CN117186798A - High-toughness high-strength low-odor acrylate adhesive and preparation process thereof - Google Patents
High-toughness high-strength low-odor acrylate adhesive and preparation process thereof Download PDFInfo
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- CN117186798A CN117186798A CN202311176124.0A CN202311176124A CN117186798A CN 117186798 A CN117186798 A CN 117186798A CN 202311176124 A CN202311176124 A CN 202311176124A CN 117186798 A CN117186798 A CN 117186798A
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 239000000853 adhesive Substances 0.000 title claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 32
- 239000000806 elastomer Substances 0.000 claims abstract description 31
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 25
- -1 acrylic ester Chemical class 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 21
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 239000012188 paraffin wax Substances 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000002978 peroxides Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 229920005862 polyol Polymers 0.000 claims description 21
- 150000003077 polyols Chemical class 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 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
- 238000004090 dissolution Methods 0.000 claims description 10
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 9
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 8
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 7
- 229950000688 phenothiazine Drugs 0.000 claims description 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 6
- 102100026735 Coagulation factor VIII Human genes 0.000 claims description 6
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 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
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 150000004053 quinones Chemical class 0.000 claims description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 5
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002681 hypalon Polymers 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 abstract description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Abstract
The invention relates to the technical field of adhesives, and provides a high-toughness high-strength low-odor acrylate adhesive and a preparation process thereof, wherein the low-odor acrylate adhesive comprises the following main component and curing agent component in parts by mass: 1, the main agent component consists of the following raw materials: vinyl acrylate monomer, elastomer, fully refined paraffin wax, CTBN modified epoxy resin, polyurethane resin at least containing 1 vinyl end, reactive liquid nitrile rubber, stabilizer and peroxide initiator; the curing agent component consists of the following raw materials: vinyl acrylate monomer, elastomer, fully refined paraffin wax, CTBN modified epoxy resin, polyurethane resin at least containing 1 vinyl end, reactive liquid nitrile rubber, stabilizer, accelerator, transition metal organic salt and auxiliary accelerator. The invention solves the problems of large smell, fragility and poor elongation of the existing double-component structure adhesive acrylic ester adhesive.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-toughness high-strength low-odor acrylate adhesive and a preparation process thereof.
Background
The two-component structure bonding acrylic acid ester adhesive has the characteristics of rapid solidification at room temperature, high strength, good toughness, oil surface bonding, strong adaptability, simple and convenient operation and the like, and is widely applied to structural bonding, emergency repair, nameplate bonding and the like in the industries of automobiles, machinery, electronics, buildings, furniture, instruments, railway vehicles, civil engineering, industrial arts and the like.
The acrylate structural adhesive commonly used in the market at present takes low-cost methyl methacrylate, methacrylic acid and other rigid monomers as raw materials, so that the product has large smell, is relatively fragile and has low elongation at break, and therefore, the adhesive is easy to open and fall off under the condition of high mechanical vibration, and normal structural bonding cannot be achieved. Therefore, development of a high-toughness high-strength low-odor acrylate adhesive is needed.
Disclosure of Invention
Therefore, aiming at the problems, the invention provides the high-toughness high-strength low-odor acrylate adhesive and the preparation process thereof, and the high-toughness high-strength low-odor acrylate adhesive has the advantages of low odor, high toughness and strength and high elongation at break.
