CN109852189A - Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof - Google Patents
Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof Download PDFInfo
- Publication number
- CN109852189A CN109852189A CN201910005675.8A CN201910005675A CN109852189A CN 109852189 A CN109852189 A CN 109852189A CN 201910005675 A CN201910005675 A CN 201910005675A CN 109852189 A CN109852189 A CN 109852189A
- Authority
- CN
- China
- Prior art keywords
- parts
- added
- modified polyester
- polyester resin
- aqueous epoxy
- 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
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 43
- 239000004645 polyester resin Substances 0.000 title claims abstract description 43
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 41
- 239000004593 Epoxy Substances 0.000 title claims abstract description 31
- -1 acrylic compound Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 30
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 28
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 19
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 15
- 239000001361 adipic acid Substances 0.000 claims abstract description 15
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 14
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960002887 deanol Drugs 0.000 claims abstract description 12
- 239000012972 dimethylethanolamine Substances 0.000 claims abstract description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000011973 solid acid Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000004640 Melamine resin Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000001723 curing Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 4
- 239000001294 propane Substances 0.000 claims 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 239000003973 paint Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of thermosetting aqueous epoxy acrylic compound modified polyester resins and preparation method thereof, including following raw material: phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, trimethylolpropane, neopentyl glycol, dimethylbenzene, epoxy resin, acrylic acid, butyl acrylate, hydroxy-ethyl acrylate, styrene, benzoyl peroxide, ethylene glycol monobutyl ether, dimethylethanolamine and deionized water.The comprehensive performance of paint film can be improved in modified polyester resin, is aqueous thermosetting resin, and organic solvent is few, and the feature of environmental protection is good, and hardness is high, and adhesive force is good, and wearability and solvent resistance are good, and tensile strength is excellent and good weatherability.
Description
Technical field
The present invention relates to a kind of coating, in particular to a kind of thermosetting aqueous epoxy acrylic compound modified polyester resin and
Preparation method belongs to technical field of polymer materials.
Background technique
Coating is one of common high molecular material as decoration, surface protection articles.Existing baking vanish polyester resin
Mostly solvent based product, needs to be added during making and using a large amount of organic solvent, and defect essentially consists in following several
A aspect: (1) unhealthy, not environmentally: a large amount of organic solvent can volatilize in air in use process, to the body of user
Health has very macrolesion, pollutes air, and the feature of environmental protection is poor；(2) at high cost: organic solvent is at high price, and transports inconvenience, will cause
Increased costs, price improve；(3) safety is poor: inflammable and explosive, risk is high.In addition to drawbacks described above, existing polyester resin is more
It is lower that there are intensity, facile hydrolysis, and the poor problem of outdoor durable, comprehensive performance, using effect are poor.
Summary of the invention
The present invention provides a kind of thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof, modified
Polyester resin the comprehensive performance of paint film can be improved, be aqueous thermosetting resin, organic solvent is few, and the feature of environmental protection is good, and hardness is high, attached
Put forth effort, wearability and solvent resistance are good, and tensile strength is excellent and good weatherability.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows: a kind of thermosetting aqueous epoxy acrylic is compound
Modified polyester resin, including following raw material: phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, trimethylolpropane, neopentyl glycol, dimethylbenzene,
Epoxy resin, acrylic acid, butyl acrylate, hydroxy-ethyl acrylate, styrene, benzoyl peroxide, ethylene glycol monobutyl ether, diformazan
Ethylethanolamine and deionized water.
As a preferred embodiment, the thermosetting aqueous epoxy acrylic compound modified polyester resin, including
The raw material of following parts by weight:
60-70 parts of phthalic anhydride, 120-140 parts of tetrahydrophthalic anhydride, 50-60 parts of adipic acid, 20-30 parts of trimethylolpropane, new penta
140-160 parts of glycol, 10-20 parts of dimethylbenzene, 20-30 parts of epoxy resin, 5-10 parts of acrylic acid, 20-30 parts of butyl acrylate, third
10-15 parts of olefin(e) acid hydroxyl ethyl ester, 15-20 parts of styrene, 2-4 parts of benzoyl peroxide, 30-50 parts of ethylene glycol monobutyl ether, dimethyl
5-10 parts and deionized water 100-200 parts of ethanol amine.
