CN115304702A - Synthetic method and application of thermosetting acrylic resin - Google Patents
Synthetic method and application of thermosetting acrylic resin Download PDFInfo
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- CN115304702A CN115304702A CN202111038882.7A CN202111038882A CN115304702A CN 115304702 A CN115304702 A CN 115304702A CN 202111038882 A CN202111038882 A CN 202111038882A CN 115304702 A CN115304702 A CN 115304702A
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- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 30
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 30
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 28
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000010790 dilution Methods 0.000 claims abstract description 11
- 239000012895 dilution Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 16
- 239000008096 xylene Substances 0.000 claims description 14
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 3
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000011010 flushing procedure Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 4
- 238000007865 diluting Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000006838 isophorone group Chemical group 0.000 description 2
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of resin, in particular to a synthetic method and application of thermosetting acrylic resin, which comprises the following steps: step (1), putting a first solvent into a reaction pot; step (2), putting a reaction monomer and a first initiator into an overhead tank to obtain a phase I; step (3), heating the reaction kettle, dropwise adding the phase one into the reaction kettle to obtain a phase two, stopping heating after dropwise adding is finished, and putting the phase two into a dilution kettle; and (4) heating the dilution pot, preserving heat, adding a second solvent and a second initiator, preserving heat, adding a third solvent and a third initiator, preserving heat, cooling, adding a fourth solvent, filtering and discharging. The thermosetting acrylic resin prepared by the invention has good compatibility, good leveling property, moderate viscosity and transparent and white appearance in fluorocarbon coating, and can be added in fluorocarbon resin in large quantity.
Description
Technical Field
The invention relates to the field of resin, in particular to a synthetic method and application of thermosetting acrylic resin.
Background
The fluorocarbon coating is a coating which takes fluororesin as a main film forming substance, has strong fluorocarbon bond energy due to the introduction of fluorine elements with large electronegativity, has excellent weather resistance, heat resistance, low temperature resistance and chemical resistance, and is widely applied to various outdoor building materials. However, fluorocarbon resin and pigment are not well compatible in a system, leveling is not good, and application of fluorocarbon resin in paint is limited, so that part of acrylic resin is generally used in fluorocarbon paint to be compounded with fluorocarbon resin, thermoplastic acrylic resin is mainly used in the market at present, and thermosetting acrylic resin causes a series of problems such as poor compatibility and the like, so that the development of a thermosetting acrylic resin which can be well compatible with fluororesin in fluorocarbon paint has market application prospect.
Disclosure of Invention
The first aspect of the present invention provides a method for synthesizing a thermosetting acrylic resin, comprising the steps of:
step (1), putting a first solvent into a reaction pot;
step (2), putting a reaction monomer and a first initiator into a head tank to obtain a phase I;
step (3), heating the reaction kettle, dropwise adding the phase I into the reaction kettle to obtain a phase II, stopping heating after dropwise adding is finished, and putting the phase II into a dilution kettle;
and (4) heating the dilution pot, preserving heat, adding a second solvent and a second initiator, preserving heat, adding a third solvent and a third initiator, preserving heat, cooling, adding a fourth solvent, filtering and discharging.
As a preferred embodiment, step (3) is carried out immediately after the first initiator is charged into the head tank for 20 to 40min in step (2).
As a preferred embodiment, the dropping time in the step (3) is 4 to 8 hours.
As a preferred embodiment, the temperature in the step (3) is raised to 110 to 130 ℃.
As a preferred embodiment, the filtration precision in the step (4) is 0.5 to 5 μm.
As a preferred embodiment, the first solvent, the second solvent, the third solvent and the fourth solvent include at least one of xylene, ethylene glycol monobutyl ether, isophorone, toluene, ethyl acetate, butyl acetate, acetone, butyl ketone, methyl isobutyl ketone, ethanol, butanol and isopropanol.
As a preferred embodiment, the reactive monomer comprises at least one of methyl methacrylate, methacrylic acid, ethyl acrylate, hydroxyethyl acrylate, acrylic acid, methyl acrylate, lauryl acrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate, acrylonitrile, styrene, acrylamide, vinyl acetate.
In a preferred embodiment, the first initiator, the second initiator, and the third initiator include at least one of a peroxy initiator and an azo initiator.
As a preferred embodiment, the first initiator, the second initiator and the third initiator comprise at least one of tert-butyl peroxybenzoate, cumene hydroperoxide, dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, azobisisobutyronitrile and azobisisoheptonitrile.
The second aspect of the invention provides the application of the synthetic method of the thermosetting acrylic resin in fluorocarbon coating.
Compared with the prior art, the invention has the following beneficial effects: the thermosetting acrylic resin prepared by the invention has good compatibility, good leveling property, moderate viscosity and transparent and white appearance in fluorocarbon coating, can be added in a large amount in fluorocarbon resin, solves the technical problem that the application of thermosetting resin in the field of fluorocarbon coating is limited in the prior art, and can also effectively solve the problem of plate adhesion of fluorocarbon coating in roller coating.
Drawings
Fig. 1-4 are graphs of experimental data of the thermosetting acrylic resin prepared in example 1 after being dried at 120 degrees for 30 min.
Wherein FIG. 1 is a molecular weight distribution diagram of a resin;
FIG. 2 is a graph of the glass transition temperature of the resin;
FIG. 3 is an infrared spectrum of a resin;
FIG. 4 shows the result of analysis by a superconducting NMR spectrometer of a resin, in which the solvent is deuterated chloroform.
Detailed Description
In order to solve the above technical problems, a first aspect of the present invention provides a method for synthesizing a thermosetting acrylic resin, comprising the steps of:
step (1), putting a first solvent into a reaction pot;
step (2), putting a reaction monomer and a first initiator into a head tank to obtain a phase I;
step (3), heating the reaction kettle, dropwise adding the phase one into the reaction kettle to obtain a phase two, stopping heating after dropwise adding is finished, and putting the phase two into a dilution kettle;
and (4) heating the dilution pot, preserving heat, adding a second solvent and a second initiator, preserving heat, adding a third solvent and a third initiator, preserving heat, cooling, adding a fourth solvent, filtering and discharging.
Preferably, the method comprises the following steps:
step (1), putting a first solvent into a reaction pot;
step (2), putting a reaction monomer and a first initiator into an overhead tank, and stirring to obtain a phase I;
introducing nitrogen, heating and preserving heat in the reaction kettle, closing the nitrogen, dropwise adding the phase I into the reaction kettle, stirring, introducing the nitrogen on the surface after dropwise adding to obtain a phase II, stopping heating after dropwise adding is finished, and putting the phase II into a dilution kettle;
and (4) heating the diluting kettle, sampling and detecting, performing subsequent procedures when the viscosity of the bubbles is greater than O, preserving heat for 0.5-5h at 120-130 ℃, adding a second solvent and a second initiator, preserving heat for 0.1-1h, adding a third solvent and a third initiator, preserving heat for 1-5h, cooling, adding a fourth solvent, filtering and discharging.
More preferably, the method comprises the following steps:
step (1), putting a first solvent into a reaction pot;
step (2), putting a reaction monomer and a first initiator into an overhead tank, stirring to obtain a phase I, and flushing a pipeline by using xylene after the phase I is put into the overhead tank;
step (3), introducing nitrogen, heating and preserving heat of the reaction kettle, closing the nitrogen, dropwise adding the first phase into the reaction kettle, stirring, flushing the head tank with xylene after dropwise adding, adding the obtained flushing fluid 1 into the reaction kettle, introducing the nitrogen on the surface after dropwise adding to obtain a second phase, stopping heating after dropwise adding, flushing the reaction kettle with a mixture of isophorone and xylene, and putting the obtained flushing fluid 2 and the second phase into a dilution kettle;
and (4) heating the diluting kettle, sampling and detecting, performing a subsequent procedure when the bubble viscosity is greater than O, preserving heat for 1h at 123-127 ℃, adding a second solvent and a second initiator, preserving heat for 0.5h, adding a third solvent and a third initiator, preserving heat for 2h at 125 ℃, cooling to 100 ℃, adding a fourth solvent, cooling to 85 ℃, dropwise adding isophorone to adjust the viscosity, filtering, and discharging.
As a preferred embodiment, step (3) is carried out immediately after the first initiator is charged into the head tank for 20 to 40min in step (2).
As a preferred embodiment, the dropping time in the step (3) is 4 to 8 hours.
As a preferred embodiment, the temperature in step (3) is raised to 110 to 130 ℃.
As a preferred embodiment, the filtration precision in the step (4) is 0.5 to 5 μm.
As a preferred embodiment, the first solvent, the second solvent, the third solvent and the fourth solvent include at least one of xylene, ethylene glycol monobutyl ether, isophorone, toluene, ethyl acetate, butyl acetate, acetone, butyl ketone, methyl isobutyl ketone, ethanol, butanol and isopropanol.
Preferably, the first solvent is xylene and ethylene glycol monobutyl ether.
Preferably, the mass ratio of the xylene to the ethylene glycol monobutyl ether is (1-2): 1.
preferably, the second solvent and the third solvent are both xylene.
Preferably, the fourth solvent is isophorone.
As a preferred embodiment, the reactive monomer comprises at least one of methyl methacrylate, methacrylic acid, ethyl acrylate, hydroxyethyl acrylate, acrylic acid, methyl acrylate, lauryl acrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate, acrylonitrile, styrene, acrylamide, vinyl acetate.
Preferably, the reactive monomer is methyl methacrylate, methacrylic acid, ethyl acrylate, hydroxyethyl acrylate.
Preferably, the mass ratio of the methyl methacrylate to the methacrylic acid to the ethyl acrylate to the hydroxyethyl acrylate is (5.1-5.3): (0.1-0.5): (4-5): (0.5-1).
In a preferred embodiment, the first initiator, the second initiator, and the third initiator include at least one of a peroxy initiator and an azo initiator.
Preferably, the first initiator and the third initiator comprise at least one of tert-butyl peroxybenzoate, cumene hydroperoxide, dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the first initiator is tert-butyl peroxybenzoate or cumene hydroperoxide.
Preferably, the mass ratio of tert-butyl peroxybenzoate to cumene hydroperoxide is 1: (3-5).
Preferably, the second initiator and the third initiator are tert-butyl peroxybenzoate.
The second aspect of the invention provides an application of a synthetic method of thermosetting acrylic resin in fluorocarbon paint.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Tert-butyl peroxybenzoate CAS:614-45-9
Cumene hydroperoxide CAS:80-15-9
T-butyl peroxyacetate CAS:107-71-1
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
In a first aspect of the present invention, there is provided a method for synthesizing a thermosetting acrylic resin, comprising the steps of:
step (1), putting a first solvent into a reaction pot;
step (2), putting a reaction monomer and a first initiator into an overhead tank, stirring to obtain a phase I, and flushing a pipeline by using xylene after the phase I is put into the overhead tank; immediately carrying out the step (3) after the first initiator is put into the head tank for 30 min;
and (3) introducing nitrogen, heating the reaction kettle to 120 ℃ and keeping the temperature, closing the nitrogen, dropwise adding the first phase into the reaction kettle for 4.5 hours, stirring, flushing the head tank with xylene after dropwise addition is finished, adding the obtained flushing fluid 1 into the reaction kettle, introducing nitrogen on the surface after dropwise addition is finished to obtain a second phase, stopping heating after dropwise addition is finished, and introducing isophorone and xylene in a mass ratio of 6.2:1, mixing and flushing the reaction kettle, and putting the obtained flushing liquid 2 and the phase two into a dilution kettle;
and (4) heating the diluting kettle, sampling and detecting, performing subsequent procedures when the bubble viscosity is greater than O, preserving heat for 1h at 126 ℃, adding a second solvent and a second initiator, preserving heat for 0.5h, adding a third solvent and a third initiator, preserving heat for 2h at 125 ℃, cooling to 100 ℃, adding a fourth solvent, cooling to 85 ℃, dropwise adding isophorone to adjust the viscosity, filtering with a 1-micron filter bag, and discharging.
The first solvent is xylene and ethylene glycol monobutyl ether, and the mass ratio of the xylene to the ethylene glycol monobutyl ether is 1.27:1 and mixing.
And the second solvent and the third solvent are both dimethylbenzene.
The fourth solvent is isophorone.
The reaction monomer is methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl acrylate, and the mass ratio of the methyl methacrylate to the methacrylic acid to the ethyl acrylate to the hydroxyethyl acrylate is 5.04:0.2:4.22:0.76 and mixing.
The first initiator is tert-butyl peroxybenzoate and cumene hydroperoxide with the mass ratio of 1: 4. and (4) mixing.
The second initiator and the third initiator are tert-butyl peroxybenzoate.
The analysis results of HPLC, superconducting NMR spectrometer, GC-MS and PGC-MS of the solid acrylic resin prepared in this example are shown in FIGS. 1 to 4.
In a second aspect of this embodiment, a method for synthesizing a thermosetting acrylic resin is provided for use in fluorocarbon coatings.
Comparative example 1
The first aspect of the present comparative example provides a method for synthesizing a thermosetting acrylic resin, which is implemented in the same manner as in example 1, except that the reactive monomers are methyl methacrylate, methacrylic acid, ethyl acrylate, and hydroxyethyl acrylate in a mass ratio of 5.04:2:4.22:3, mixing.
The second aspect of the present comparative example provides the use of a method for synthesizing a thermosetting acrylic resin in a fluorocarbon coating.
