CN113736031A - Acrylic acid modified polyester for water-based automobile paint floating coat and preparation method thereof - Google Patents
Acrylic acid modified polyester for water-based automobile paint floating coat and preparation method thereof Download PDFInfo
- Publication number
- CN113736031A CN113736031A CN202110929992.6A CN202110929992A CN113736031A CN 113736031 A CN113736031 A CN 113736031A CN 202110929992 A CN202110929992 A CN 202110929992A CN 113736031 A CN113736031 A CN 113736031A
- Authority
- CN
- China
- Prior art keywords
- water
- initiator
- modified polyester
- heating
- preserving heat
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003973 paint Substances 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229920000728 polyester Polymers 0.000 title claims abstract description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000007667 floating Methods 0.000 title claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 carboxylic acid glycidyl ester Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- 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 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 7
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 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 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 229960002887 deanol Drugs 0.000 claims description 5
- 239000000539 dimer Substances 0.000 claims description 5
- 239000012972 dimethylethanolamine Substances 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 description 8
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses acrylic acid modified polyester for water-based automobile paint floating coat and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a prepolymer: putting the group A materials into a high-temperature reaction kettle, heating to 160 ℃, preserving heat for 1h, slowly heating to 200 ℃, namely heating to 10 ℃ every 1h, preserving heat for 1h after reaching 200 ℃, cooling to 160 ℃, adding tertiary carboxylic acid glycidyl ester and maleic anhydride, heating to 180 ℃, preserving heat for 1h, then heating to 210 and 220 ℃, preserving heat until the viscosity and acid value are qualified, and preparing to obtain a prepolymer; adding a proper amount of alcohol ether solvent into the prepolymer, heating to 140-150 ℃, dropwise adding an acrylic monomer and an initiator consisting of the group B materials, adding a neutralizer, cooling and discharging to obtain the acrylic modified polyester for the water-based automobile paint intercoat.
Description
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to acrylic acid modified polyester for water-based automobile paint floating coat and a preparation method thereof.
Background
The adoption of the water-based paint is an effective way for reducing the VOC emission in the automobile coating process. The technology of aqueous intermediate coatings is well established and commonly used in europe. In the automobile industry of China, after a water-based base coat coating line is used in 2004, a water-based intermediate coating is also used in 2007. In China, a plurality of paint manufacturing companies are in the process of localization and self-research and development of the water-based intermediate paint. The choice of resin is an important part of the coating formulation technology. The inventor finds that the prior arts have at least the following technical problems in the practical use process:
automotive intermediate coats are used as a part of automotive composite coating systems, can improve the appearance of finish coats and can improve the stone chip resistance of the whole coating system, and therefore are increasingly paid more attention. The traditional solvent-based automobile intermediate coating is difficult to meet the requirement of modern automobile decorative protection, and the modern automobile intermediate coating has to solve two problems: excellent workability and stone chip resistance.
Disclosure of Invention
Aiming at the problems of troublesome construction and weak stone impact resistance in the prior art, the invention provides a preparation method of acrylic acid modified polyester for water-based automobile paint floating coat, which aims to: the acrylic acid modified polyester with good stone-impact resistance and strong matching performance is developed, so that the problems of poor construction performance and poor stone-impact resistance of the existing water-based paint are effectively solved, the protection effect of the automobile exterior paint is improved, and the effects of decoration and protection are achieved.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the acrylic acid modified polyester for the water-based automobile paint intermediate coat comprises the following steps:
(1) preparing a prepolymer: putting the group A materials into a high-temperature reaction kettle, heating to 160 ℃, preserving heat for 1h, slowly heating to 200 ℃, namely heating to 10 ℃ every 1h, preserving heat for 1h after reaching 200 ℃, cooling to 160 ℃, adding tertiary carboxylic acid glycidyl ester and maleic anhydride, heating to 180 ℃, preserving heat for 1h, then heating to 210 and 220 ℃, preserving heat until the viscosity and the acid value are qualified, and preparing a prepolymer;
(2) polymerization modification: adding a proper amount of alcohol ether solvent into the prepolymer prepared in the step (1), heating to 140-150 ℃, dropwise adding an acrylic monomer and an initiator consisting of the group B materials, finishing dropping for 3-6 hours, preserving heat for 2-3 hours after dropping, replenishing the initiator for the first time, preserving heat for 2-3 hours at 80-150 ℃ after replenishing, replenishing the initiator for the second time, preserving heat for 3-4 hours at 80-150 ℃, cooling to 80 ℃, adding a neutralizing agent, cooling and discharging to obtain the acrylic modified polyester for coating in the water-based automobile paint.