A kind of preparation method of thermosetting aqueous epoxy acrylic compound modified polyester resin, comprising the following steps:
A, by 20-30 parts of epoxy resin, 60-70 parts of phthalic anhydride, 120-140 parts of tetrahydrophthalic anhydride, 50-60 parts of adipic acid, three hydroxyls
20-30 parts of methylpropane, 140-160 parts of neopentyl glycol, 10-20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 150-180 DEG C of melting to stir evenly, is warming up to 180-200 DEG C after reacting 1-2h, protects
After temperature reaction 1-2h, start middle control measurement acid value；
C, when solid acid value reaches 20-30mg KOH/g in step b, 90-105 DEG C is cooled to, ethylene glycol only son is added
Ether thinning to solid content is 60-70%, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added ethylene glycol monobutyl ether 20-30 parts, is heated to 110-
125 DEG C, stirring mixes well it；
E, by 5-10 parts of acrylic acid, 15-20 parts of styrene, 20-30 parts of butyl acrylate, 10-15 parts of hydroxy-ethyl acrylate,
It 1-2 parts of benzoyl peroxide, is uniformly mixed, is added drop-wise to the prepolymer A's obtained in step d under 110-125 DEG C of environment
In ethylene glycol monobutyl ether solution；
F, after step e is added dropwise to complete, 2-3h is kept the temperature under 110-125 DEG C of environment, adds benzoyl peroxide on the way, so that
Monomer polymerization is complete；
G, obtained product in step f is cooled to 60-70 DEG C, is added dimethylethanolamine 5-10 part, stirring, be added go from
Sub- water adjusts solid content to 60-65%, stirs under 60-70 DEG C of environment, cool down filtering and discharging, and thermosetting aqueous epoxy third is made
Olefin(e) acid compound modified polyester resin.
As a preferred embodiment, the preparation of the thermosetting aqueous epoxy acrylic compound modified polyester resin
Method, comprising the following steps:
A, by 20-30 parts of epoxy resin, 60-70 parts of phthalic anhydride, 120-140 parts of tetrahydrophthalic anhydride, 50-60 parts of adipic acid, three hydroxyls
20-30 parts of methylpropane, 140-160 parts of neopentyl glycol, 10-20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 160 DEG C of meltings to stir evenly, is warming up to 200 DEG C after reacting 2h, insulation reaction 2h
Afterwards, start middle control measurement acid value；
C, when solid acid value reaches 30mgKOH/g in step b, 100 DEG C are cooled to, ethylene glycol monobutyl ether thinning is added extremely
Solid content is 70%, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added ethylene glycol monobutyl ether 20-30 parts, is heated to 120-
125 DEG C, stirring mixes well it；
E, by 5-10 parts of acrylic acid, 15-20 parts of styrene, 20-30 parts of butyl acrylate, 10-15 parts of hydroxy-ethyl acrylate,
It 2 parts of benzoyl peroxide, is uniformly mixed, the second of the prepolymer A obtained in step d is added drop-wise under 120-125 DEG C of environment
In glycol monobutyl ether solution, process 2h is added dropwise；
F, after step e is added dropwise to complete, 3h is kept the temperature under 120-125 DEG C of environment, adds benzoyl peroxide 0.5-1 on the way
Part, so that monomer polymerization is complete；
G, obtained product in step f is cooled to 70 DEG C, is added dimethylethanolamine 5-10 parts, stir 0.5h, addition is gone
Ionized water adjusts solid content to 65%, 1h is stirred under 70 DEG C of environment, cool down filtering and discharging, and thermosetting aqueous propylene oxide is made
Sour compound modified polyester resin.
As a preferred embodiment, the solidification of the thermosetting aqueous epoxy acrylic compound modified polyester resin
Method: thermosetting aqueous epoxy acrylic compound modified polyester resin and aqueous methyl-etherified melamine resin are pressed to the ratio of 6:1
Example is mixed evenly, and is adjusted to viscosity with deionized water and applies between four glasss of 20-25s, solid content 55-65%, in 150 DEG C of environment
Under, solidify 30min.