Comparative example 2
The first aspect of the present comparative example provides a method for synthesizing a thermosetting acrylic resin, which is the same as example 1 except that the reactive monomers are ethyl methacrylate, methacrylic acid, ethyl acrylate, and hydroxyethyl acrylate in a mass ratio of 5.04:0.2:4.22:0.76 and mixing.
The second aspect of the present comparative example provides the use of a method for synthesizing a thermosetting acrylic resin in a fluorocarbon coating.
Performance test
Viscosity test standard reference: GB 2794-81
Acid value test standard reference: GB/T2895-2008
Solid content test standard reference: GB/T2793-1995
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosed embodiment into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The method for synthesizing the thermosetting acrylic resin is characterized by comprising the following steps of:
step (1), putting a first solvent into a reaction pot;
step (2), putting a reaction monomer and a first initiator into an overhead tank to obtain a phase I;
step (3), heating the reaction kettle, dropwise adding the phase one into the reaction kettle to obtain a phase two, stopping heating after dropwise adding is finished, and putting the phase two into a dilution kettle;
and (4) heating the dilution pot, preserving heat, adding a second solvent and a second initiator, preserving heat, adding a third solvent and a third initiator, preserving heat, cooling, adding a fourth solvent, filtering and discharging.
2. The method for synthesizing a thermosetting acrylic resin as claimed in claim 1, wherein the step (3) is performed immediately after the first initiator is charged into the head tank for 20-40min in the step (2).
3. The method for synthesizing a thermosetting acrylic resin as claimed in claim 1, wherein the dropping time in the step (3) is 4-8h.
4. The method for synthesizing thermosetting acrylic resin as claimed in claim 1, wherein the temperature in step (3) is raised to 110-130 ℃.
5. The method for synthesizing a thermosetting acrylic resin as claimed in claim 1, wherein the filtration precision in the step (4) is 0.5-5 μm.
6. The method for synthesizing a thermosetting acrylic resin as claimed in claim 1, wherein the first, second, third and fourth solvents comprise at least one of xylene, ethylene glycol monobutyl ether, isophorone, toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, butanol and isopropanol.
7. The method as claimed in claim 1, wherein the reactive monomer comprises at least one of methyl methacrylate, methacrylic acid, ethyl acrylate, hydroxyethyl acrylate, acrylic acid, methyl acrylate, lauryl acrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate, acrylonitrile, styrene, acrylamide, and vinyl acetate.
8. The method for synthesizing a thermosetting acrylic resin as claimed in claim 1, wherein the first initiator, the second initiator, and the third initiator comprise at least one of a peroxy initiator and an azo initiator.
9. The method as claimed in claim 8, wherein the first, second and third initiators comprise at least one of tert-butyl peroxybenzoate, cumene hydroperoxide, dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, azobisisobutyronitrile and azobisisoheptonitrile.
10. Use of a method of synthesizing a thermosetting acrylic resin according to any one of claims 1-9 in a fluorocarbon coating.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185403A (en) * | 1991-07-31 | 1993-02-09 | Morton Coatings, Inc. | Thermosetting acrylic polymers and coating compositions containing said acrylic polymers and fluorocarbon resins |
| US20070185296A1 (en) * | 2006-02-03 | 2007-08-09 | Basf Corporation | Acrylic resin for use in fluorocarbon coating compositions and method of forming the same |
| CN107602756A (en) * | 2017-09-01 | 2018-01-19 | 广东依斯特新材料有限公司 | A kind of PVDF fluorocarbon coatings acrylic resin and its synthetic method |
| CN112094369A (en) * | 2020-08-05 | 2020-12-18 | 佛山市坚洛涂料科技有限公司 | Reactive acrylic resin and preparation method and application thereof |
-
2021
- 2021-09-06 CN CN202111038882.7A patent/CN115304702A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185403A (en) * | 1991-07-31 | 1993-02-09 | Morton Coatings, Inc. | Thermosetting acrylic polymers and coating compositions containing said acrylic polymers and fluorocarbon resins |
| US20070185296A1 (en) * | 2006-02-03 | 2007-08-09 | Basf Corporation | Acrylic resin for use in fluorocarbon coating compositions and method of forming the same |
| CN107602756A (en) * | 2017-09-01 | 2018-01-19 | 广东依斯特新材料有限公司 | A kind of PVDF fluorocarbon coatings acrylic resin and its synthetic method |
| CN112094369A (en) * | 2020-08-05 | 2020-12-18 | 佛山市坚洛涂料科技有限公司 | Reactive acrylic resin and preparation method and application thereof |
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Application publication date: 20221108 |