In order to solve the technical problem, the invention adopts the following scheme: a high-toughness high-strength low-odor acrylate adhesive comprises a main component and a curing agent component in parts by mass of 1:1 is prepared by mixing the components according to a proportion,
the main agent comprises the following raw materials in percentage by mass:
(A) 20 to 60 percent of vinyl acrylic ester monomer;
(B) 5-35% wt. elastomer;
(C) 0.1 to 2 percent of Wt total refined paraffin;
(D) 1-10% WtCTBN modified epoxy resin;
(E) 5 to 10% wt. of a polyurethane resin containing at least 1 vinyl end-capping;
(F) 1-10% wt. reactive liquid nitrile rubber;
(G) 0.01 to 5 percent of Wt stabilizer;
(H) 1 to 8 percent of Wt peroxide initiator;
the curing agent comprises the following raw materials in percentage by mass:
(A) 20 to 60 percent of Wt vinyl Shan Guan acrylic ester monomer;
(B) 5-35% wt. elastomer;
(C) 0.1 to 2 percent of Wt total refined paraffin;
(D) 1-10% WtCTBN modified epoxy resin;
(E) 5 to 10% wt. of a polyurethane resin containing at least 1 vinyl end-capping;
(F) 1-10% wt. reactive liquid nitrile rubber;
(G) 0.01 to 5 percent of Wt stabilizer;
(H) 1 to 10 percent of Wt accelerant;
(I) 0.01 to 2 percent of Wt transition metal organic salt;
(J) 1 to 5 percent of Wt auxiliary accelerator;
the vinyl acrylic ester monomer is one or a mixture of more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate, 2-phenoxyethyl methacrylate and tetrahydrofuran methacrylate; the elastomer is MBS rubber elastomer or the elastomer is mixture of MBS rubber elastomer and one or more of nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene and SBS rubber elastomer; the CTBN modified epoxy resin is o-cresol formaldehyde epoxy resin modified by CTBN; the polyurethane resin containing at least one vinyl end-capping is a polyurethane resin obtained by polymerizing a polyether polyol with a molecular weight of 3000 with isophorone diisocyanate and end-capping with a methacrylate monomer, and the peroxide initiator is any one of cumene hydroperoxide, tert-butyl hydroperoxide or a mixture thereof.
Further, the fully refined paraffin WAX is one or a mixture of WAX-120, WAX-145 and WAX-156.
Further, the reactive liquid nitrile rubber is one of 1300X33LC, 1300X43LC or a mixture thereof.
Further, the accelerator is an amine.
Further, the transition metal organic salt is any one or a mixture of a plurality of cobalt acetylacetonate, copper acetylacetonate, zinc acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate and titanium acetylacetonate.
Further, the auxiliary accelerator is one of a phosphate monomer, an acrylated polyester adhesion accelerator or a mixture thereof.
Further, the stabilizer of the main component is one or a mixture of more of phenolic compounds, quinone compounds, oxalic acid, sodium salts and phenothiazine.
Further, the stabilizer of the curing agent component is one of phenolic compounds and quinone compounds or a mixture thereof.
The preparation method of the high-toughness high-strength low-odor acrylate adhesive comprises the following steps of:
(1) Modification of CTBN epoxy resin:
1. putting the o-cresol formaldehyde epoxy resin and liquid CTBN into a reaction bottle;
2. heating to 70-90deg.C, stirring for 30-60 min;
3. pouring triphenylphosphine into a reaction bottle;
4. heating to 110-125deg.C, stirring for 120-150 min;
5. the color was observed during stirring, changing from dark brown to pale yellow, stirring was stopped and cooled.
(2) Modification of polyether polyol:
1. putting polyether polyol with molecular weight of 3000 into a reaction bottle, heating to 115-120 ℃, vacuum dehydrating for 2 hours, and cooling for standby;
2. putting IPDI into a reaction bottle, controlling the temperature to be 70-80 ℃, and stirring for 30 minutes;
3. putting dibutyl tin dilaurate into a reaction bottle, controlling the temperature to 75-80 ℃, and stirring for 90 minutes;
4. adding HEMA and LMA into a reaction bottle, controlling the temperature to 70-80 ℃, and stirring for 90 minutes;
5. putting the HQ into a reaction bottle, controlling the temperature to be 75-80 ℃, stirring for 90 minutes, stopping stirring and cooling;
(3) Main agent components: adding vinyl acrylic ester monomer and refined paraffin into a reaction kettle, heating to 70-74 ℃, adding elastomer and CTBN modified epoxy resin, stirring until complete dissolution, stopping heating, adding polyurethane resin at least containing 1 vinyl end cap and reactive liquid nitrile rubber, stirring until complete dissolution, adding stabilizer, stirring uniformly, cooling to below 30 ℃, adding peroxide initiator, stirring uniformly, and obtaining a main component;
(4) And (3) a curing agent component: adding vinyl acrylic ester monomer and refined paraffin into a reaction kettle, heating to 70-74 ℃, adding elastomer and CTBN modified epoxy resin, stirring until complete dissolution, stopping heating, adding polyurethane resin at least containing 1 vinyl end cap and reactive liquid nitrile rubber, stirring until complete dissolution, adding stabilizer, stirring uniformly, cooling to below 40 ℃, adding accelerator, transition metal salt and auxiliary accelerator, stirring uniformly, and obtaining curing agent component;
(5) The main component prepared in the step (3) and the curing agent prepared in the step (4) are mixed according to the mass portion of 1:1, mixing uniformly to obtain the low-odor acrylate adhesive with high toughness and high strength.
