CN117801726A - Bi-component acrylic ester adhesive and preparation method and application method thereof - Google Patents
Bi-component acrylic ester adhesive and preparation method and application method thereof Download PDFInfo
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- CN117801726A CN117801726A CN202311833801.1A CN202311833801A CN117801726A CN 117801726 A CN117801726 A CN 117801726A CN 202311833801 A CN202311833801 A CN 202311833801A CN 117801726 A CN117801726 A CN 117801726A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- -1 acrylic ester Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 58
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 45
- 239000003112 inhibitor Substances 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- 239000004814 polyurethane Substances 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 13
- 239000011324 bead Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 84
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- 239000003292 glue Substances 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 18
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims 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 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- 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 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 8
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 6
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 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 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 125000005396 acrylic acid ester group Chemical group 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010000496 acne Diseases 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 description 1
- SMNGQGWPUVVORF-UHFFFAOYSA-N 3,5-ditert-butyl-4-methylphenol Chemical compound CC1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C SMNGQGWPUVVORF-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000013027 odor testing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009849 vacuum degassing 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
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application relates to a bi-component acrylic ester adhesive and a preparation method and a using method thereof. The double-component acrylic ester adhesive comprises a component A and a component B; the component A comprises the following components in parts by weight: 30-50 parts of polyurethane modified acrylate prepolymer, 10-20 parts of rubber prepolymer, 10-20 parts of toughening agent, 0.1-5 parts of first polymerization inhibitor, 0.5-5 parts of reducing agent, 0.1-5 parts of adhesion promoter and 1-5 parts of first tackifier; the component B comprises the following components in parts by weight: 10-30 parts of epoxy modified acrylate prepolymer, 10-30 parts of plasticizer, 10-30 parts of oxidant, 0.1-5 parts of second polymerization inhibitor, 5-15 parts of filler and 1-5 parts of second tackifier, wherein the filler comprises glass beads. The interaction among the components in the bi-component acrylic ester adhesive can effectively reduce the odor and the shrinkage rate of the bi-component acrylic ester adhesive.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a bi-component acrylic ester adhesive and a preparation method and a use method thereof.
Background
The bi-component acrylic ester adhesive has the characteristics of high room temperature curing speed, adjustable curing speed, convenient use, convenient automation and the like; the bonding surface is not required to be strictly treated, the oil surface can be bonded, and the bonding material is wide; the impact resistance, the stripping resistance and the bonding comprehensive performance are excellent; the method is widely applied to industries such as electronic appliances, machinery, buildings, furniture, automobiles, rail transit and the like. However, the conventional two-component acrylate adhesives have the common problems of large odor and high shrinkage.
Therefore, there is a need for improvements over the conventional art.
Disclosure of Invention
Based on the two-component acrylate adhesive, the preparation method and the application method thereof have the advantages of low odor and low shrinkage.
The technical scheme for solving the technical problems is as follows.
The first aspect of the application provides a two-component acrylate adhesive, which comprises an A component and a B component;
the component A comprises the following components in parts by weight: 30-50 parts of polyurethane modified acrylate prepolymer, 10-30 parts of rubber prepolymer, 10-20 parts of toughening agent, 0.1-5 parts of first polymerization inhibitor, 0.5-5 parts of reducing agent, 0.1-5 parts of adhesion promoter and 1-5 parts of first tackifier;
the component B comprises the following components in parts by weight: 10-30 parts of epoxy modified acrylate prepolymer, 10-30 parts of plasticizer, 10-30 parts of oxidant, 0.1-5 parts of second polymerization inhibitor, 5-15 parts of filler and 1-5 parts of second tackifier; the filler comprises glass beads.
In some embodiments, the mass ratio of the polyurethane modified acrylate prepolymer to the rubber prepolymer in the two-component acrylate glue is (1-4): 1.
In some of these embodiments, the polyurethane modified acrylate prepolymer is prepared from a first polyether diol, a diisocyanate, a first acrylate monomer containing hydroxyl groups, and a first catalyst.
In some embodiments, in the two-component acrylate adhesive, the mass ratio of the first polyether glycol, the diisocyanate, the first acrylate monomer and the first catalyst is (30-50)/(15-25)/(30-50)/(0.01-0.1).
In some of these embodiments, the two-part acrylate gel meets at least one of the following characteristics:
(1) The first polyether glycol comprises at least one of PPG1000, PPG2000, PTMG1000 and PTMG 2000;
(2) The diisocyanate comprises at least one of IPDI, TDI and HDI;
(3) The first acrylate monomer comprises at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate;
(4) The first catalyst comprises at least one of dibutyltin dilaurate, an organotitanium, an organobismuth, and a bis-dimethylaminoethyl ether.
In some of these embodiments, the epoxy modified acrylate prepolymer is made from an epoxy resin, a second polyether diol, a second catalyst, a third polymerization inhibitor, acrylic acid, and a second acrylate monomer.
In some embodiments, in the two-component acrylate adhesive, the mass ratio of the epoxy resin to the second polyether glycol to the second catalyst to the third polymerization inhibitor to the acrylic acid to the second acrylate monomer is (30-40): (3-5): (0.1-3): (0.1-5): (30-50): (10-20).
In some of these embodiments, the two-part acrylate gel meets at least one of the following characteristics:
(1) The epoxy resin comprises at least one of bisphenol A epoxy resin and bisphenol F epoxy resin;
(2) The second polyether glycol comprises at least one of PPG1000, PPG2000, PTMG1000 and PTMG 2000;
(3) The second catalyst comprises at least one of triethylamine, N-dimethylaniline and triphenylphosphine;
(4) The third polymerization inhibitor comprises at least one of p-methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl p-cresol respectively and independently;
(5) The second acrylate monomer comprises at least one of lauryl acrylate, lauryl methacrylate, N-dimethylacrylamide and acryloylmorpholine.