The further preferable technical scheme is as follows: the initiator is one or more of benzoyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide and tert-butyl peroxybenzoate.
The further preferable technical scheme is as follows: the alcohol ether solvent is one or more of propylene glycol monobutyl ether, isopropanol, isobutanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether and dipropylene glycol methyl ether.
The further preferable technical scheme is as follows: the group A material comprises the following components in percentage by weight: 3-5% of dimer acid, 2-4% of neopentyl glycol, 6-8% of trimethylolpropane, 1-3% of adipic acid, 2-4% of isophthalic acid, 0-0.5% of xylene and 6-8% of phthalic anhydride;
the group B material comprises the following components in percentage by weight: 6-8% of methyl methacrylate, 5-15% of styrene, 0.2-0.5% of acrylic acid, 6-9% of butyl acrylate, 2-3% of butyl methacrylate and 2-4% of hydroxypropyl acrylate;
the initiator consists of the following components in percentage by weight: 1 to 1.5 percent of benzoyl peroxide and 0.5 to 0.8 percent of tert-butyl peroxybenzoate; the weight percentage of the tertiary carbonic acid glycidyl ester is 2-5 percent, and the weight percentage of the maleic anhydride is 1-2 percent;
the alcohol ether solvent consists of the following components in percentage by weight: 1-3% of 1, 6-hexanediol, 9-11% of ethylene glycol monobutyl ether and 9-11% of propylene glycol methyl ether.
The further preferable technical scheme is as follows: the neutralizing agent is dimethylethanolamine.
The further preferable technical scheme is as follows: (1) in preparing the prepolymer, the viscosity pass value is as follows: 10000-20000mpa.s/25 ℃, the qualified value of acid value is: 40-50 mgKOH/g.
The further preferable technical scheme is as follows: (2) in the polymerization modification, the mass of the initiator added with the initiator is the mass of the initiator
80% of the total amount, the mass of the initiator replenished for the first time is 10% of the total mass of the initiator, and the mass of the initiator replenished for the second time is 10% of the total mass of the initiator.
The further preferable technical scheme is as follows: (1) in the preparation of the prepolymer, after the viscosity and acid value are qualified, the redundant dimethylbenzene needs to be extracted.
The further preferable technical scheme is as follows: an acrylic modified polyester for water-based automotive paint intercoat, characterized by being obtained by the method according to any one of claims 1 to 8.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the acrylic acid modified polyester for the water-based automobile paint intermediate coat prepared by the preparation method has excellent stability, and the VOC content is lower than that of the traditional coating, so that the harm to constructors and natural environment is effectively reduced.
2. In addition, the protective and stone-impact resistant effects of the paint on the automobile outer coating are ideal, the acrylic modified polyester for the water-based automobile paint has excellent dielectric resistance, excellent hardness, impact strength, adhesion capacity and construction convenience, and compared with the traditional automobile paint, the paint has wider practicability and stronger durability.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, not all of the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention.