By adopting the technical scheme, the invention has the beneficial effects that: compared with most of acrylate adhesives in the current market, the acrylate adhesive has lower odor, the isopropyl benzene hydroperoxide or tert-butyl hydroperoxide firstly generates free radicals under the action of an accelerator, vinyl acrylate monomers, an elastomer, CTBN modified epoxy resin and at least 1 vinyl terminated polyurethane resin are contained, the reaction of reactive liquid nitrile rubber and the free radicals generated by the isopropyl benzene hydroperoxide or tert-butyl hydroperoxide and the accelerator is used for improving the chemical bond and mechanical binding force between the acrylate adhesive and a substrate, so that the adhesive strength of the acrylate adhesive to a metal material is improved, the acrylate adhesive can generate very good adhesive performance and adhesive strength with the metal material, the methyl methacrylate is replaced by methacrylic acid higher ester, the material odor is low, in addition, the thixotropic property of a product is improved by introducing the MBS through the elastomer, and the elongation at break of the product is improved by the polymerization reaction of CTBN modified epoxy resin, polyether polyol (molecular weight 3000) and isophorone diisocyanate and the polyurethane resin terminated by the methacrylate monomers.
Detailed Description
The invention will now be further described with reference to specific embodiments.
Examples
The preferable high-toughness high-strength low-odor acrylate adhesive comprises the following main component and curing agent component in parts by weight: 1, proportioning:
modification of CTBN epoxy resin:
1. putting 90% of o-cresol formaldehyde epoxy resin and 10% of liquid CTBN into a reaction bottle;
2. heating to 70-90deg.C, stirring for 30-60 min;
3. charging 0.2% triphenylphosphine into a reaction flask;
4. heating to 110-125deg.C, stirring for 120-150 min;
5. the color was observed during stirring, changing from dark brown to pale yellow, stirring was stopped and cooled.
Modification of polyether polyol:
1. putting polyether polyol (molecular weight 3000) into a reaction bottle, heating to 115-120 ℃, vacuum dehydrating for 2 hours, and cooling for standby;
2. putting IPDI into a reaction bottle, controlling the temperature to be 70-80 ℃, and stirring for 30 minutes;
3. putting dibutyl tin dilaurate into a reaction bottle, controlling the temperature to 75-80 ℃, and stirring for 90 minutes;
4. adding HEMA and LMA into a reaction bottle, controlling the temperature to 70-80 ℃, and stirring for 90 minutes;
5. putting HQ into a reaction bottle, controlling the temperature to be 75-80 ℃, stirring for 90 minutes, stopping stirring and cooling.