By adopting the above technical scheme, due to using epoxy resin and acrylic resin composite modified, polyester tree is prepared
Rouge is aqueous thermosetting resin, can disperse in water；Entire preparation process avoids largely using organic solvent, only uses few
Environmentally friendly solvent is measured, while replacing a large amount of organic solvent using deionized water, VOC content can be reduced, dropped while environmentally friendly, healthy
Low cost improves security performance；Meanwhile the compound modified polyester resin being prepared is to the adhesive force and film strength of ground
Good, tensile strength is excellent, and hardness is high；It is wear-resisting, water-fast, solvent resistant ability is strong, outdoor durable, good weatherability greatly improve paint film
Comprehensive performance.
Specific embodiment
Below with reference to embodiment, specific embodiments of the present invention will be further explained.It should be noted that right
It is used to help understand the present invention in the explanation of these embodiments, but and does not constitute a limitation of the invention.In addition, being retouched below
Technical characteristic involved in each embodiment of the present invention stated can be combined with each other as long as they do not conflict with each other.
Embodiment 1:
A kind of thermosetting aqueous epoxy acrylic compound modified polyester resin, the raw material including following parts by weight:
60 parts of phthalic anhydride, 120 parts of tetrahydrophthalic anhydride, 50 parts of adipic acid, 20 parts of trimethylolpropane, 140 parts of neopentyl glycol, diformazan
10 parts of benzene, 20 parts of epoxy resin, 5 parts of acrylic acid, 20 parts of butyl acrylate, 10 parts of hydroxy-ethyl acrylate, 15 parts of styrene, peroxide
Change 3 parts of benzoyl, 30 parts of ethylene glycol monobutyl ether, 5 parts and 100 parts of deionized water of dimethylethanolamine.
1. a kind of preparation method of thermosetting aqueous epoxy acrylic compound modified polyester resin, comprising the following steps:
A, by 20 parts of epoxy resin, 60 parts of phthalic anhydride, 120 parts of tetrahydrophthalic anhydride, 50 parts of adipic acid, 20 parts of trimethylolpropane,
140 parts of neopentyl glycol, 10 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 160 DEG C of meltings and stirs evenly, and reacts and is warming up to 200 DEG C after 2h, after insulation reaction 2h,
Control measurement acid value in beginning；
C, when solid acid value reaches 30mgKOH/g in step b, 100 DEG C are cooled to, ethylene glycol monobutyl ether thinning is added and arrives
Solid content is 70%, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added 20 parts of ethylene glycol monobutyl ether, is heated to 120-125
DEG C, stirring mixes well it；
E, by 5 parts of acrylic acid, 15 parts of styrene, 20 parts of butyl acrylate, 10 parts of hydroxy-ethyl acrylate, benzoyl peroxide
It 2 parts, is uniformly mixed, the ethylene glycol monobutyl ether that the prepolymer A obtained in step d is added drop-wise under 120-125 DEG C of environment is molten
In liquid, process 2h is added dropwise；
F, after step e is added dropwise to complete, 3h is kept the temperature under 120-125 DEG C of environment, adds 1 part of benzoyl peroxide on the way, with
Keep monomer polymerization complete；
G, obtained product in step f is cooled to 70 DEG C, is added 5 parts of dimethylethanolamine, stir 0.5h, deionization is added
Water adjusts solid content to 65%, 1h is stirred under 70 DEG C of environment, cool down filtering and discharging, and it is multiple that thermosetting aqueous epoxy acrylic is made
Close modified polyester resin.
2. performance test:
Above-mentioned thermosetting aqueous epoxy acrylic compound modified polyester resin 120g, methyl-etherified melamine resin 20g are taken,
It is mixed evenly, a small amount of deionized water is added and adjusts viscosity, system is white viscous liquid, and standing is clear after defoaming
Liquid；
Surface of bottom material is cleaned up, is painted using spray gun, is controlled after film curing with a thickness of between 15 to 20 μm；
The ground coated is put into 50 DEG C of baking ovens preheating 10min, avoids directly being heated at high temperature and generates surface defect, after will be pre-
The good ground of heat toasts 30min at 150 DEG C；
High by the cured paint film richness of above step, appearance is good, and hardness reaches 3H, and 0 grade of adhesive force, impact resistance reaches
50cmKg, resistance to ethyl alcohol, acetone wipe 90 times, 24 hours bubble-frees resistant to salt corrosion.
