation process of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid comprises the following steps:
(1) Adding epoxy resin E-20, fluoroglycidyl ether, vinyl hydroxyl monomer and catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 160 ℃, stirring at a speed of 200 r/min for 2 hours, then adding high-iodine value oleic acid, continuously reacting for 2 hours, cooling to room temperature when the acid value is reduced to 3.9mgKOH/g, then adding vinyl hard monomer, vinyl soft monomer, hydrophilic monomer and 50% cosolvent, uniformly mixing to obtain mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 60 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 130 r/min, and the prepolymer B is obtained after constant-temperature reaction for 4 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to be 60 ℃, controlling the dropwise adding time to be 4.5 hours, and continuing to react for 3 hours after the dropwise adding is finished; then heating to 95 ℃, continuing to react for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 400 r/min, and reacting for 30 minutes; then adding deionized water slowly, dispersing and stirring for 1 hour, finally adding a drier, and continuously stirring for 30 minutes to obtain the styrene segment homo-polymer with the solid content of 42 percent and the acrylic ester segment random copolymerized aqueous acrylic resin dispersoid.
For the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion prepared in example 5, the particle size of the dispersion was measured by a laser particle sizer, and the result is shown in FIG. 6, in which it can be seen that the particle size distribution of the prepared resin dispersion was uniform, with Dv (90) of 108nm and Dv (50) of 62nm.
Example 6
The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid is prepared from the following components in parts by weight:
e-20 epoxy resin: 580 parts of octafluorobiphenyl diglycidyl ether: 201 parts;
arachidonic acid: 104 parts;
hydroxypropyl methacrylate: 45 parts;
tetrabutylammonium bromide: 40 parts;
styrene: 990 parts;
azobisisobutyronitrile: 121 parts;
cumene dithiobenzoate: 240 parts;
methyl methacrylate: 462 parts of methyl acrylate: 258 parts;
n-butyl acrylate: 765 parts;
methacrylic acid: 144 parts of butenoic acid: 27 parts;
triethylamine: 272 parts;
propylene glycol methyl ether: 450 parts of dipropylene glycol methyl ether: 385 parts;
deionized water: 6209 parts;
the borsch boc1101 drier: 70 parts.
The preparation process of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersoid comprises the following steps:
(1) Adding epoxy resin E-20, fluoroglycidyl ether, vinyl hydroxyl monomer and catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 115 ℃, stirring at a speed of 240 r/min, reacting for 4 hours, then adding high-iodine value oleic acid, continuously reacting for 4 hours, cooling to room temperature when the acid value is reduced to 2.4mgKOH/g, then adding vinyl hard monomer, vinyl soft monomer, hydrophilic monomer and 55% cosolvent, uniformly mixing to obtain mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 80 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 130 r/min, and the prepolymer B is obtained after constant-temperature reaction for 4 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, controlling the reaction temperature to be 60 ℃, dropwise adding for 4.6 hours, continuously reacting for 2 hours after dropwise adding is finished, then heating to 90 ℃, continuously reacting for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 500 r/min, and reacting for 20 minutes; then adding deionized water slowly, dispersing and stirring for 1 hour, finally adding a drier, and continuously stirring for 30 minutes to obtain the aqueous acrylic resin dispersion with 40% of solid content and random copolymerization of styrene segments and acrylic ester segments.
To further illustrate the self-reinforced oxidative crosslinking aqueous acrylic resin dispersions disclosed in the present invention, the self-reinforced oxidative crosslinking aqueous acrylic resin dispersions and coating film properties prepared in examples 1 to 6 were tested by the following test methods:
dispersion storage stability test: and (3) placing the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion sample in a 50 ℃ oven, standing at constant temperature for 4 weeks, taking out, standing in a room temperature environment, and observing if no gel or layering phenomenon exists, and passing the test.
Particle size of dispersion test: the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion was diluted into deionized water and the dispersion particle size and distribution were tested with a laser particle sizer.
Resin film adhesion measurement: the adhesion of the coating films of the dispersions prepared in the examples was determined according to the method of GB/T9286-1998.
Resin coating film hardness test: the hardness of the paint film was measured by pencil method according to GB/T6739-2006 standard.
Resin coating film volatile oil resistance test: according to GB/T9274-1988, 5.4. Immersing in solvent oil meeting the requirements of 0004-1990, taking out the sample plate until a specified time, standing for 10min, and observing to evaluate the result according to the specification of GB/T1766-2008.