In some of these embodiments, the rubber prepolymer is made from a third acrylate monomer and rubber particles in a two-component acrylate gum.
In some of these embodiments, the two-part acrylate gel meets at least one of the following characteristics:
(1) The third acrylate monomer comprises at least one of lauryl acrylate, lauryl methacrylate, N-dimethylacrylamide and acryloylmorpholine;
(2) The rubber particles include at least one of neoprene, nitrile rubber, and polyacrylate rubber.
In some of these embodiments, the two-part acrylate gel meets at least one of the following characteristics:
(1) The toughening agent comprises styrene-butadiene-styrene;
(2) The reducing agent comprises N, N-dimethyl-p-toluidine;
(3) The adhesion promoter comprises PM-2;
(4) The first tackifier and the second tackifier each independently comprise fumed silica;
(5) The plasticizer comprises diethylene glycol dibenzoate;
(6) The oxidizing agent comprises benzoyl peroxide;
(7) The first polymerization inhibitor and the second polymerization inhibitor each independently include at least one of p-methoxyphenol, hydroquinone, 2, 5-dimethylhydroquinone, and 2, 6-di-t-butyl-p-cresol.
The second aspect of the present application provides a method for preparing a two-component acrylate adhesive, comprising the steps of:
according to the mass portion, 30-50 portions of polyurethane modified acrylic ester prepolymer, 10-20 portions of rubber prepolymer, 10-20 portions of toughening agent, 0.1-5 portions of first polymerization inhibitor, 0.5-5 portions of reducing agent, 0.1-5 portions of adhesion promoter and 1-5 portions of first tackifier are mixed to prepare a component A;
according to the mass portion, 10-30 portions of epoxy modified acrylic prepolymer, 10-30 portions of plasticizer, 10-30 portions of oxidant, 0.1-5 portions of second polymerization inhibitor, 5-15 portions of filler and 1-5 portions of second tackifier are mixed to prepare a component B; the filler comprises glass beads.
The third aspect of the application provides a use method of the bi-component acrylic acid ester adhesive or the bi-component acrylic acid ester adhesive prepared by the preparation method, wherein the use mass ratio of the component A to the component B is (8-12): 1.
Compared with the prior art, the bi-component acrylic ester adhesive has the following beneficial effects:
the double-component acrylate adhesive comprises a component A and a component B, wherein the component A comprises a polyurethane modified acrylate prepolymer, a rubber prepolymer, a toughening agent, a first polymerization inhibitor, a reducing agent, an adhesion promoter and a first tackifier in specific parts by weight, and the component B comprises an epoxy modified acrylate prepolymer, a plasticizer, an oxidizing agent, a second polymerization inhibitor, a filler and a second tackifier in specific parts by weight, and controls specific types of the filler; the components interact with each other, so that the odor and the shrinkage rate of the bi-component acrylic acid ester adhesive can be effectively reduced, the bi-component acrylic acid ester adhesive has higher shear strength, meanwhile, the characteristics of fast room temperature curing, adjustable curing speed, convenient use, no need of strictly treating the bonding surface, oil surface bonding, wide bonding material, impact resistance, stripping resistance and excellent bonding comprehensive performance of the bi-component acrylic acid ester adhesive are maintained.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
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 terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The meaning of "a plurality of" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the present invention may be mass units known in the chemical industry field such as μ g, mg, g, kg.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
An embodiment of the application provides a two-component acrylate adhesive, which comprises an A component and a B component;
the component A comprises the following components in parts by weight: 30-50 parts of polyurethane modified acrylate prepolymer, 10-30 parts of rubber prepolymer, 10-20 parts of toughening agent, 0.1-5 parts of first polymerization inhibitor, 0.5-5 parts of reducing agent, 0.1-5 parts of adhesion promoter and 1-5 parts of first tackifier;
the component B comprises the following components in parts by weight: 10-30 parts of epoxy modified acrylate prepolymer, 10-30 parts of plasticizer, 10-30 parts of oxidant, 0.1-5 parts of second polymerization inhibitor, 5-15 parts of filler and 1-5 parts of second tackifier; the filler comprises glass beads.
The double-component acrylate adhesive comprises a component A and a component B, wherein the component A comprises a polyurethane modified acrylate prepolymer, a rubber prepolymer, a toughening agent, a first polymerization inhibitor, a reducing agent, an adhesion promoter and a first tackifier in specific parts by weight, and the component B comprises an epoxy modified acrylate prepolymer, a plasticizer, an oxidizing agent, a second polymerization inhibitor, a filler and a second tackifier in specific parts by weight, and controls specific types of the filler; the components interact with each other, so that the odor and the shrinkage rate of the bi-component acrylic acid ester adhesive can be effectively reduced, the bi-component acrylic acid ester adhesive has higher shear strength, meanwhile, the characteristics of fast room temperature curing, adjustable curing speed, convenient use, no need of strictly treating the bonding surface, oil surface bonding, wide bonding material, impact resistance, stripping resistance and excellent bonding comprehensive performance of the bi-component acrylic acid ester adhesive are maintained.