Example 1:
putting 50g of dimer acid, 40g of neopentyl glycol, 80g of trimethylolpropane, 30g of adipic acid, 40g of isophthalic acid, 5g of xylene and 80g of phthalic anhydride into a high-temperature reaction kettle, heating to 160 ℃, preserving heat for 1h, slowly heating to 200 ℃, namely heating every 1h to 10 ℃, preserving heat for 1h after reaching 200 ℃, cooling to 160 ℃, adding 50g of tertiary carboxylic acid glycidyl ester and 20g of maleic anhydride, heating to 180 ℃, preserving heat for 1h, then heating to 220 ℃, preserving heat until the viscosity reaches 10000-;
uniformly mixing 80g of methyl methacrylate, 150g of styrene, 5g of acrylic acid, 90g of butyl acrylate, 30g of butyl methacrylate and 40g of hydroxypropyl acrylate to obtain an acrylic monomer;
mixing 15g of benzoyl peroxide 1-1.5% and 8g of tert-butyl peroxybenzoate to obtain an initiator;
and mixing 30g of 1,6 g of hexanediol, 11g of ethylene glycol monobutyl ether and 11g of propylene glycol methyl ether to obtain the alcohol ether solvent.
Adding a proper amount of alcohol ether solvent into the obtained prepolymer, heating to 150 ℃, dropwise adding an acrylic monomer and 80% of initiator, finishing dropping for 6 hours, preserving heat for 3 hours after dropping, replenishing the initiator for 10% for the first time, preserving heat for 3 hours at 150 ℃ after replenishing, replenishing the initiator for the second time, finishing dropping the initiator, preserving heat for 4 hours at 150 ℃, cooling to 80 ℃, adding a neutralizer dimethylethanolamine, cooling, and discharging to obtain the acrylic acid modified polyester for water-based automobile paint intermediate coating.
Example 2:
30g of dimer acid, 20g of neopentyl glycol, 60g of trimethylolpropane, 10g of adipic acid, 20g of isophthalic acid and 60g of phthalic anhydride are put into a high-temperature reaction kettle, the temperature is raised to 160 ℃, the temperature is kept for 1h, then the temperature is slowly raised to 200 ℃, namely the temperature is raised to 10 ℃ every 1h, the temperature is kept for 1h after the temperature reaches 200 ℃, the temperature is lowered to 160 ℃, 20g of tertiary carboxylic acid glycidyl ester and 10g of maleic anhydride are added, the temperature is raised to 180 ℃, the temperature is kept for 1h, then the temperature is raised to 210 ℃, the temperature is kept until the viscosity reaches 10000-;
uniformly mixing 80g of methyl methacrylate, 50g of styrene, 2g of acrylic acid, 60g of butyl acrylate, 20g of butyl methacrylate and 20g of hydroxypropyl acrylate to obtain an acrylic monomer;
mixing 10g of benzoyl peroxide and 5g of tert-butyl peroxybenzoate to obtain an initiator;
mixing 10g of 1,6 g of hexanediol, 9g of ethylene glycol monobutyl ether and 9g of propylene glycol methyl ether to obtain the alcohol ether solvent.
Adding a proper amount of alcohol ether solvent into the obtained prepolymer, heating to 140 ℃, dropwise adding an acrylic monomer and 80% of initiator, finishing dropping for 3 hours, preserving heat for 2 hours after dropping, replenishing the initiator for 10% for the first time, preserving heat for 2 hours at 80 ℃ after replenishing, replenishing the initiator for the second time, finishing dropping the initiator, preserving heat for 3 hours at 80 ℃ after replenishing, adding a neutralizer dimethylethanolamine, cooling and discharging to obtain the acrylic acid modified polyester for the water-based automobile paint.