Salt spray resistance test of resin coating: the neutral salt spray resistance of the resin coating film is tested by adopting the GB/T1771-2007 standard, the coating film is not foamed or shed in 500 hours, and slight color change is allowed, and the resin coating film passes the test;
resin coating film water resistance test: the water resistance of the resin coating film was measured by the method of GB/T1733-1993, and the film was not foamed, not peeled off, and allowed to slightly change color after 500 hours, and was regarded as passing the test.
TABLE 1 test Table for film Properties of resin Dispersion obtained in examples 1 to 6
As shown by the experimental results in Table 1, the particle size Dv (50) < 75nm, dv (90) < 135nm of the self-reinforced oxidative crosslinking aqueous acrylic resin dispersion prepared in examples 1-6 of the present invention is at the nano-scale and distributed uniformly, thus ensuring the storage stability of the dispersion and downstream paint products; the adhesive force of the coating film of the aqueous acrylic resin dispersoid prepared by the method reaches 0 level, and the problem of poor adhesive force of the traditional aqueous acrylic resin coating is solved; in terms of water resistance and salt spray resistance, the prepared dispersion coating exceeds 500 hours, and is superior to similar products in line standard and market.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the invention, but any modifications, equivalent substitutions, improvements, etc. within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. The self-reinforced oxidative crosslinking type aqueous acrylic resin dispersion is characterized by being prepared from the following raw materials in parts by weight:
epoxy monomer: 361-783 parts;
oleic acid with high iodine value: 104-342 parts;
vinyl hydroxyl monomer: 45-165 parts;
catalyst: 22-40 parts of a lubricant;
styrene: 525-990 parts;
and (3) an initiator: 41-148 parts;
chain transfer agent: 95-349 parts;
vinyl hard monomer: 350-810 parts;
vinyl soft monomer: 315-765 parts;
hydrophilic monomer: 70-175 parts;
neutralizing agent: 115-272 parts;
cosolvent: 835-1930 parts;
deionized water: 1708-6209 parts;
drier: 22-70 parts of a lubricant;
the solids content of the dispersion is 35% -45%.
2. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the epoxy monomer is E-20 epoxy resin and fluoro-glycidyl ether, and the fluoro-glycidyl ether is one or two of 2, 2-bisphenol hexafluoropropane diglycidyl ether and octafluorobiphenyl diglycidyl ether.
3. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the high-iodine value oleic acid is one or two of linoleic acid, linoleic acid and arachidonic acid; the vinyl hydroxyl monomer is one or two of hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxyethyl acrylate.
4. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the catalyst is tetrabutylammonium bromide; the initiator is one or two of azodiisobutyronitrile and azodiisoheptonitrile; the chain transfer agent is one or two of (1-phenyl) ethyl dithiobenzoate and cumyl dithiobenzoate.
5. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the vinyl hard monomer is one or a combination of more of methyl methacrylate, acrylonitrile, methyl acrylate, tert-butyl methacrylate and norbornene methacrylate; the vinyl soft monomer is one or a combination of more of n-butyl acrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate.
6. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the hydrophilic monomer is one or two of methacrylic acid, acrylic acid and butenoic acid; the neutralizing agent is one or two of N, N-dimethylethanolamine and triethylamine.
7. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the cosolvent is one or two of propylene glycol methyl ether, propylene glycol butyl ether and dipropylene glycol methyl ether.
8. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion of claim 1, wherein: the drier is the type Bochester 1101.
9. The method for producing a self-reinforced oxidative crosslinking aqueous acrylic resin dispersion according to any one of claims 1 to 8, comprising the steps of:
(1) Adding an epoxy monomer, a vinyl hydroxyl monomer and a catalyst into a reactor filled with inert gas and having an initial temperature of 80 ℃, then heating to 115-160 ℃, stirring at a speed of 110-240 r/min, reacting for 2-4 hours, then adding high-iodine value oleic acid, continuously reacting for 2-4 hours, cooling to room temperature when the acid value is reduced to below 5mgKOH/g, then adding a vinyl hard monomer, a vinyl soft monomer, a hydrophilic monomer and 50-60% of cosolvent, uniformly mixing to obtain a mixed solution A, and discharging for later use;
(2) Another new reactor is taken, the initial temperature is set at 60-80 ℃, residual cosolvent and styrene are added after nitrogen replacement, an initiator and a chain transfer agent are added when the temperature is stable, the stirring speed is set at 130-200 r/min, and the prepolymer B is obtained after constant temperature reaction for 3-4 hours;
(3) Slowly dropwise adding the mixed solution A prepared in the step (1) into the prepolymer B, wherein the reaction temperature is 60-80 ℃, the dropwise adding time is 2-5 hours, and the reaction is continued for 1.5-3 hours after the dropwise adding is completed; then heating to 90-100 ℃, continuing to react for 1 hour, and cooling to 50 ℃ to obtain a polymer C;
(4) Continuously slowly adding a neutralizing agent into the reactor, adjusting the stirring speed to 300-500 r/min, and reacting for 20-30 min; then adding deionized water slowly, dispersing and stirring for 1 hour, and finally adding a drier, continuously stirring and dispersing for 30 minutes to obtain the oxidative crosslinking type aqueous acrylic resin dispersoid.