Embodiment 2:
A kind of thermosetting aqueous epoxy acrylic compound modified polyester resin, the raw material including following parts by weight:
70 parts of phthalic anhydride, 140 parts of tetrahydrophthalic anhydride, 60 parts of adipic acid, 30 parts of trimethylolpropane, 160 parts of neopentyl glycol, diformazan
20 parts of benzene, 30 parts of epoxy resin, 10 parts of acrylic acid, 30 parts of butyl acrylate, 15 parts of hydroxy-ethyl acrylate, 20 parts of styrene, mistake
3 parts of Benzoyl Oxide, 50 parts of ethylene glycol monobutyl ether, 10 parts and 200 parts of deionized water of dimethylethanolamine.
1. a kind of preparation method of thermosetting aqueous epoxy acrylic compound modified polyester resin, comprising the following steps:
A, by 30 parts of epoxy resin, 70 parts of phthalic anhydride, 140 parts of tetrahydrophthalic anhydride, 60 parts of adipic acid, 30 parts of trimethylolpropane,
160 parts of neopentyl glycol, 20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 160 DEG C of meltings and stirs evenly, and is warming up to 200 DEG C after reacting 2h, opens after insulation reaction 2h
Control measurement acid value in beginning；
C, when solid acid value reaches 30mg KOH/g in step b, 100 DEG C are cooled to, ethylene glycol monobutyl ether thinning is added
It is 70% to solid content, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added 30 parts of ethylene glycol monobutyl ether, is heated to 120-125
DEG C, stirring mixes well it；
E, by 10 parts of acrylic acid, 20 parts of styrene, 30 parts of butyl acrylate, 15 parts of hydroxy-ethyl acrylate, benzoyl peroxide first
It 2 parts of acyl, is uniformly mixed, the ethylene glycol monobutyl ether of the prepolymer A obtained in step d is added drop-wise under 120-125 DEG C of environment
In solution, process 2h is added dropwise；
F, after step e is added dropwise to complete, 3h is kept the temperature under 120-125 DEG C of environment, adds benzoyl peroxide 0.5-1 on the way
Part, so that monomer polymerization is complete；
G, obtained product in step f is cooled to 70 DEG C, is added 10 parts of dimethylethanolamine, stir 0.5h, addition go from
Sub- water adjusts solid content to 65%, 1h is stirred under 70 DEG C of environment, cool down filtering and discharging, and thermosetting aqueous epoxy acrylic is made
Compound modified polyester resin.
2. performance test:
Above-mentioned thermosetting aqueous epoxy acrylic compound modified polyester resin 120g, methyl-etherified melamine resin 20g are taken,
It is mixed evenly, a small amount of deionized water is added and adjusts viscosity, system is white viscous liquid, and standing is clear after defoaming
Liquid；
Surface of bottom material is cleaned up, is painted using spray gun, is controlled after film curing with a thickness of between 15 to 20 μm；
The ground coated is put into 50 DEG C of baking ovens preheating 10min, avoids directly being heated at high temperature and generates surface defect, after will preheating
Good ground toasts 30min at 150 DEG C；
High by the cured paint film richness of above step, appearance is good, and hardness reaches 3H, and 0 grade of adhesive force, impact resistance reaches
50cmKg, resistance to ethyl alcohol, acetone wipe 90 times, and 24 hours resistant to salt corrosion without gas skin.