It will be appreciated that in component a, the polyurethane modified acrylate prepolymer includes, but is not limited to, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts by mass; rubber prepolymers include, but are not limited to, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts; toughening agents include, but are not limited to, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts; the first polymerization inhibitor includes, but is not limited to, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; reducing agents include, but are not limited to, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; adhesion promoters include, but are not limited to, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; the first tackifier includes, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; the epoxy modified acrylate prepolymer in the component B comprises, by mass, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts and 30 parts; plasticizers include, but are not limited to, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts; oxidizing agents include, but are not limited to, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts; the second polymerization inhibitor includes, but is not limited to, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; fillers include, but are not limited to, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 13 parts, 14 parts, 15 parts; the second tackifier includes, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts. The following holds true for the range that any two of these point values may be made up as end values in some examples.
In some examples, the mass ratio of the polyurethane modified acrylate prepolymer to the rubber prepolymer in the two-component acrylate glue is (1-4): 1.
It is understood that the mass ratio of polyurethane modified acrylate prepolymer to rubber prepolymer includes, but is not limited to, 1:1, 2:1, 3:1, 4:1.
The bi-component acrylic ester rubber replaces the acrylic ester monomer which is easy to volatilize and has large smell through the synthetic resin, introduces the rubber system and the glass bead, and solves the problems of large smell and high shrinkage rate of the traditional acrylic ester rubber.
In some examples, the polyurethane modified acrylate prepolymer is prepared from a first polyether diol, a diisocyanate, a first acrylate monomer containing hydroxyl groups, and a first catalyst.
In some examples, the mass ratio of the first polyether glycol, the diisocyanate, the first acrylate monomer and the first catalyst in the two-component acrylate glue is (30-50): (15-25): (30-50): (0.01-0.1).
It is understood that in the mass ratio of the first polyether glycol, the diisocyanate, the first acrylate monomer to the first catalyst, (30-50) includes, but is not limited to, 30, 32, 35, 38, 40, 42, 45, 48, 50; (15-25) including but not limited to 15, 18, 20, 22, 25; (0.01-0.1) including but not limited to 0.01, 0.02, 0.05, 0.08, 0.1. The mass ratio of the first polyether glycol, the diisocyanate, the first acrylate monomer and the first catalyst can be (35-50): (15-20): (30-45): (0.01-0.5), (30-45): (20-25): (40-50): (0.05-0.1), (35-45): (18-22): (35-45): (0.02-0.08) and the like.
In some examples, the first polyether glycol comprises at least one of PPG1000, PPG2000, PTMG1000, PTMG2000 in the two-component acrylate glue.
It is understood that common diisocyanates include, but are not limited to, at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI), and the like.
In some of these examples, the diisocyanate comprises at least one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), and HDI (hexamethylene diisocyanate) in the two-part acrylate adhesive.
In some examples, the first catalyst comprises at least one of dibutyltin dilaurate, an organotitanium, an organobismuth, and a bis-dimethylaminoethyl ether in the two-component acrylate gel.
In some of these examples, the epoxy modified acrylate prepolymer is made from an epoxy resin, a second polyether diol, a second catalyst, a third polymerization inhibitor, acrylic acid, and a second acrylate monomer.
In some examples, the mass ratio of the epoxy resin, the second polyether glycol, the second catalyst, the third polymerization inhibitor, the acrylic acid and the second acrylic ester monomer in the two-component acrylic ester adhesive is (30-40)/(3-5)/(0.1-3)/(0.1-5)/(30-50)/(10-20).
It is understood that in the mass ratio of epoxy resin, second polyether glycol, second catalyst, third polymerization inhibitor, acrylic acid and second acrylate monomer, (30-40) includes, but is not limited to, 30, 32, 35, 38, 40; (3-5) including but not limited to 3, 3.5, 4, 4.5, 5; (0.1-3) including but not limited to 0.1, 0.5, 1, 1.5, 2, 2.5, 3; (0.1-5) including but not limited to 0.1, 0.5, 1, 2, 3, 4, 5; (30-50) including, but not limited to, 30, 32, 35, 38, 40, 42, 45, 48, 50; (10-20) include, but are not limited to, 10, 12, 15, 18, 20. The mass ratio of the epoxy resin, the second polyether glycol, the second catalyst, the third polymerization inhibitor, the acrylic acid and the second acrylic ester monomer can be (35-40): (4-5): (0.5-3): (1-5): (30-40): (10-15), (30-35): (3-4): (0.1-2): (0.1-3): (40-50): (15-20), (32-38): (3.5-4.5): (1-2): (1-3): (35-45): (12-18) and the like.
In some of these examples, the epoxy resin comprises at least one of a bisphenol a epoxy resin and a bisphenol F epoxy resin in the two-part acrylate glue.
In some examples, the second polyether diol comprises at least one of PPG1000, PPG2000, PTMG1000, PTMG2000 in the two-component acrylate glue.
In some examples, the second catalyst comprises at least one of triethylamine, N-dimethylaniline, and triphenylphosphine in the two-component acrylate gum.
In some examples, the second polymerization inhibitor comprises at least one of p-methoxyphenol, hydroquinone, 2, 5-dimethylhydroquinone, and 2, 6-di-t-butyl-p-cresol.
In some examples, the second acrylate monomer in the two-part acrylate gel comprises at least one of lauryl acrylate, lauryl methacrylate, N-dimethylacrylamide, and acryloylmorpholine.
In some of these examples, the two-component acrylate gum, the rubber prepolymer is made from a third acrylate monomer and rubber particles.
In some examples, the mass ratio of the third acrylate monomer to the rubber particles in the two-component acrylate glue is (60-70): (30-40).
It is understood that in the mass ratio of the third acrylate monomer to the rubber particles, (60-70) includes, but is not limited to 60, 62, 65, 68, 70; (30-40) include, but are not limited to, 30, 32, 35, 38, 40. Namely, the mass ratio of the third acrylate monomer to the rubber particles can be (60-65): (35-40), (65-70): (30-35), (62-68): (32-38), and the like.
In some examples, the third acrylate monomer comprises at least one of lauryl acrylate, lauryl methacrylate, N-dimethylacrylamide, and acryloylmorpholine.
In some examples, the two-component acrylate gel comprises at least one of neoprene, nitrile rubber, and polyacrylate rubber.
In some of these examples, the toughening agent comprises styrene-butadiene-styrene in the two-part acrylate glue.
In some of these examples, the reducing agent comprises N, N-dimethyl-p-toluidine in the two-component acrylate glue.
In some of these examples, the adhesion promoter comprises PM-2 in a two-part acrylate glue.
In some of these examples, the first tackifier and the second tackifier each independently comprise fumed silica.
In some of these examples, the plasticizer comprises diethylene glycol dibenzoate in the two-part acrylate glue.
In some of these examples, the oxidizing agent comprises benzoyl peroxide in the two-component acrylate glue.
In some examples, the two-component acrylate glue comprises at least one of p-methoxyphenol, hydroquinone, 2, 5-dimethylhydroquinone, and 2, 6-di-tert-butyl-p-cresol, each of the first and second polymerization inhibitors independently.
An embodiment of the present application provides a preparation method of a two-component acrylate adhesive, including the following steps:
step S10: according to the mass portion, 30-50 portions of polyurethane modified acrylic ester prepolymer, 10-20 portions of rubber prepolymer, 10-20 portions of toughening agent, 0.1-5 portions of first polymerization inhibitor, 0.5-5 portions of reducing agent, 0.1-5 portions of adhesion promoter and 1-5 portions of first tackifier are mixed to prepare the component A.
In some examples, in step S10, after the polyurethane modified acrylate prepolymer, the rubber prepolymer, the toughening agent, the first polymerization inhibitor and the reducing agent are mixed and stirred, the adhesion promoter and the tackifier are added to continue stirring, and then vacuum degassing is performed to obtain the component a.
In some of these examples, in step S10, the preparation of the polyurethane modified acrylate prepolymer includes step S100:
after mixing the first polyether glycol and diisocyanate, adding the first acrylate monomer containing hydroxyl and the catalyst for mixing reaction.
In some examples, in step S100, the temperature of the mixing reaction is 70℃to 90 ℃.
It is understood that the temperature of the mixing reaction includes, but is not limited to, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃.
In some examples, in step S100, before the step of mixing the first polyether diol and the diisocyanate, the step S11 of pre-treating the first polyether diol is further included:
stirring the first polyether glycol at 80-90 ℃ for 0.5-2 hours, vacuumizing and removing water, and introducing nitrogen for protection.
In some examples, in step S100, after mixing the first polyether diol and the diisocyanate, stirring at 70-90 ℃ for 0.5-2 hours, adding the first acrylate monomer containing hydroxyl group and the catalyst, and mixing and reacting for 1-3 hours.
In some examples, in step S100, the stirring rate of each step is 100 r/min-300 r/min.
It is understood that in step S100, the stirring rates of the respective steps are respectively and independently 100 r/min, 120 r/min, 150 r/min, 180 r/min, 200 r/min, 220 r/min, 250 r/min, 280 r/min and 300 r/min.
In some of these examples, in step S10, the preparation of the rubber prepolymer includes step S110:
mixing the acrylic acid monomer and the rubber particles at 50-70 ℃ and stirring to dissolve the rubber particles, thus obtaining the rubber prepolymer.
It is understood that in step S110, the temperature of the agitation includes, but is not limited to, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃.
Step S20: according to the mass portion, 10-30 portions of epoxy modified acrylic prepolymer, 10-30 portions of plasticizer, 10-30 portions of oxidant, 0.1-5 portions of second polymerization inhibitor, 5-15 portions of filler and 1-5 portions of second tackifier are mixed to prepare a component B, wherein the filler comprises glass microspheres.
It can be appreciated that the preparation method of the two-component acrylate glue can be used for preparing the two-component acrylate glue, and the two-component acrylate glue can be prepared by the preparation method of the two-component acrylate glue. It will further be appreciated that the features of the two-component acrylate glue and the method of preparing the two-component acrylate glue may be mutually applicable.
In some examples, in step S20, after mixing and stirring the epoxy modified acrylate prepolymer, the plasticizer, the oxidant and the polymerization inhibitor, adding the filler and the tackifier, continuing stirring, and then performing vacuumizing and defoaming to obtain the component B.
In some of these examples, in step S20, the preparation of the epoxy-modified acrylate prepolymer includes step S200:
carrying out a first reaction on epoxy resin, second polyether glycol and a second catalyst at 100-120 ℃ to obtain a first reaction solution;
mixing a third polymerization inhibitor, acrylic acid and the first reaction solution, and performing a second reaction at 105-125 ℃ to obtain a second reaction solution;
and mixing the second acrylate monomer with the second reaction liquid to prepare the epoxy modified acrylate prepolymer.
It will be appreciated that the second acrylate monomer acts primarily as a diluent.
In some examples, in step S200, the first reaction solution is mixed with the third polymerization inhibitor and acrylic acid when the temperature of the first reaction solution is reduced to 40-60 ℃.
It is understood that the temperature of the first reaction includes, but is not limited to, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃.
In some examples, in step S200, the time of the first reaction is 2 h to 3 h.
It is understood that the time of the first reaction includes, but is not limited to, 2 h, 2.5h, 3 h.
It is understood that the temperature of the second reaction includes, but is not limited to, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃.
In some examples, in step S200, the second reaction time is 3 h to 4 h.
It is understood that the time of the second reaction includes, but is not limited to, 3 h, 3.5h, 4 h.
The bi-component acrylic ester adhesive prepared by the preparation method of the bi-component acrylic ester adhesive has low odor and shrinkage.
The application provides a use method of a bi-component acrylic acid ester adhesive, wherein the use mass ratio of the component A to the component B in the bi-component acrylic acid ester adhesive or the bi-component acrylic acid ester adhesive prepared by the preparation method is (8-12): 1.
It is understood that the mass ratio of the A component to the B component used includes, but is not limited to, 8:1, 9:1, 10:1, 11:1, 12:1.
The present application will be described in further detail with reference to the following specific embodiments, but embodiments of the present application are not limited thereto.
Example 1
(1) 36.5 parts of PTMG1000 was stirred at 90℃and 200 r/min and evacuated to remove water 1 h, and N was introduced 2 And (3) protecting, adding 25 parts of TDI (toluene diisocyanate) after stirring and cooling to 80 ℃, continuously controlling the temperature to 70-90 ℃ and stirring for 1-h, then adding 38 parts of hydroxyethyl methacrylate and 0.5 part of dibutyltin dilaurate, continuously controlling the temperature to 70-90 ℃ and stirring for 2-h, thus obtaining the polyurethane modified acrylate prepolymer for standby.
(2) 65 parts of N, N-dimethylacrylamide and 35 parts of polyacrylate rubber are added into a kettle, and the temperature is controlled to be 60 ℃ and stirred, so that rubber particles are completely dissolved, and a rubber prepolymer is prepared for standby.
(3) 50 parts of the polyurethane modified acrylic prepolymer prepared in the step (1), 24.9 parts of the rubber prepolymer prepared in the step (2), 20 parts of a toughening agent (styrene-butadiene-styrene SBS), 0.1 part of a polymerization inhibitor (2, 6-di-tert-butyl-p-toluene) and 1 part of a reducing agent (N, N-dimethyl-p-toluidine) are stirred for 3 h, 1 part of an adhesion promoter (PM-2) and 3 parts of a tackifier (hydrophobic fumed silica) are added after stirring is finished, stirring is continued for 30 min, and vacuumizing and defoaming are carried out after stirring is finished, so that a component A is prepared; wherein the mass ratio of the polyurethane modified acrylate prepolymer to the rubber prepolymer is about 2:1.
(4) 36 parts of bisphenol A epoxy resin and 4 parts of PPG1000 are heated to 110 ℃ and reacted for 2.5 hours under the action of 1 part of triphenylphosphine; cooling to 50 ℃, adding 0.5 part of p-methoxyphenol, slowly dropwise adding 40 parts of acrylic acid, heating to 115 ℃, reacting for 3.5 hours, and adding 18.5 parts of lauryl methacrylate to prepare the epoxy modified acrylate prepolymer.
(5) And (3) stirring 30 parts of the epoxy modified acrylate prepolymer prepared in the step (4), 26.9 parts of diethylene glycol dibenzoate, 30 parts of benzoyl peroxide and 0.1 part of 2, 6-di-tert-butyl-p-cresol for 3 h, adding 10 parts of filler (glass beads) and 3 parts of fumed silica after stirring, stirring for 20 min, and vacuumizing and defoaming after stirring is finished to prepare the component B.
Example 2
(1) Stirring 32.5 parts of PPG1000 at 90deg.C and 200 r/min, vacuumizing to remove water 1 h, and introducing N 2 And (3) protecting, adding 20 parts of IPDI (IPDI) after stirring is finished and the temperature is reduced to 80 ℃, continuously controlling the temperature to 70-90 ℃ and stirring for 1-h, then adding 47 parts of hydroxyethyl methacrylate and 0.5 part of dibutyltin dilaurate, continuously controlling the temperature to 70-90 ℃ and stirring for 2-h to obtain the polyurethane modified acrylate prepolymer for later use.
(2) 65 parts of N, N-dimethylacrylamide and 35 parts of polyacrylate rubber are added into a kettle, and the temperature is controlled to be 60 ℃ and stirred, so that rubber particles are completely dissolved, and a rubber prepolymer is prepared for standby.
(3) 50 parts of the polyurethane modified acrylic prepolymer prepared in the step (1), 24.9 parts of the rubber prepolymer prepared in the step (2), 20 parts of styrene-butadiene-styrene SBS, 0.1 part of 2, 6-di-tert-butyl p-cresol and 1 part of N, N-dimethyl-p-toluidine are stirred for 3 h, 1 part of PM-2 and 3 parts of hydrophobic fumed silica are added after stirring is finished, stirring is continued for 30 min, and vacuumizing and defoaming are carried out after stirring is finished, so that the component A is prepared.
(4) Heating 40 parts of bisphenol A epoxy resin and 5 parts of PTMG1000 to 110 ℃ to react for 2.5 hours under the action of 1 part of triphenylphosphine; cooling to 50 ℃, adding 0.5 part of p-methoxyphenol, slowly dropwise adding 38 parts of acrylic acid, heating to 115 ℃, reacting for 3.5 hours, and adding 15.5 parts of lauryl methacrylate to prepare the epoxy modified acrylate prepolymer.
(5) And (3) stirring 25.9 parts of the epoxy modified acrylate prepolymer prepared in the step (4), 30 parts of diethylene glycol dibenzoate, 30 parts of benzoyl peroxide and 0.1 part of 2, 6-di-tert-butyl-p-cresol for 3 h, adding 11 parts of glass beads and 3 parts of fumed silica after stirring, stirring for 20 min, and vacuumizing and defoaming after stirring is finished to prepare the component B.
Example 3
(1) 45.5 parts of PPG2000 are reacted at 90℃,200 Stirring at r/min, vacuumizing to remove water 1 h, and introducing N 2 And (3) protecting, adding 25 parts of TDI (toluene diisocyanate) after stirring and cooling to 80 ℃, continuously controlling the temperature to 70-90 ℃ and stirring for 1-h, then adding 39 parts of hydroxyethyl methacrylate and 0.5 part of dibutyltin dilaurate, continuously controlling the temperature to 70-90 ℃ and stirring for 2-h to obtain the polyurethane modified acrylate prepolymer for later use.
(2) 65 parts of N, N-dimethylacrylamide and 35 parts of polyacrylate rubber are added into a kettle, and the temperature is controlled to be 60 ℃ and stirred, so that rubber particles are completely dissolved, and a rubber prepolymer is prepared for standby.
(3) 50 parts of the polyurethane modified acrylic prepolymer prepared in the step (1), 24.9 parts of the rubber prepolymer prepared in the step (2), 20 parts of styrene-butadiene-styrene SBS, 0.1 part of 2, 6-di-tert-butyl p-cresol and 1 part of N, N-dimethyl-p-toluidine are stirred for 3 h, 1 part of PM-2 and 3 parts of hydrophobic fumed silica are added after stirring is finished, stirring is continued for 30 min, and vacuumizing and defoaming are carried out after stirring is finished, so that the component A is prepared.
(4) Heating 40 parts of bisphenol A epoxy resin and 3 parts of PPG1000 to 110 ℃ to react for 2.5 hours under the action of 1 part of triphenylphosphine; cooling to 50 ℃, adding 0.5 part of p-methoxyphenol, slowly dropwise adding 42 parts of acrylic acid, heating to 115 ℃, reacting for 3.5 hours, and adding 13.5 parts of lauryl methacrylate to prepare the epoxy modified acrylate prepolymer.
(5) And (3) stirring 28.9 parts of the epoxy modified acrylate prepolymer prepared in the step (4), 30 parts of diethylene glycol dibenzoate, 30 parts of benzoyl peroxide and 0.1 part of 2, 6-di-tert-butyl-p-cresol for 3 h parts, adding 8 parts of glass beads and 3 parts of fumed silica after stirring, stirring for 20 min, and vacuumizing and defoaming after stirring is finished to prepare the component B.
Example 4
Substantially the same as in example 1, except that step (3) of example 4 was as follows:
(3) Stirring 30 parts of the polyurethane modified acrylate prepolymer prepared in the step (1), 30 parts of the rubber prepolymer prepared in the step (2), 10 parts of a toughening agent (styrene-butadiene-styrene SBS), 5 parts of a polymerization inhibitor (2, 6-di-tert-butyl-p-toluol) and 5 parts of a reducing agent (N, N-dimethyl-p-toluidine) for 3 h, adding 5 parts of an adhesion promoter (PM-2) and 1 part of a tackifier (hydrophobic fumed silica) after stirring is finished, continuously stirring for 30 min, and vacuumizing and defoaming after stirring is finished to prepare a component A; wherein the mass ratio of the polyurethane modified acrylate prepolymer to the rubber prepolymer is about 1:1.
Example 5
Substantially the same as in example 1, except that in step (3), the part of the urethane-modified acrylate prepolymer of example 5 was 40 parts, and the part of the rubber prepolymer was 10 parts, i.e., the mass ratio of the urethane-modified acrylate prepolymer to the rubber prepolymer was 4:1.
Example 6
Substantially the same as in example 1, except that step (5) of example 6 was as follows:
(5) And (3) stirring 3 h parts of the epoxy modified acrylate prepolymer prepared in the step (4), 10 parts of diethylene glycol dibenzoate, 10 parts of benzoyl peroxide and 5 parts of 2, 6-di-tert-butyl-p-cresol, adding 15 parts of filler (glass beads) and 5 parts of fumed silica after stirring, stirring for 20 min, and vacuumizing and defoaming after stirring is finished to prepare the component B.
Comparative example 1
(1) 46.9 parts of methyl methacrylate, 5 parts of methacrylic acid, 5 parts of lauryl methacrylate, 18 parts of tetrahydrofuran methacrylate, 20 parts of styrene-butadiene-styrene SBS, 0.1 part of 2, 6-di-tert-butyl p-cresol and 1 part of N, N-dimethyl-p-toluidine are stirred for 3 h, 1 part of PM-2 and 3 parts of hydrophobic fumed silica are added after stirring is finished, stirring is continued for 30 min, and vacuumizing and defoaming are carried out after stirring is finished, so that the component A is prepared.
(2) 10.9 parts of epoxy resin, 30 parts of diethylene glycol dibenzoate, 50 parts of benzoyl peroxide and 0.1 part of 2, 6-di-tert-butyl-p-cresol are stirred for 3 h, 7 parts of SBS and 2 parts of fumed silica are added after stirring is finished, stirring is carried out for 20 min, and vacuumizing and defoaming are carried out after stirring is finished, so that the component B is prepared.
Comparative example 2
Substantially the same as in example 1, except that comparative example 2 was replaced with equal mass of hydroxyethyl methacrylate by the urethane-modified acrylate prepolymer in step (3) of example 1.
Comparative example 3
Substantially the same as in example 1, except that the rubber prepolymer in step (3) of example 1 was replaced with a polyacrylate rubber of equal mass in comparative example 3.
The final component A prepared in comparative example 3 has pimples, and the pimples cannot be extruded normally by a glue gun, so that the muzzle can be blocked, and the actual use is affected.
Comparative example 4
Substantially the same as in example 1, except that the B component of comparative example 4 is as follows: 30 parts of epoxy resin, 26.9 parts of diethylene glycol dibenzoate, 30 parts of benzoyl peroxide and 0.1 part of 2, 6-di-tert-butyl-p-cresol are stirred for 3 h, 10 parts of SBS and 3 parts of fumed silica are added after stirring is finished, stirring is carried out for 20 min, and vacuumizing and defoaming are carried out after stirring is finished, so that the component B is prepared.
Comparative example 5
Substantially the same as in example 1, except that in step (5), the filler (glass beads) of example 1 was replaced with paraffin wax of equal mass in comparative example 5.
The final component B of comparative example 5 had lumps, which could not be extruded normally with a glue gun, and could block the muzzle, affecting the practical use.
Each of the examples and comparative examples was packaged into a two-component hose (mass ratio of a component to B component of 10:1) and tested for odor, shrinkage, and shear strength, respectively.
(1) The odor test method is as follows:
the odor test is mainly based on the sense of personnel and is classified into 6 grades:
1-no peculiar smell; 2-slightly odorous; 3-tasty but not irritating; 4-having a pungent odor; 5-strong pungent odor; 6-intolerable odor.
(2) The shrinkage test method is as follows:
glue is filled in a 10:1 rubber tube, and the mixed glue is injected into a die by a glue gun to be solidified and demoulded. Accurately measuring the length, width and height of the die to 0.01mm at the temperature of 23+/-2 ℃, and then testing the volume of the solidified colloid by a buoyancy method.
And (3) shrinkage rate calculation: v= (V 1 －V 2 ）／V 1
V-volume shrinkage,%; v (V) 1 -a mold volume; v (V) 2 -colloid volume after curing.
(3) Shear strength is tested with reference to national standard GB/T7124-2008.
The test results are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the two-component acrylate adhesives prepared in the examples have lower odor, lower shrinkage, and higher shear strength than the comparative examples.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. It should be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached in the present application. The scope of the patent application is therefore intended to be indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (10)
1. The bi-component acrylic ester adhesive is characterized by comprising an A component and a B component;
the component A comprises the following components in parts by weight: 30-50 parts of polyurethane modified acrylate prepolymer, 10-30 parts of rubber prepolymer, 10-20 parts of toughening agent, 0.1-5 parts of first polymerization inhibitor, 0.5-5 parts of reducing agent, 0.1-5 parts of adhesion promoter and 1-5 parts of first tackifier;
the component B comprises the following components in parts by weight: 10-30 parts of epoxy modified acrylate prepolymer, 10-30 parts of plasticizer, 10-30 parts of oxidant, 0.1-5 parts of second polymerization inhibitor, 5-15 parts of filler and 1-5 parts of second tackifier; the filler comprises glass beads.
2. The two-component acrylate gel according to claim 1, wherein the mass ratio of the polyurethane modified acrylate prepolymer to the rubber prepolymer is (1-4): 1.
3. The two-component acrylate glue according to any one of claims 1-2, wherein the polyurethane modified acrylate prepolymer is prepared from a first polyether glycol, a diisocyanate, a first acrylate monomer containing hydroxyl groups and a first catalyst.
4. The two-part acrylate gel of claim 3 wherein said two-part acrylate gel meets at least one of the following characteristics:
(1) The mass ratio of the first polyether glycol to the diisocyanate to the first acrylate monomer to the first catalyst is (30-50), 15-25, 30-50 and 0.01-0.1;
(2) The first polyether glycol comprises at least one of PPG1000, PPG2000, PTMG1000 and PTMG 2000;
(3) The diisocyanate comprises at least one of IPDI, TDI and HDI;
(4) The first acrylate monomer comprises at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate;
(5) The first catalyst comprises at least one of dibutyltin dilaurate, an organotitanium, an organobismuth, and a bis-dimethylaminoethyl ether.
5. The two-component acrylate glue according to any one of claims 1-2 and 4, wherein the epoxy modified acrylate prepolymer is prepared from an epoxy resin, a second polyether glycol, a second catalyst, a third polymerization inhibitor, acrylic acid and a second acrylate monomer.
6. The two-part acrylate gel according to claim 5, wherein said two-part acrylate gel meets at least one of the following characteristics:
(1) The mass ratio of the epoxy resin to the second polyether glycol to the second catalyst to the third polymerization inhibitor to the acrylic acid to the second acrylic ester monomer is (30-40), 3-5, 0.1-3, 0.1-5, 30-50 and 10-20;
(2) The epoxy resin comprises at least one of bisphenol A epoxy resin and bisphenol F epoxy resin;
(3) The second polyether glycol comprises at least one of PPG1000, PPG2000, PTMG1000 and PTMG 2000;
(4) The second catalyst comprises at least one of triethylamine, N-dimethylaniline and triphenylphosphine;
(5) The third polymerization inhibitor comprises at least one of p-methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl p-cresol respectively and independently;
(6) The second acrylate monomer comprises at least one of lauryl acrylate, lauryl methacrylate, N-dimethylacrylamide and acryloylmorpholine.