Example 3:
putting 40g of dimer acid, 30g of neopentyl glycol, 70g of trimethylolpropane, 20g of adipic acid, 30g of isophthalic acid, 2.5g of dimethylbenzene and 70g of phthalic anhydride into a high-temperature reaction kettle, heating to 160 ℃, preserving heat for 1h, slowly heating to 200 ℃, namely heating every 1h to 10 ℃, preserving heat for 1h after reaching 200 ℃, cooling to 160 ℃, adding 35g of tertiary carboxylic acid glycidyl ester and 15g of maleic anhydride, heating to 180 ℃, preserving heat for 1h, then heating to 205 ℃, preserving heat until the viscosity reaches 10000-;
uniformly mixing 70g of methyl methacrylate, 10g of styrene, 3.5g of acrylic acid, 75g of butyl acrylate, 25g of butyl methacrylate and 30g of hydroxypropyl acrylate to obtain an acrylic monomer;
mixing 12.5g of benzoyl peroxide and 6.5g of tert-butyl peroxybenzoate to obtain an initiator;
2g of 1,6 g of hexanediol, 10g of ethylene glycol monobutyl ether and 10g of propylene glycol methyl ether are mixed to obtain the alcohol ether solvent.
Adding a proper amount of alcohol ether solvent into the obtained prepolymer, heating to 115 ℃, dropwise adding an acrylic monomer and 80% of initiator, finishing dropping for 3.5h, preserving heat for 2.5h after dropping, replenishing the initiator for 10% for the first time, preserving heat for 2.5h at 115 ℃ after replenishing, replenishing the initiator for the second time, finishing dropping the initiator, preserving heat for 3.5h at 115 ℃, cooling to 80 ℃, adding a neutralizer dimethylethanolamine, cooling, discharging, and thus obtaining the acrylic acid modified polyester for coating in the water-based automobile paint.
According to test results, the acrylic acid modified polyester for the water-based automobile paint intermediate coat prepared by the preparation method disclosed by the invention has the impact strength of over 80kg/cm, can replace the seventh automobile in the current market, and has a certain market prospect. In the present invention, an anionic emulsifier is added to provide dispersing and emulsifying organic monomers, so that a heterogeneous system becomes an emulsion, the monomers are coated, static electricity is eliminated to prevent agglomeration, and the pre-emulsion is used as a seed for growth. The nonionic emulsifier provides space separation, dispersion, surface tension reduction, emulsion breaking prevention and mechanical stabilization for rear-end application.
In the invention, the inventor effectively improves the grafting rate of the prepolymer by adding maleic anhydride and adjusting the dosage of the maleic anhydride, and avoids the technical problem that the dispersion is difficult to disperse with water. The flexibility, water resistance and weather resistance of the acrylic acid modified polyester for water-based automobile paint coating are endowed by introducing E-10P, namely tertiary carbonic acid glycidyl ester. Because the tertiary carbonic acid glycidyl ester has an epoxy group, the tertiary carbonic acid glycidyl ester can carry out ring-opening reaction with the tertiary carbonic acid glycidyl ester, thereby greatly improving the flexibility, the extensibility, the weather resistance and the water resistance of the material. Meanwhile, after the ring-opening reaction, the side chain of the tertiary carbonic acid glycidyl ester has larger steric hindrance, so that the viscosity of the resin can be greatly reduced, and the method plays an important role in material polymerization and grafting.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A preparation method of acrylic acid modified polyester for water-based automobile paint intermediate coating is characterized by comprising the following preparation steps:
(1) preparing a prepolymer: putting the group A materials into a high-temperature reaction kettle, heating to 160 ℃, preserving heat for 1h, slowly heating to 200 ℃, namely heating to 10 ℃ every 1h, preserving heat for 1h after reaching 200 ℃, cooling to 160 ℃, adding tertiary carboxylic acid glycidyl ester and maleic anhydride, heating to 180 ℃, preserving heat for 1h, then heating to 210 and 220 ℃, preserving heat until the viscosity and the acid value are qualified, and preparing a prepolymer;
(2) polymerization modification: adding a proper amount of alcohol ether solvent into the prepolymer prepared in the step (1), heating to 140-150 ℃, dropwise adding an acrylic monomer and an initiator consisting of the group B materials, finishing dropping for 3-6 hours, preserving heat for 2-3 hours after dropping, replenishing the initiator for the first time, preserving heat for 2-3 hours at 80-150 ℃ after replenishing, replenishing the initiator for the second time, preserving heat for 3-4 hours at 80-150 ℃, cooling to 80 ℃, adding a neutralizing agent, cooling and discharging to obtain the acrylic modified polyester for coating in the water-based automobile paint.
2. The method for preparing the acrylic modified polyester for the water-based automobile paint floating coat according to claim 1, wherein the initiator is one or more of benzoyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide and tert-butyl peroxybenzoate.
3. The method for preparing the acrylic modified polyester for the water-based automobile paint intercoat according to claim 1, wherein the alcohol ether solvent is one or more of propylene glycol monobutyl ether, isopropanol, isobutanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether and dipropylene glycol methyl ether.
4. The method for preparing acrylic modified polyester for water-based automobile paint middle coating according to claim 1, wherein the group A material comprises the following components by weight percent: 3-5% of dimer acid, 2-4% of neopentyl glycol, 6-8% of trimethylolpropane, 1-3% of adipic acid, 2-4% of isophthalic acid, 0-0.5% of xylene and 6-8% of phthalic anhydride; the group B material comprises the following components in percentage by weight: 6-8% of methyl methacrylate, 5-15% of styrene, 0.2-0.5% of acrylic acid, 6-9% of butyl acrylate, 2-3% of butyl methacrylate and 2-4% of hydroxypropyl acrylate;
the initiator consists of the following components in percentage by weight: 1 to 1.5 percent of benzoyl peroxide and 0.5 to 0.8 percent of tert-butyl peroxybenzoate; the weight percentage of the tertiary carbonic acid glycidyl ester is 2-5 percent, and the weight percentage of the maleic anhydride is 1-2 percent; the alcohol ether solvent consists of the following components in percentage by weight: 1-3% of 1, 6-hexanediol, 9-11% of ethylene glycol monobutyl ether and 9-11% of propylene glycol methyl ether.
5. The method for preparing acrylic acid modified polyester for water-based automobile paint intercoat according to claims 1-4, wherein the neutralizing agent is dimethylethanolamine.
6. The method for preparing the acrylic modified polyester for the water-based automobile paint midcoat according to claim 1, wherein in (1) preparing the prepolymer, the viscosity qualified value is as follows: 10000-20000mpa.s/25 ℃, the qualified value of acid value is: 40-50 mgKOH/g.
7. The method for preparing acrylic modified polyester for water-based automobile paint intercoat according to claim 1, wherein in the polymerization modification (2), the mass of the initiator added dropwise is 80% of the total mass of the initiator, the mass of the initiator supplemented for the first time is 10% of the total mass of the initiator, and the mass of the initiator supplemented for the second time is 10% of the total mass of the initiator.
8. The method for preparing acrylic modified polyester for water-based automobile paint intercoat according to claim 1, wherein (1) in preparing prepolymer, excess xylene is extracted after viscosity acid value is qualified.
9. An acrylic modified polyester for water-based automotive paint intercoat, characterized by being obtained by the method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110929992.6A CN113736031A (en) | 2021-08-13 | 2021-08-13 | Acrylic acid modified polyester for water-based automobile paint floating coat and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110929992.6A CN113736031A (en) | 2021-08-13 | 2021-08-13 | Acrylic acid modified polyester for water-based automobile paint floating coat and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113736031A true CN113736031A (en) | 2021-12-03 |
Family
ID=78731024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110929992.6A Pending CN113736031A (en) | 2021-08-13 | 2021-08-13 | Acrylic acid modified polyester for water-based automobile paint floating coat and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113736031A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761685A (en) * | 2013-10-21 | 2015-07-08 | 北京金汇利应用化工制品有限公司 | Preparation method of waterborne acrylic modified saturated polyester resin |
| CN105968271A (en) * | 2016-06-08 | 2016-09-28 | 浙江德尚化工科技有限公司 | Preparation method of acrylic acid grafted and modified saturated polyester resin |
| CN109679468A (en) * | 2018-12-29 | 2019-04-26 | 江西原石科技有限公司 | A kind of waterborne polyester-acrylic resin hybrid and preparation method |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
-
2021
- 2021-08-13 CN CN202110929992.6A patent/CN113736031A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761685A (en) * | 2013-10-21 | 2015-07-08 | 北京金汇利应用化工制品有限公司 | Preparation method of waterborne acrylic modified saturated polyester resin |
| CN105968271A (en) * | 2016-06-08 | 2016-09-28 | 浙江德尚化工科技有限公司 | Preparation method of acrylic acid grafted and modified saturated polyester resin |
| CN109679468A (en) * | 2018-12-29 | 2019-04-26 | 江西原石科技有限公司 | A kind of waterborne polyester-acrylic resin hybrid and preparation method |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冯鹏程等: "汽车中涂用水性丙烯酸改性聚酯树脂的合成及其性能", 中国涂料, vol. 35, no. 5, pages 31 - 36 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1270704A (en) | Multilayer coating having a clear top coat formed on a color base coat and method of forming the same | |
| US4170582A (en) | Process for preparing a polymer resin aqueous dispersion | |
| CN101914185B (en) | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom | |
| CN107522821B (en) | Acrylic acid modified polyester water-based resin for coil coating and preparation method thereof | |
| CN106749945B (en) | Polyester modified water-based acrylic resin, preparation and application in varnish | |
| CN109734884B (en) | Deep drawing resistant waterborne acrylic modified polyester resin and preparation method thereof | |
| CN110511388B (en) | Modified hydroxyl acrylic emulsion for water-based metal decorating paint and preparation method thereof | |
| JPH09501732A (en) | Aqueous branched polymer dispersion | |
| CA1101576A (en) | Aqueous coating composition of an acrylic-vinyl oxazoline ester polymer | |
| CA2024623A1 (en) | Waterbased methylol (meth)acrylamide acrylic polymer and polyurethane containing coating composition | |
| CN111138603B (en) | Water-based alkyd-acrylate dispersion and preparation method and application thereof | |
| CN110054722A (en) | A kind of high richness Aqueous acrylic urethane coating composition and preparation method thereof including water-based hydroxyl acrylic acid dispersion resin | |
| CN108264643B (en) | Copolymer P, aqueous dispersion resin and application of aqueous dispersion resin in aqueous coating | |
| EP2342242B1 (en) | Process for preparing aqueous copolymer dispersions | |
| EP0667371A2 (en) | Curable resin composition, coating composition and process for forming a cured film | |
| CN102219873A (en) | Triallyl isocyanurate modified aqueous hydroxyl acrylic resin and preparation method thereof | |
| CN114044881B (en) | Phosphate modified waterborne epoxy ester resin, antirust primer thereof and preparation method thereof | |
| WO1994004581A1 (en) | Waterborne latices adapted for spray application | |
| CN109503738B (en) | Phosphoric acid modified polyisoprene rubber, polyisoprene rubber modified acrylate resin dispersion, preparation method and application | |
| CN113736031A (en) | Acrylic acid modified polyester for water-based automobile paint floating coat and preparation method thereof | |
| CN1159399C (en) | Water-based acrylic acid modified alcoholic acid amino baking paint | |
| CN110317302B (en) | Acrylic acid modified alkyd resin and preparation method thereof | |
| CN111732686A (en) | Hydroxyl acrylic acid dispersion composition for water-based amino baking paint and preparation method thereof | |
| JPH01138216A (en) | Aqueous graft copolymer emulsion, its production and its use as binder for water dilutable automatic drying paint | |
| CN112759720B (en) | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211203 |
|
| RJ01 | Rejection of invention patent application after publication |