Comparative example 1:
1. a kind of preparation method of thermosetting aqueous epoxy acrylic compound modified polyester resin, comprising the following steps:
A, by 30 parts of epoxy resin, 70 parts of phthalic anhydride, 140 parts of tetrahydrophthalic anhydride, 60 parts of adipic acid, 30 parts of trimethylolpropane,
160 parts of neopentyl glycol, 20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 160 DEG C of meltings and stirs evenly, and is warming up to 200 DEG C after reacting 2h, opens after insulation reaction 2h
Control measurement acid value in beginning；
C, when solid acid value reaches 30mg KOH/g in step b, 100 DEG C are cooled to, ethylene glycol monobutyl ether thinning is added
It is 70% to solid content, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added 30 parts of ethylene glycol monobutyl ethers, is heated to 120-125
DEG C, stirring mixes well it；
E, it by 20 parts of styrene, 2 parts of benzoyl peroxide, is uniformly mixed, step is added drop-wise under 120-125 DEG C of environment
In the ethylene glycol monobutyl ether solution of the prepolymer A obtained in rapid d, process 2h is added dropwise；
F, after step e is added dropwise to complete, 3h is kept the temperature under 120-125 DEG C of environment, adds benzoyl peroxide 0.5-1 on the way
Part, so that monomer polymerization is complete；
G, obtained product in step f is cooled to 70 DEG C, is added 10 parts of dimethylethanolamine, stir 0.5h, addition go from
Sub- water adjusts solid content to 65%, 1h is stirred under 70 DEG C of environment, cool down filtering and discharging, and thermosetting aqueous epoxy resin is made and changes
Property polyester resin.
2. performance test:
Above-mentioned thermosetting aqueous epoxy resin modification polyester resin 120g, methyl-etherified melamine resin 20g are taken, mixing is stirred
It mixes uniformly, a small amount of deionized water is added and adjusts viscosity, system is white viscous liquid, and standing is clear liquid after defoaming；
Surface of bottom material is cleaned up, is painted using spray gun, is controlled after film curing with a thickness of between 15 to 20 μm；
The ground coated is put into 50 DEG C of baking ovens preheating 10min, avoids directly being heated at high temperature and generates surface defect, after will preheating
Good ground toasts 30min at 160 DEG C；
Preferable by the cured paint film richness of above step, compactness is general, and hardness reaches H, and 2 grades of adhesive force, impact resistance
Power reaches 30cmKg, and resistance to ethyl alcohol, acetone wipe 30 times, and 12 hours resistant to salt corrosion without gas skin.
Comparative example 2:
1. a kind of preparation method of thermosetting aqueous epoxy acrylic compound modified polyester resin, comprising the following steps:
A, by 140 parts of tetrahydrophthalic anhydride, 60 parts of phthalic anhydride, 60 parts of adipic acid, 30 parts of trimethylolpropane, 160 parts of neopentyl glycol,
20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 160 DEG C of meltings to stir evenly, is warming up to 200 DEG C after reacting 2h, insulation reaction 2h
Afterwards, start middle control measurement acid value；
C, when solid acid value reaches 30mg KOH/g in step b, 100 DEG C are cooled to, ethylene glycol monobutyl ether thinning is added
It is 70% to solid content, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added 30 parts of ethylene glycol monobutyl ethers, is heated to 120-125
DEG C, stirring mixes well it；
E, by 10 parts of acrylic acid, 20 parts of styrene, 30 parts of butyl acrylate, 15 parts of hydroxy-ethyl acrylate, benzoyl peroxide first
It 2 parts of acyl, is uniformly mixed, the ethylene glycol monobutyl ether of the prepolymer A obtained in step d is added drop-wise under 120-125 DEG C of environment
In solution, process 2h is added dropwise；
F, after step e is added dropwise to complete, 3h is kept the temperature under 120-125 DEG C of environment, adds benzoyl peroxide 0.5-1 on the way
Part, so that monomer polymerization is complete；
G, obtained product in step f is cooled to 70 DEG C, is added 10 parts of dimethylethanolamine, stir 0.5h, addition go from
Sub- water adjusts solid content to 65%, 1h is stirred under 70 DEG C of environment, cool down filtering and discharging, and thermosetting aqueous epoxy resin is made and changes
Property polyester resin.
2. performance test:
Above-mentioned thermosetting aqueous epoxy resin modification polyester resin 120g, methyl-etherified melamine resin 20g are taken, mixing is stirred
It mixes uniformly, a small amount of deionized water is added and adjusts viscosity, system is white viscous liquid, and standing is clear liquid after defoaming；
Surface of bottom material is cleaned up, is painted using spray gun, is controlled after film curing with a thickness of between 15 to 20 μm；
The ground coated is put into 50 DEG C of baking ovens preheating 10min, avoids directly being heated at high temperature and generates surface defect, after will preheating
Good ground toasts 30min at 150 DEG C；
Good by the cured compact in paint film of above step, hardness reaches 1H, and 3 grades of adhesive force, impact resistance reaches
30cmKg, resistance to ethyl alcohol, acetone wipe 60 times, and 12 hours resistant to salt corrosion without gas skin.