10. The self-reinforced oxidative crosslinking aqueous acrylic resin dispersion prepared by the process of any one of claims 1 to 9 wherein the oxidative crosslinking aqueous acrylic resin dispersion has a regular homopolymerization of its styrene segments followed by a random copolymerization of acrylate segments; the dispersion particle diameter Dv (50) is less than 75nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311357370.6A CN117247504A (en) | 2023-10-19 | 2023-10-19 | Self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311357370.6A CN117247504A (en) | 2023-10-19 | 2023-10-19 | Self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117247504A true CN117247504A (en) | 2023-12-19 |
Family
ID=89133044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311357370.6A Pending CN117247504A (en) | 2023-10-19 | 2023-10-19 | Self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117247504A (en) |
-
2023
- 2023-10-19 CN CN202311357370.6A patent/CN117247504A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nabuurs et al. | Alkyd-acrylic hybrid systems for use as binders in waterborne paints | |
| JP5156160B2 (en) | Leveling agent for surface coating | |
| Zhang et al. | Synthesis and characterization of crosslinkable latex with interpenetrating network structure based on polystyrene and polyacrylate | |
| Tan et al. | Preparation and performance of waterborne UV‐curable polyurethane containing long fluorinated side chains | |
| Moreno et al. | From fatty acid and lactone biobased monomers toward fully renewable polymer latexes | |
| Vitale et al. | Nanoheterogeneous networks by photopolymerization of perfluoropolyethers and acrylic co‐monomers | |
| Ataei et al. | Fast physical drying, high water and salt resistant coatings from non-drying vegetable oil | |
| CA1210882A (en) | Process for producing stable large particle size latices | |
| Dong et al. | Preparation and characterization of UV-curable waterborne polyurethane using isobornyl acrylate modified via copolymerization | |
| Ning et al. | Synthesis of amphiphilic block–graft copolymers [poly (styrene‐b‐ethylene‐co‐butylene‐b‐styrene)‐g‐poly (acrylic acid)] and their aggregation in water | |
| CN103193678A (en) | Urethane acrylate low polymer and preparation method and application thereof | |
| CN117247504A (en) | Self-reinforced oxidative crosslinking type aqueous acrylic resin dispersoid and preparation method thereof | |
| Shu et al. | “One pot” synthesis of fluorinated block copolymers using a surface-active ATRP initiator under emulsion polymerization conditions | |
| Lv et al. | Polystyrene‐b‐poly (2, 2, 2‐trifluoroethyl acrylate)‐b‐polystyrene copolymers: Synthesis and fabrication of their hydrophobic porous films, spheres, and fibers | |
| Zang et al. | Synthesis and characterization of fluorine‐containing polyacrylate latex with core–shell structure by UV‐initiated seeded emulsion polymerization | |
| He et al. | Fluorinated polyacrylates containing amino side chains for the surface modification of waterborne epoxy resin | |
| Kuo et al. | Synthesis of high‐solid‐content, acrylic pressure‐sensitive adhesives by solvent polymerization | |
| Tingting et al. | Soap‐free emulsion copolymerization of perfluoroalkyl acrylates in the presence of a reactive surfactant | |
| Minami et al. | Preparation of composite polymer particles by seeded dispersion polymerization in ionic liquids | |
| Zhou et al. | Preparation and characterization of self‐emulsifying poly (ethylene glycol) methyl ether methacrylate grafted polyacrylate copolymers modified by waterborne polyester | |
| Tan et al. | A novel mono‐methacryloyloxy terminated fluorinated macromonomer used for the modification of UV curable acrylic copolymers | |
| Wang et al. | Considerations of functional fluoropolymer structure in the design of acrylic–fluorine hybrid PSAs: Graft versus telechelic cooligomers | |
| CN113980209A (en) | Acrylic resin aqueous dispersion and preparation method thereof | |
| KR890006675A (en) | Grafted Ethylene Polymers and Copolymers and Their Applications as Coating Binders | |
| Hu et al. | Secondary nucleation of styrenated hydroxyl‐functionalized latexes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |