CN116102983A - Epoxy-containing unsaturated acrylate adhesive and preparation method thereof - Google Patents
Epoxy-containing unsaturated acrylate adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN116102983A CN116102983A CN202211615860.7A CN202211615860A CN116102983A CN 116102983 A CN116102983 A CN 116102983A CN 202211615860 A CN202211615860 A CN 202211615860A CN 116102983 A CN116102983 A CN 116102983A
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- Prior art keywords
- parts
- acrylate
- reaction
- epoxy group
- containing unsaturated
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- 239000000853 adhesive Substances 0.000 title claims abstract description 62
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 62
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004593 Epoxy Substances 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 45
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 150000003254 radicals Chemical class 0.000 claims abstract description 17
- 230000014759 maintenance of location Effects 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 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 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- -1 3, 4-epoxy cyclohexyl Chemical group 0.000 claims description 18
- 229920006222 acrylic ester polymer Polymers 0.000 claims description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 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 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- VWMQMAAMNRYYPM-UHFFFAOYSA-N 2-prop-2-enoyloxyhexanoic acid Chemical compound CCCCC(C(O)=O)OC(=O)C=C VWMQMAAMNRYYPM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JSZCJJRQCFZXCI-UHFFFAOYSA-N 6-prop-2-enoyloxyhexanoic acid Chemical compound OC(=O)CCCCCOC(=O)C=C JSZCJJRQCFZXCI-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses an epoxy group-containing unsaturated acrylate adhesive and a preparation method thereof, wherein the adhesive comprises the following components in parts by mass: 60-80 parts of soft monomer, 1-10 parts of hard monomer, 10-25 parts of first functional monomer, 2-10 parts of second functional monomer, 80-100 parts of solvent, 0.01-0.2 part of free radical initiator, 0.1-2 parts of catalyst and 0.01-0.5 part of polymerization inhibitor, wherein the soft monomer and the hard monomer are acrylate monomers. The epoxy group-containing unsaturated acrylate adhesive is obtained by firstly synthesizing an epoxy group-containing acrylate oligomer and then grafting unsaturated double bonds through ring opening reaction of the epoxy group. The preparation method is simple, the process is easy to control, the cost is low, acrylate monomers are adopted for polymerization, the compatibility is good, the reaction is quick, the viscosity of the adhesive can be effectively reduced, the Tg is low, the flexibility of the adhesive after being cured is effectively improved, and the double bond retention rate is high.
Description
Technical Field
The invention relates to the technical field of adhesive preparation, in particular to an epoxy group-containing unsaturated acrylate adhesive and a preparation method thereof.
Background
The polyacrylate adhesive is mainly prepared by polymerizing acrylate monomers in a certain proportion, has the characteristics of stable chemical structure, easy synthesis, easy adhesion, good durability, good low-temperature performance, low toxicity, wide bonding surface, excellent corrosion resistance and the like, is suitable for bonding various base materials, and is widely applied to the industries and civil fields of airplanes, automobiles, instruments and equipment, buildings, furniture and the like.
The Epoxy Acrylate (EA) is obtained by ring-opening esterification reaction of epoxy resin and (methyl) acrylic acid in the presence of a catalyst, a polymerization inhibitor and an antioxidant, has excellent comprehensive performance, has the advantages of low price, strong adhesive force and the like, and is the photocuring oligomer with the most wide application range and the largest dosage at present. At present, the technology for industrially producing the epoxy acrylate is to add all raw materials at one time, and heat the raw materials to about 110-115 ℃ for addition reaction. The epoxy acrylate prepared by the preparation method has uneven molecular weight distribution, higher viscosity, difficult coating and increased operation difficulty. In order to reduce the viscosity of the epoxy acrylate, a large amount of active monomer is required to be added for dilution during preparation, and the addition of the large amount of active monomer causes the increase of cost on one hand and the reduction of the total performance of the cured adhesive film, such as the reduction of glossiness and the deterioration of mechanical performance, on the other hand, due to the reduction of the content of the EA prepolymer resin.
In addition, the existing epoxy acrylate has the problems of poor flexibility, poor mechanical property, high brittleness, poor compatibility and the like after curing, so that development of the epoxy acrylate capable of effectively reducing the viscosity and improving the flexibility of the adhesive film after curing is needed.
Disclosure of Invention
The invention aims to provide the epoxy group-containing unsaturated acrylate adhesive and the preparation method thereof, and the epoxy group-containing unsaturated acrylate adhesive is prepared by polymerizing acrylate monomers, has good raw material compatibility and quick reaction, can effectively reduce the viscosity of a product by controlling the adding mode and the reaction condition of each component, has high double bond retention rate and low Tg, and effectively improves the flexibility of an adhesive film after curing.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides an epoxy group-containing unsaturated acrylate adhesive, which comprises the following components in parts by mass: 60 to 80 parts of soft monomer, 1 to 10 parts of hard monomer, 10 to 25 parts of first functional monomer, 2 to 10 parts of second functional monomer, 80 to 100 parts of solvent, 0.01 to 0.2 part of free radical initiator, 0.1 to 2 parts of catalyst and 0.01 to 0.5 part of polymerization inhibitor;
the soft monomer and the hard monomer are acrylate monomers;
the first functional monomer is selected from one or more of 3, 4-epoxy cyclohexyl methacrylate, glycidyl methacrylate and 4- (2-epoxy ethylmethoxy) butyl acrylate; the second functional monomer is selected from one or more of acrylic acid, methacrylic acid, beta-acryloxypropionic acid and 6- (acryloxyhexanoic acid).
Further, the solid content of the epoxy group-containing unsaturated acrylate adhesive is not less than 30%, for example, 30% -40%, the viscosity is 3000-5000 mPa.s, and the double bond retention rate is more than 95%.
Further, the soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate, lauryl acrylate and n-propyl acrylate; the hard monomer is selected from one or more of methyl acrylate, ethyl methacrylate and methyl methacrylate.
Further, the mass ratio of the first functional monomer to the second functional monomer is 1:0.1-0.6.
Further, the solvent is selected from one or more of dimethyl carbonate, ethyl acetate, toluene, butyl acetate, methyl acetate, methanol and butanone.
Further, the free radical initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, azodiisovaleronitrile, benzoyl peroxide and tert-butyl hexahydro terephthalate.
Further, the catalyst is selected from one or more of triethylamine, tributylphosphine, tri (4-methylphenyl) phosphine, stannous octoate and dibutyl tin dilaurate.
Further, the polymerization inhibitor is selected from one or more of hydroquinone, methyl hydroquinone, p-hydroxyanisole, tert-butyl hydroquinone and p-benzoquinone.
The second aspect of the invention provides a preparation method of the epoxy group-containing unsaturated acrylate adhesive, which is characterized by comprising the following steps:
(1) Uniformly mixing a soft monomer, a hard monomer, a first functional monomer and a part of free radical initiator to obtain a first mixed solution, dropwise adding the first mixed solution into a solvent under the protection of inert gas to react, carrying out heat preservation reaction after dropwise adding, and finally adding the rest of free radical initiator to continue reaction to obtain an acrylic ester polymer;
(2) Uniformly mixing a polymerization inhibitor, a catalyst and a second functional monomer to obtain a second mixed solution, dropwise adding the second mixed solution into an acrylic ester polymer in the presence of oxygen to react, and continuing to perform heat preservation reaction after the dropwise adding is finished to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Further, in the step (1), the mass ratio of the partial free radical initiator to the residual free radical initiator is 1:1-3.
The invention adopts the distributed addition of the initiator, and controls the reaction process by controlling the addition amount of the initiator, so as to obtain the adhesive with moderate viscosity and low polydispersion. If the mass ratio of part of free radical initiator to the rest of free radical initiator is less than 1:3, the molecular weight of the obtained adhesive is too large, and more initiator residues can be caused, so that the subsequent coating is not facilitated; if the mass ratio is greater than 1:1, the heat release amount in the early stage of the reaction is excessive, the temperature is difficult to control, even the explosion polymerization phenomenon occurs, and the obtained adhesive has high polydispersity and influences the product performance.
Further, in the step (1), a proper free radical initiator is selected according to the reaction temperature, and when the reaction temperature is 60-80 ℃, the initiator is azobisisobutyronitrile or azobisisoheptonitrile; or when the reaction temperature is 70-100 ℃, the initiator is benzoyl peroxide or tert-butyl hexahydro terephthalate peroxide.
Further, in the step (1), the inert gas is nitrogen.
Further, in the step (1), the first mixed solution is dripped into a solvent for reaction under the protection of inert gas, the dripping time is 2-5 h, and the reaction temperature is 70-90 ℃; the reaction time of the heat preservation is 1-2 h, and the reaction continuing time is 3-5 h.
Further, in the step (2), the second mixed solution is dripped into the acrylic ester polymer to react in the presence of oxygen, the dripping time is 1-3 h, and the reaction temperature is 80-100 ℃; the reaction is continued for 3-5 h.
The reaction in the step (1) is carried out under the protection of inert gas to ensure that the raw materials and the equipment do not contain water and oxygen, thereby avoiding the reaction of monomers, initiator and the like in the raw materials with water or oxygen and the like to influence the purity of the unsaturated acrylic ester adhesive containing epoxy groups and further influence the quality of the adhesive; the reaction in the step (2) is preferably carried out in the presence of oxygen (air), and the presence of oxygen has a polymerization inhibition effect and can protect carbon-carbon double bonds in the second functional monomer, thereby improving the double bond retention rate.
In addition, in the steps (1) and (2), firstly, mixing a monomer and an auxiliary agent (a free radical initiator, a polymerization inhibitor, a catalyst and the like) to obtain a mixed solution, and then, dripping the mixed solution into a solvent or an acrylic polymer; the reaction process is an exothermic process, and the mixed liquid which is uniformly mixed is dripped into the system, so that the adding rate of reactants is controlled, and the rapid rising of the temperature of the system caused by the excessively high adding rate of the reactants is avoided, thereby influencing the preparation quality of the adhesive.
According to the invention, in the step (2), the catalyst, the polymerization inhibitor and the second functional monomer are added into the acrylate polymer, wherein the addition of the catalyst can promote the ring-opening reaction of the epoxy group, the grafting rate of the second functional monomer is improved, and the addition of the polymerization inhibitor can further protect the carbon-carbon double bond in the second functional monomer and improve the retention rate of the double bond.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an epoxy group-containing unsaturated acrylate adhesive which is prepared by firstly synthesizing an epoxy group-containing acrylate oligomer and then grafting an unsaturated double bond through a ring opening reaction of an epoxy group. The preparation method provided by the invention is simple to operate and controllable in process, the raw materials for preparing the epoxy-containing unsaturated acrylate adhesive do not contain epoxy resin, acrylate monomers are adopted, the compatibility is good, the reaction is quick, the prepared epoxy-containing unsaturated acrylate adhesive is low in viscosity and easy to coat, and meanwhile, the adhesive is low in Tg, so that the flexibility of the adhesive film is improved. In addition, the adhesive prepared by the preparation method provided by the invention has high double bond retention rate and good processability.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Example 1
The embodiment relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which comprises the following steps:
(1) 60 parts by weight of toluene and 40 parts by weight of ethyl acetate were added to a drying vessel, the temperature was raised to 80℃with stirring, and nitrogen gas was introduced for 1.5 hours until the air was exhausted. Under the constant temperature condition of 80 ℃, 50 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate, 15 parts of glycidyl methacrylate and 0.05 part of azobisisobutyronitrile are uniformly mixed in a nitrogen atmosphere, then the mixture is continuously dropwise added into a reaction kettle for 2 hours, and the temperature is raised to 80 ℃ after the completion of dropwise addition to continue the reaction for 1 hour. 0.1 part of azobisisobutyronitrile was added to the reaction system and reacted for 4 hours to obtain an acrylic polymer.
(2) Heating to 90 ℃, introducing air for 1 hour, uniformly mixing 0.2 part of para-hydroxyanisole, 1 part of tris (4-methylphenyl) phosphine and 8 parts of acrylic acid, continuously dropwise adding the mixture into an acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after the dropwise adding is finished to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Example 2
The embodiment relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which comprises the following steps:
(1) 80 parts of butyl acetate are added into a drying container according to parts by weight, the temperature is raised to 90 ℃ while stirring, and nitrogen is introduced for 1 hour until the air is exhausted. Under the constant temperature condition of 90 ℃, 30 parts of n-butyl acrylate, 40 parts of isooctyl acrylate, 10 parts of ethyl acrylate, 20 parts of 3, 4-epoxy cyclohexyl methacrylate and 0.05 part of benzoyl peroxide are uniformly mixed in a nitrogen atmosphere, then the mixture is continuously dropwise added into a reaction kettle for 2 hours, and the temperature is raised to 90 ℃ after the dropwise addition is finished, and the reaction is continued for 1 hour. 0.15 part of benzoyl peroxide is added into the reaction system to react for 5 hours, and the acrylic ester polymer is obtained.
(2) Heating to 90 ℃, introducing air for 1.5 hours, uniformly mixing 0.15 part of methyl hydroquinone, 0.5 part of triethylamine and 5 parts of methacrylic acid, continuously dripping the mixture into an acrylic ester polymer for 1 hour, and carrying out heat preservation reaction for 5 hours after dripping to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Example 3
The embodiment relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which comprises the following steps:
(1) 90 parts of toluene are added into a drying container according to the weight parts, the temperature is raised to 85 ℃ while stirring, and nitrogen is introduced for 1 hour until the air is exhausted. Under the constant temperature condition of 85 ℃,40 parts of n-butyl acrylate, 35 parts of isooctyl acrylate, 10 parts of ethyl acrylate, 15 parts of 3, 4-epoxy cyclohexyl methacrylate and 0.1 part of azobisisobutyronitrile are uniformly mixed and then continuously added into a reaction kettle in a dropwise manner for 2 hours, and the temperature is raised to 85 ℃ after the dropwise addition is finished and the reaction is continued for 2 hours. 0.1 part of azobisisobutyronitrile was added to the reaction system and reacted for 4 hours to obtain an acrylic polymer.
(2) Heating to 90 ℃, introducing air for 1.5 hours, uniformly mixing 0.1 part of p-benzoquinone, 1.5 parts of stannous octoate and 5 parts of beta-acryloxypropionic acid, continuously dropwise adding the mixture into an acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after the dropwise adding is finished to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Example 4
The embodiment relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which comprises the following steps:
(1) 100 parts by weight of butyl acetate was added to the drying vessel, the temperature was raised to 95℃with stirring, and nitrogen was introduced for 1.5 hours until the air was exhausted. Under the constant temperature condition of 95 ℃, 30 parts of n-butyl acrylate, 50 parts of isooctyl acrylate, 5 parts of methyl acrylate, 15 parts of 4- (2-oxiranylmethoxy) butyl acrylate and 0.05 part of benzoyl peroxide are uniformly mixed in a nitrogen atmosphere, and are continuously added into a reaction kettle in a dropwise manner for 2 hours, and the temperature is raised to 95 ℃ after the dropwise addition is finished, and the reaction is continued for 1 hour. Adding 0.1 part of benzoyl peroxide into a reaction system, and reacting for 4 hours to obtain an acrylic ester polymer;
(2) Heating to 95 ℃, introducing air for 1 hour, uniformly mixing 0.3 part of p-hydroxyanisole, 1 part of tris (4-methylphenyl) phosphine and 8 parts of 6- (acryloyloxy) hexanoic acid, continuously dropwise adding the mixture into an acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after the dropwise adding, thus obtaining the epoxy group-containing unsaturated acrylic ester adhesive.
Comparative example 1
The comparative example relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which specifically comprises the following steps:
(1) 60 parts of toluene, 40 parts of ethyl acetate, 50 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate and 15 parts of glycidyl methacrylate are added into a drying container according to parts by weight, the temperature is raised to 80 ℃ while stirring, and nitrogen is introduced for 1.5 hours until air is exhausted. Under the constant temperature condition of 80 ℃, 0.05 part of azodiisobutyronitrile is added in the nitrogen atmosphere to continue the reaction for 1 hour, and then 0.1 part of azodiisobutyronitrile is added in the reaction system to react for 4 hours, thus obtaining the acrylic ester polymer.
(2) Heating to 90 ℃, introducing air for 1 hour, uniformly mixing 0.2 part of para-hydroxyanisole, 1 part of tris (4-methylphenyl) phosphine and 7 parts of acrylic acid, continuously dropwise adding the mixture into an acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after the dropwise adding to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Comparative example 2
The comparative example relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which specifically comprises the following steps:
(1) 60 parts of toluene and 40 parts of ethyl acetate are added into a drying container according to parts by weight, the temperature is raised to 80 ℃ while stirring, and nitrogen is introduced for 1.5 hours until the air is exhausted. Under the constant temperature condition of 80 ℃, 50 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate, 15 parts of glycidyl methacrylate and 0.15 part of azobisisobutyronitrile are uniformly mixed in a nitrogen atmosphere, then the mixture is continuously dropwise added into a reaction kettle for 2 hours, and the temperature is raised to 80 ℃ after the completion of dropwise addition to continue the reaction for 1 hour. 0.05 part of azobisisobutyronitrile was added to the reaction system, and reacted for 4 hours to obtain an acrylic polymer.