The curing method of thermosetting aqueous epoxy acrylic compound modified polyester resin are as follows: by thermosetting aqueous propylene oxide
Sour compound modified polyester resin and aqueous methyl-etherified melamine resin are mixed evenly in the ratio of 6:1, with deionized water
It is adjusted to viscosity to apply between four glasss of 20-25s, solid content 20-30%, under 150 DEG C of environment, solidifies 30min.
The present invention screens to obtain optimal raw material composition and proportion by many experiments, and is preferably gone out most by many experiments
Good synthesis technology.By comparison above embodiments and the performance test results of comparative example, it is also seen that the present invention produces
The superiority of product comprehensive performance, technical effect are promoted significant.
By adopting the above technical scheme, due to using epoxy resin and acrylic resin composite modified, polyester tree is prepared
Rouge is aqueous thermosetting resin, can disperse in water；Entire preparation process avoids largely using organic solvent, only uses few
Environmentally friendly solvent is measured, while replacing a large amount of organic solvent using deionized water, VOC content can be reduced, dropped while environmentally friendly, healthy
Low cost improves security performance；Meanwhile the compound modified polyester resin being prepared is to the adhesive force and film strength of ground
Good, tensile strength is excellent, and hardness is high；It is wear-resisting, water-fast, solvent resistant ability is strong, outdoor durable, good weatherability greatly improve paint film
Comprehensive performance.
The embodiments of the present invention are described in detail in conjunction with the embodiments above, but the present invention is not limited to described realities
Apply mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiment party
Formula carries out a variety of change, modification, replacement and modification, still falls in protection scope of the present invention.
Claims (5)
1. a kind of thermosetting aqueous epoxy acrylic compound modified polyester resin, which is characterized in that including following raw material: phthalic anhydride,
Tetrahydrophthalic anhydride, adipic acid, trimethylolpropane, neopentyl glycol, dimethylbenzene, epoxy resin, acrylic acid, butyl acrylate, propylene
Sour hydroxyl ethyl ester, styrene, benzoyl peroxide, ethylene glycol monobutyl ether, dimethylethanolamine and deionized water.
2. thermosetting aqueous epoxy acrylic compound modified polyester resin according to claim 1, which is characterized in that including
The raw material of following parts by weight:
60-70 parts of phthalic anhydride, 120-140 parts of tetrahydrophthalic anhydride, 50-60 parts of adipic acid, 20-30 parts of trimethylolpropane, neopentyl glycol
140-160 parts, 10-20 parts of dimethylbenzene, 20-30 parts of epoxy resin, 5-10 parts of acrylic acid, 20-30 parts of butyl acrylate, acrylic acid
10-15 parts of hydroxyl ethyl ester, 15-20 parts of styrene, 2-4 parts of benzoyl peroxide, 30-50 parts of ethylene glycol monobutyl ether, dimethyl ethanol
5-10 parts and deionized water 100-200 parts of amine.
3. a kind of preparation of such as described in any item thermosetting aqueous epoxy acrylic compound modified polyester resins of claim 1-2
Method, which comprises the following steps:
A, by 20-30 parts of epoxy resin, 60-70 parts of phthalic anhydride, 120-140 parts of tetrahydrophthalic anhydride, 50-60 parts of adipic acid, trihydroxy methyl
20-30 parts of propane, 140-160 parts of neopentyl glycol, 10-20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 150-180 DEG C of melting to stir evenly, is warming up to 180-200 DEG C after reacting 1-2h, heat preservation is anti-
After answering 1-2h, start middle control measurement acid value；
C, when solid acid value reaches 20-30mg KOH/g in step b, 90-105 DEG C is cooled to, ethylene glycol monobutyl ether is added and converts
It is dilute to solid content be 60-70%, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added ethylene glycol monobutyl ether 20-30 parts, is heated to 110-125 DEG C,
Stirring mixes well it；
E, by 5-10 parts of acrylic acid, 15-20 parts of styrene, 20-30 parts of butyl acrylate, 10-15 parts of hydroxy-ethyl acrylate, peroxide
Change benzoyl 1-2 parts, is uniformly mixed, the second two of the prepolymer A obtained in step d is added drop-wise under 110-125 DEG C of environment
In alcohol only son's ethereal solution；
F, after step e is added dropwise to complete, 2-3h is kept the temperature under 110-125 DEG C of environment, adds benzoyl peroxide on the way, so that monomer
Polymerization is complete；
G, obtained product in step f is cooled to 60-70 DEG C, is added dimethylethanolamine 5-10 parts, deionized water is added in stirring
Solid content is adjusted to 60-65%, is stirred under 60-70 DEG C of environment, cool down filtering and discharging, and thermosetting aqueous epoxy acrylic is made
Compound modified polyester resin.