7. The two-component acrylate gel according to any one of claims 1-2, 4 and 6, wherein the rubber prepolymer is prepared from a third acrylate monomer and rubber particles, and wherein the rubber prepolymer satisfies at least one of the following characteristics:
(1) The mass ratio of the third acrylic ester monomer to the rubber particles is (60-70): (30-40)
(2) The third acrylate monomer comprises at least one of lauryl acrylate, lauryl methacrylate, N-dimethylacrylamide and acryloylmorpholine;
(3) The rubber particles include at least one of neoprene, nitrile rubber, and polyacrylate rubber.
8. The two-component acrylate glue of any one of claims 1-2, 4 and 6, wherein the two-component acrylate glue meets at least one of the following characteristics:
(1) The toughening agent comprises styrene-butadiene-styrene;
(2) The reducing agent comprises N, N-dimethyl-p-toluidine;
(3) The adhesion promoter comprises PM-2;
(4) The first tackifier and the second tackifier each independently comprise fumed silica;
(5) The plasticizer comprises diethylene glycol dibenzoate;
(6) The oxidizing agent comprises benzoyl peroxide;
(7) The first polymerization inhibitor and the second polymerization inhibitor each independently include at least one of p-methoxyphenol, hydroquinone, 2, 5-dimethylhydroquinone, and 2, 6-di-t-butyl-p-cresol.
9. The preparation method of the bi-component acrylic ester adhesive is characterized by comprising the following steps of:
according to the mass portion, 30-50 portions of polyurethane modified acrylic ester prepolymer, 10-20 portions of rubber prepolymer, 10-20 portions of toughening agent, 0.1-5 portions of first polymerization inhibitor, 0.5-5 portions of reducing agent, 0.1-5 portions of adhesion promoter and 1-5 portions of first tackifier are mixed to prepare a component A;
according to the mass portion, 10-30 portions of epoxy modified acrylic prepolymer, 10-30 portions of plasticizer, 10-30 portions of oxidant, 0.1-5 portions of second polymerization inhibitor, 5-15 portions of filler and 1-5 portions of second tackifier are mixed to prepare a component B; the filler comprises glass beads.
10. The use method of the two-component acrylate adhesive according to any one of claims 1 to 8 or the two-component acrylate adhesive prepared by the preparation method according to claim 9, wherein the use mass ratio of the component A to the component B is (8 to 12): 1.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792576A (en) * | 2010-03-18 | 2010-08-04 | 上海新天和树脂有限公司 | Epoxy acrylate prepolymer resin, preparation method thereof and application thereof in bicomponent structural adhesive |
| CN106978130A (en) * | 2017-04-07 | 2017-07-25 | 广州旭川合成材料有限公司 | A kind of tag identifier UV pressure sensitive adhesives |
| CN109810665A (en) * | 2018-12-07 | 2019-05-28 | 中昊北方涂料工业研究设计院有限公司 | A kind of one-component acrylic acid anaerobic adhesive and preparation method thereof |
| US20200140727A1 (en) * | 2017-08-15 | 2020-05-07 | Ddp Specialty Electronics Materials Us, Inc. | Two-component room temperature curable toughened epoxy adhesives |
| CN111117497A (en) * | 2019-12-19 | 2020-05-08 | 北京高盟新材料股份有限公司 | Double-component acrylate structural adhesive and preparation method thereof |
| CN114561153A (en) * | 2022-03-01 | 2022-05-31 | 浙江商林科技股份有限公司 | Low-odor high-strength acrylic acid structure adhesive |
| CN115536784A (en) * | 2022-09-16 | 2022-12-30 | 华东理工大学华昌聚合物有限公司 | Low-temperature-resistant hybrid vinyl ester resin and preparation method thereof |
| CN116254080A (en) * | 2023-02-22 | 2023-06-13 | 固诺（天津）实业有限公司 | Double-component adhesive and preparation method and application thereof |
-
2023
- 2023-12-28 CN CN202311833801.1A patent/CN117801726A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792576A (en) * | 2010-03-18 | 2010-08-04 | 上海新天和树脂有限公司 | Epoxy acrylate prepolymer resin, preparation method thereof and application thereof in bicomponent structural adhesive |
| CN106978130A (en) * | 2017-04-07 | 2017-07-25 | 广州旭川合成材料有限公司 | A kind of tag identifier UV pressure sensitive adhesives |
| US20200140727A1 (en) * | 2017-08-15 | 2020-05-07 | Ddp Specialty Electronics Materials Us, Inc. | Two-component room temperature curable toughened epoxy adhesives |
| CN109810665A (en) * | 2018-12-07 | 2019-05-28 | 中昊北方涂料工业研究设计院有限公司 | A kind of one-component acrylic acid anaerobic adhesive and preparation method thereof |
| CN111117497A (en) * | 2019-12-19 | 2020-05-08 | 北京高盟新材料股份有限公司 | Double-component acrylate structural adhesive and preparation method thereof |
| CN114561153A (en) * | 2022-03-01 | 2022-05-31 | 浙江商林科技股份有限公司 | Low-odor high-strength acrylic acid structure adhesive |
| CN115536784A (en) * | 2022-09-16 | 2022-12-30 | 华东理工大学华昌聚合物有限公司 | Low-temperature-resistant hybrid vinyl ester resin and preparation method thereof |
| CN116254080A (en) * | 2023-02-22 | 2023-06-13 | 固诺（天津）实业有限公司 | Double-component adhesive and preparation method and application thereof |
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