Main agent components:
37.80% wt. of 2-phenoxyethyl methacrylate
Hydroxypropyl methacrylate 22.00% wt
Nitrile rubber 9.00 wt%
MBS 9.00%Wt
WAX-156 1.00%Wt
CTBN modified epoxy resin 5.00 wt%
8.00% wt. polyether polyol polyurethane dimethacrylate
1300X33LC 5.00%Wt
BHT 0.10%Wt
Hydroquinone 0.10 wt%
Cumene hydroperoxide 3.00% wt
Curing agent component:
2-phenoxyethyl methacrylate 32.10% wt
Hydroxypropyl methacrylate 22.50% wt
Nitrile rubber 9.50 wt%
MBS 9.50%Wt
WAX-156 1.00%Wt
CTBN modified epoxy resin 5.00 wt%
8.00% wt. polyether polyol polyurethane dimethacrylate
1300X33LC 5.00%Wt
MEHQ 0.10%Wt
Phenothiazine 0.10% wt
N, N-dimethyl-p-toluidine 2.00% wt
0.20% wt. transition metal salt
P-2M 5.00%Wt。
The preparation method of the high-toughness high-strength low-odor acrylate adhesive comprises the following steps:
(1) Modification of CTBN epoxy resin:
1. putting the o-cresol formaldehyde epoxy resin and liquid CTBN into a reaction bottle;
2. heating to 70-90deg.C, stirring for 30-60 min;
3. putting the% triphenylphosphine into a reaction bottle;
4. heating to 110-125deg.C, stirring for 120-150 min;
5. the color was observed during stirring, changing from dark brown to pale yellow, stirring was stopped and cooled.
(2) Modification of polyether polyol:
1. putting polyether polyol (molecular weight 3000) into a reaction bottle, heating to 115-120 ℃, vacuum dehydrating for 2 hours, and cooling for standby;
2. putting IPDI into a reaction bottle, controlling the temperature to be 70-80 ℃, and stirring for 30 minutes;
3. putting dibutyl tin dilaurate into a reaction bottle, controlling the temperature to 75-80 ℃, and stirring for 90 minutes;
4. adding HEMA and LMA into a reaction bottle, controlling the temperature to 70-80 ℃, and stirring for 90 minutes;
5. putting HQ into a reaction bottle, controlling the temperature to be 75-80 ℃, stirring for 90 minutes, stopping stirring and cooling.
(3) Main agent components: adding vinyl acrylic ester monomer and refined paraffin into a reaction kettle, heating to 70-74 ℃, adding elastomer and CTBN modified epoxy resin, stirring until the mixture is completely dissolved, stopping heating, adding polyurethane resin at least containing 1 vinyl end cap and plasticizer, stirring until the mixture is completely dissolved, adding stabilizer, stirring uniformly, cooling to below 30 ℃, adding peroxide initiator, and stirring uniformly to obtain a main agent component;
(4) And (3) a curing agent component: adding vinyl acrylic ester monomer and refined paraffin into a reaction kettle, heating to 70-74 ℃, adding elastomer and CTBN modified epoxy resin, stirring until complete dissolution, stopping heating, adding polyurethane resin at least containing 1 vinyl end cap and plasticizer, stirring until complete dissolution, adding stabilizer, stirring uniformly, cooling to below 40 ℃, adding accelerator, transition metal salt and auxiliary accelerator, and stirring uniformly to obtain curing agent component;
(5) The main component prepared in the step (3) and the curing agent prepared in the step (4) are mixed according to the mass portion of 1:1, mixing uniformly to obtain the low-odor acrylate adhesive with high toughness and high strength.
Performance test:
tensile shear strength: according to GB/T7124-2008.
Elongation at break: according to GB/T1040.1-2018.
Examples
The preferable high-toughness high-strength low-odor acrylate adhesive comprises the following main component and curing agent component in parts by weight: 1, proportioning:
modification of CTBN epoxy resin:
1. putting 85% of o-cresol formaldehyde epoxy resin and 15% of liquid CTBN into a reaction bottle;
2. heating to 70-90deg.C, stirring for 30-60 min;
3. pouring 0.3% triphenylphosphine into a reaction flask;
4. heating to 110-125deg.C, stirring for 120-150 min;
5. the color was observed during stirring, changing from dark brown to pale yellow, stirring was stopped and cooled.
Modification of polyether polyol:
1. putting polyether polyol (molecular weight 3000) into a reaction bottle, heating to 115-120 ℃, vacuum dehydrating for 2 hours, and cooling for standby;
2. putting IPDI into a reaction bottle, controlling the temperature to be 70-80 ℃, and stirring for 30 minutes;
3. putting dibutyl tin dilaurate into a reaction bottle, controlling the temperature to 75-80 ℃, and stirring for 90 minutes;
4. adding HEMA and LMA into a reaction bottle, controlling the temperature to 70-80 ℃, and stirring for 90 minutes;
5. putting HQ into a reaction bottle, controlling the temperature to be 75-80 ℃, stirring for 90 minutes, stopping stirring and cooling.