4. the preparation method of thermosetting aqueous epoxy acrylic compound modified polyester resin according to claim 3, special
Sign is, comprising the following steps:
A, by 20-30 parts of epoxy resin, 60-70 parts of phthalic anhydride, 120-140 parts of tetrahydrophthalic anhydride, 50-60 parts of adipic acid, trihydroxy methyl
20-30 parts of propane, 140-160 parts of neopentyl glycol, 10-20 parts of dimethylbenzene are added in reaction system；
B, step a reaction system is heated to 160 DEG C of meltings to stir evenly, is warming up to 200 DEG C after reacting 2h, after insulation reaction 2h, opened
Control measurement acid value in beginning；
C, 100 DEG C are cooled to when solid acid value reaches 30mgKOH/g in step b, ethylene glycol monobutyl ether thinning is added to containing admittedly
Amount is 70%, as prepolymer A；
D, 100 parts of the prepolymer A for taking step c to be prepared is added ethylene glycol monobutyl ether 20-30 parts, is heated to 120-125 DEG C,
Stirring mixes well it；
E, by 5-10 parts of acrylic acid, 15-20 parts of styrene, 20-30 parts of butyl acrylate, 10-15 parts of hydroxy-ethyl acrylate, peroxide
Change 2 parts of benzoyl, is uniformly mixed, the ethylene glycol of the prepolymer A obtained in step d is added drop-wise under 120-125 DEG C of environment
In only son's ethereal solution, process 2h is added dropwise；
F, after step e is added dropwise to complete, 3h is kept the temperature under 120-125 DEG C of environment, adds 0.5-1 parts of benzoyl peroxide on the way, with
Keep monomer polymerization complete；
G, obtained product in step f is cooled to 70 DEG C, is added dimethylethanolamine 5-10 parts, stir 0.5h, deionization is added
Water adjusts solid content to 65%, 1h is stirred under 70 DEG C of environment, cool down filtering and discharging, and it is multiple that thermosetting aqueous epoxy acrylic is made
Close modified polyester resin.
5. the curing method of thermosetting aqueous epoxy acrylic compound modified polyester resin according to claim 1 or 2,
It is characterized in that, thermosetting aqueous epoxy acrylic compound modified polyester resin and aqueous methyl-etherified melamine resin is pressed into 6:1
Ratio be mixed evenly, with deionized water be adjusted to viscosity apply four glasss of 20-25s between, solid content 20-30%, at 150 DEG C
Under environment, solidify 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910005675.8A CN109852189A (en) | 2019-01-03 | 2019-01-03 | Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910005675.8A CN109852189A (en) | 2019-01-03 | 2019-01-03 | Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109852189A true CN109852189A (en) | 2019-06-07 |
Family
ID=66893773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910005675.8A Pending CN109852189A (en) | 2019-01-03 | 2019-01-03 | Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109852189A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909553A (en) * | 2020-08-10 | 2020-11-10 | 淮北金邦新型材料有限公司 | Adhesion promoting resin and production method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3513208A1 (en) * | 1984-04-14 | 1985-10-17 | Victor Company Of Japan, Ltd., Yokohama, Kanagawa | MAGNETIC RECORDING MEDIUM CONTAINING A SPECIAL COPOLYMER BINDING AGENT |
| CN101864044A (en) * | 2010-07-02 | 2010-10-20 | 湖南湘江涂料集团有限公司 | Aqueous acrylic modified epoxy ester resin and synthesizing method thereof |
| CN103725145A (en) * | 2013-12-13 | 2014-04-16 | 武汉工程大学 | Aqueous alkide resin-acrylic acid resin hybrid coating and preparation method thereof |
| CN106281001A (en) * | 2016-08-15 | 2017-01-04 | 中山大桥化工集团有限公司 | A kind of water paint for dip-coating and preparation method thereof |