(2) Heating to 90 ℃, introducing air for 1 hour, uniformly mixing 0.2 part of para-hydroxyanisole, 1 part of tris (4-methylphenyl) phosphine and 7 parts of acrylic acid, continuously dropwise adding the mixture into an acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after the dropwise adding to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Comparative example 3
The comparative example relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which specifically comprises the following steps:
(1) 60 parts of toluene and 40 parts of ethyl acetate are added into a drying container according to parts by weight, the temperature is raised to 80 ℃ while stirring, and nitrogen is introduced for 1.5 hours until the air is exhausted. Under the constant temperature condition of 80 ℃, 50 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate, 15 parts of glycidyl methacrylate and 0.05 part of azobisisobutyronitrile are uniformly mixed in a nitrogen atmosphere, then the mixture is continuously dropwise added into a reaction kettle for 2 hours, and the temperature is raised to 80 ℃ after the completion of dropwise addition to continue the reaction for 1 hour. 0.1 part of azobisisobutyronitrile was added to the reaction system and reacted for 4 hours to obtain an acrylic polymer.
(2) Heating to 90 ℃, introducing air for 1 hour, uniformly mixing 1.2 parts of tri (4-methylphenyl) phosphine and 7 parts of acrylic acid, continuously dripping the mixture into an acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after dripping to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Comparative example 4
The comparative example relates to preparation of an epoxy group-containing unsaturated acrylate adhesive, which specifically comprises the following steps:
(1) 60 parts of toluene and 40 parts of ethyl acetate are added into a drying container according to parts by weight, the temperature is raised to 80 ℃ while stirring, and nitrogen is introduced for 1.5 hours until the air is exhausted. Under the constant temperature condition of 80 ℃, 50 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate, 15 parts of glycidyl methacrylate and 0.05 part of azobisisobutyronitrile are uniformly mixed in a nitrogen atmosphere, then the mixture is continuously dropwise added into a reaction kettle for 2 hours, and the temperature is raised to 80 ℃ after the completion of dropwise addition to continue the reaction for 1 hour. 0.1 part of azobisisobutyronitrile was added to the reaction system and reacted for 4 hours to obtain an acrylic polymer.
(2) Heating to 90 ℃, introducing air for 1 hour, uniformly mixing 0.5 part of para-hydroxyanisole and 7 parts of acrylic acid, continuously dripping the mixture into the acrylic ester polymer for 2 hours, and carrying out heat preservation reaction for 4 hours after dripping to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
Performance testing
The performance of the epoxy group-containing unsaturated acrylate adhesives prepared in the above examples and comparative examples was tested as follows:
solid content: testing was performed according to the method in Standard GB/T2793-1995;
viscosity: testing was performed according to the method in standard GB/T21059-2007;
glass transition temperature (Tg): testing was performed according to the method in Standard GB/T13464-1992;
molecular weight: testing was performed according to the method in standard GB/T27843-2011;
acid value: testing was performed according to the method in standard GB/T2895-2008;
double bond retention: double bond retention= (total moles of acrylic acid in polymer)/(total moles of acrylic acid used in synthesis) ×100%, wherein the moles of acrylic acid used in synthesis is regarded as the number of polymerizable double bonds in the polymeric acrylic acid ester. The calculated double bond retention may be regarded as an average value corresponding to the double bond retention of the synthesized high molecular acrylic acid ester.
The test and calculation results are shown in table 1 below:
TABLE 1 Performance data for the adhesives prepared in the different examples and comparative examples
As is clear from the above table, the adhesives prepared in examples 1 to 4 have low viscosity of 3000 to 5000 mPas and are easy to coat; tg values are less than minus 34 ℃, so that the flexibility of the cured adhesive film is improved; the polydispersity of the obtained adhesive is less than 3, so that the preparation method provided by the invention has good process controllability, and the prepared adhesive has narrow molecular weight distribution; in addition, the acid value of the adhesive is less than 1 mgKOH/g, the double bond retention rate is more than 95%, and the processing performance is good.
Compared with examples 1-4, the epoxy group-containing unsaturated acrylate adhesive prepared by adopting a one-step feeding method in comparative example 1 has the advantages of high viscosity, high polydispersity of more than 6, low double bond retention rate, difficult coating and poor processability.
Compared with examples 1-4, in comparative example 2, the mass ratio of the initiator added in the step (1) before and after the initiator added in the first time to the initiator added in the second time is 3:1, and the temperature is difficult to control due to the excessive amount of the initiator added in the first time and the excessive heat release amount in the early stage of the reaction, so that the prepared epoxy group-containing unsaturated acrylate adhesive has low viscosity and high dispersibility.
Compared with examples 1-4, the epoxy group-containing unsaturated acrylate adhesive prepared in the comparative example 3 in the step (2) is not added with a polymerization inhibitor, and has a double bond retention rate of only 20.4%.
Compared with examples 1-4, the epoxy group-containing unsaturated acrylate adhesive prepared in comparative example 4 in the step (2) is not added with a catalyst, and has high acid value and low double bond retention rate.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The epoxy group-containing unsaturated acrylate adhesive is characterized by comprising the following components in parts by weight: 60 to 80 parts of soft monomer, 1 to 10 parts of hard monomer, 10 to 25 parts of first functional monomer, 2 to 10 parts of second functional monomer, 80 to 100 parts of solvent, 0.01 to 0.2 part of free radical initiator, 0.1 to 2 parts of catalyst and 0.01 to 0.5 part of polymerization inhibitor;
the soft monomer and the hard monomer are acrylate monomers;
the first functional monomer is selected from one or more of 3, 4-epoxy cyclohexyl methacrylate, glycidyl methacrylate and 4- (2-epoxy ethylmethoxy) butyl acrylate; the second functional monomer is selected from one or more of acrylic acid, methacrylic acid, beta-acryloxypropionic acid and 6- (acryloxyhexanoic acid).
2. The epoxy group-containing unsaturated acrylate adhesive according to claim 1, wherein the epoxy group-containing unsaturated acrylate adhesive has a solid content of not less than 30%, a viscosity of 3000 to 5000 mPa-s, and a double bond retention of > 95%.
3. The epoxy group-containing unsaturated acrylate adhesive according to claim 1, wherein the soft monomer is one or more selected from butyl acrylate, isooctyl acrylate, lauryl acrylate and n-propyl acrylate; the hard monomer is selected from one or more of methyl acrylate, ethyl methacrylate and methyl methacrylate.
4. The epoxy group-containing unsaturated acrylate adhesive according to claim 1, wherein the mass ratio of the first functional monomer to the second functional monomer is 1:0.1-0.6.
5. The epoxy group-containing unsaturated acrylate adhesive according to claim 1, wherein the solvent is one or more selected from the group consisting of dimethyl carbonate, ethyl acetate, toluene, butyl acetate, methyl acetate, methanol, and butanone;
the free radical initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, azodiisovaleronitrile, benzoyl peroxide and tert-butyl hexahydro terephthalate;
the catalyst is one or more selected from triethylamine, tributylphosphine, tri (4-methylphenyl) phosphine, stannous octoate and dibutyl tin dilaurate;
the polymerization inhibitor is one or more selected from hydroquinone, methyl hydroquinone, p-hydroxyanisole, tert-butyl hydroquinone and p-benzoquinone.
6. A method for preparing the epoxy group-containing unsaturated acrylate adhesive according to any one of claims 1 to 5, comprising the following steps:
(1) Uniformly mixing a soft monomer, a hard monomer, a first functional monomer and a part of free radical initiator to obtain a first mixed solution, dropwise adding the first mixed solution into a solvent under the protection of inert gas to react, carrying out heat preservation reaction after dropwise adding, and then adding the rest of free radical initiator to continue to react to obtain an acrylic ester polymer;
(2) Uniformly mixing a polymerization inhibitor, a catalyst and a second functional monomer to obtain a second mixed solution, dropwise adding the second mixed solution into an acrylic ester polymer in the presence of oxygen to react, and continuing to perform heat preservation reaction after the dropwise adding is finished to obtain the epoxy group-containing unsaturated acrylic ester adhesive.
7. The process according to claim 6, wherein in the step (1), the mass ratio of the partial radical initiator to the remaining radical initiator is 1:1 to 3.
8. The process according to claim 6, wherein in the step (1), the initiator is azobisisobutyronitrile or azobisisoheptonitrile at a reaction temperature of 60 to 80 ℃; or when the reaction temperature is 70-100 ℃, the initiator is benzoyl peroxide or tert-butyl hexahydro terephthalate peroxide.
9. The preparation method according to claim 6, wherein in the step (1), the first mixed solution is dripped into a solvent under the protection of inert gas to react, the dripping time is 2-5 h, and the temperature of the reaction is 70-90 ℃; the reaction time of the heat preservation is 1-2 h, and the reaction continuing time is 3-5 h.
10. The method according to claim 6, wherein in the step (2), the second mixed solution is added dropwise to the acrylic ester polymer in the presence of oxygen for a period of 1 to 3 hours, and the temperature of the reaction is 80 to 100 ℃; the reaction is continued for 3-5 h.
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