| CN107141425A (en) * | 2017-05-19 | 2017-09-08 | 江苏三木化工股份有限公司 | A kind of baking vanish aqueous epoxy resins and preparation method and application |
| CN109280139A (en) * | 2018-09-19 | 2019-01-29 | 江苏三木化工股份有限公司 | Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof |
-
2019
- 2019-01-03 CN CN201910005675.8A patent/CN109852189A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3513208A1 (en) * | 1984-04-14 | 1985-10-17 | Victor Company Of Japan, Ltd., Yokohama, Kanagawa | MAGNETIC RECORDING MEDIUM CONTAINING A SPECIAL COPOLYMER BINDING AGENT |
| CN101864044A (en) * | 2010-07-02 | 2010-10-20 | 湖南湘江涂料集团有限公司 | Aqueous acrylic modified epoxy ester resin and synthesizing method thereof |
| CN103725145A (en) * | 2013-12-13 | 2014-04-16 | 武汉工程大学 | Aqueous alkide resin-acrylic acid resin hybrid coating and preparation method thereof |
| CN106281001A (en) * | 2016-08-15 | 2017-01-04 | 中山大桥化工集团有限公司 | A kind of water paint for dip-coating and preparation method thereof |
| CN107141425A (en) * | 2017-05-19 | 2017-09-08 | 江苏三木化工股份有限公司 | A kind of baking vanish aqueous epoxy resins and preparation method and application |
| CN109280139A (en) * | 2018-09-19 | 2019-01-29 | 江苏三木化工股份有限公司 | Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909553A (en) * | 2020-08-10 | 2020-11-10 | 淮北金邦新型材料有限公司 | Adhesion promoting resin and production method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4414173A (en) | In-mold coating | |
| CN102002305B (en) | Water-based precoated coiled material coating back paint and preparation method thereof | |
| US10513566B2 (en) | Epoxidized oil and resin compositions | |
| CN107141425A (en) | A kind of baking vanish aqueous epoxy resins and preparation method and application | |
| US4534888A (en) | In-mold coating | |
| KR101818348B1 (en) | high-gloss high-leveling powder coating composition | |
| JPS6019941B2 (en) | Compositions useful for in-mold coatings | |
| US10913829B2 (en) | Epoxidized oil binder compositions and process for preparation of thermoset hardened products | |
| CN109852189A (en) | Thermosetting aqueous epoxy acrylic compound modified polyester resin and preparation method thereof | |
| CN110256905A (en) | A kind of filled-type UV colorant and preparation method thereof | |
| CN114213608A (en) | Aqueous hydroxyl acrylic acid dispersion and preparation method and application thereof | |
| CN109280139B (en) | Thermosetting water-based epoxy acrylic acid composite modified polyester resin and preparation method thereof | |
| CN100396725C (en) | Surface treatment method of scale resin with glass scale and prepn process of scale resin | |
| CN105440897B (en) | A kind of piano fire-retardant black gel coat and preparation method | |
| CN113683942B (en) | Polyimide water-based epoxy coating and preparation method thereof | |
| JP3145144B2 (en) | In-mold coating composition | |
| CN109486398A (en) | A kind of painting dressing automobiles paint and preparation method thereof | |
| CN107011785A (en) | A kind of wear-resistant polyester mirror surface coating of hard and preparation method thereof | |
| CN107523197A (en) | A kind of novel aqueous polyester resin | |
| CN108373625A (en) | A kind of metallic paint for the protection of power equipment plastic shell | |
| CN107434837A (en) | A kind of priming paint acrylic resin and preparation method thereof | |
| CN106752355A (en) | The preparation method of ink used for plastic coating | |
| CN100372900C (en) | Mirror back paint resin and spraying paint | |
| US7160961B1 (en) | Melt coating method using a polyester resin composition | |
| JPS60110702A (en) | Branched acrylic resin, its production and coating resin composition |
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: 20190607 |
|
| RJ01 | Rejection of invention patent application after publication |