Main agent components:
32.80% wt. of 2-phenoxyethyl methacrylate
Tetrahydrofuran methacrylate 25.00% wt
Nitrile rubber 10.00 wt%
MBS 10.00%Wt
WAX-156 0.50%Wt
WAX-145 0.50%Wt
CTBN modified epoxy resin 8.00 wt%
Polyether polyol polyurethane dimethacrylate 5.00% wt
1300X33LC 5.00%Wt
BHT 0.10%Wt
Hydroquinone 0.10 wt%
Cumene hydroperoxide 3.00% wt
Curing agent component:
31.10% wt. of 2-phenoxyethyl methacrylate
Hydroxypropyl methacrylate 22.50% wt
Nitrile rubber 10.50 wt%
MBS 10.50%Wt
WAX-156 0.50%Wt
WAX-145 0.50%Wt
CTBN modified epoxy resin 8.00 wt%
Polyether polyol polyurethane dimethacrylate 5.00% wt
1300X33LC 5.00%Wt
MEHQ 0.10%Wt
Phenothiazine 0.10% wt
N, N-dimethylaniline 2.00% wt
0.20% wt. transition metal salt
P-2M 4.00%Wt。
The preparation method of the high-toughness high-strength low-odor acrylate adhesive is the same as that of experiment 1.
Examples
The preferable high-toughness high-strength low-odor acrylate adhesive comprises the following main component and curing agent component in parts by weight: 1, proportioning:
modification of CTBN epoxy resin:
1. putting 87% of o-cresol formaldehyde epoxy resin and 13% of liquid CTBN into a reaction bottle;
2. heating to 70-90deg.C, stirring for 30-60 min;
3. charging 0.4% triphenylphosphine into a reaction flask;
4. heating to 110-125deg.C, stirring for 120-150 min;
5. the color was observed during stirring, changing from dark brown to pale yellow, stirring was stopped and cooled.
Modification of polyether polyol:
1. putting polyether polyol (molecular weight 3000) into a reaction bottle, heating to 115-120 ℃, vacuum dehydrating for 2 hours, and cooling for standby;
2. putting IPDI into a reaction bottle, controlling the temperature to be 70-80 ℃, and stirring for 30 minutes;
3. putting dibutyl tin dilaurate into a reaction bottle, controlling the temperature to 75-80 ℃, and stirring for 90 minutes;
4. adding HEMA and LMA into a reaction bottle, controlling the temperature to 70-80 ℃, and stirring for 90 minutes;
5. putting HQ into a reaction bottle, controlling the temperature to be 75-80 ℃, stirring for 90 minutes, stopping stirring and cooling.
Main agent components:
34.80% wt. of 2-phenoxyethyl methacrylate
Lauryl methacrylate 22.00% wt
Nitrile rubber 9.00 wt%
SBS 9.00%Wt
WAX-156 1.00%Wt
CTBN modified epoxy resin 8.00 wt%
Polyether polyol polyurethane dimethacrylate 5.00% wt
1300X43LC 8.00%Wt
BHT 0.10%Wt
Hydroquinone 0.10 wt%
Cumene hydroperoxide 3.00% wt
Curing agent component:
2-phenoxyethyl methacrylate 29.10% wt
Lauryl methacrylate 22.50% wt
Nitrile rubber 9.50 wt%
SBS 9.50%Wt
WAX-156 1.00%Wt
CTBN modified epoxy resin 8.00 wt%
Polyether polyol polyurethane dimethacrylate 5.00% wt
1300X43LC 8.00%Wt
MEHQ 0.10%Wt
Phenothiazine 0.10% wt
N, N-dimethylaniline 2.00% wt
0.20% wt. transition metal salt
P-2M 5.00%Wt。
The preparation method of the high-toughness high-strength low-odor acrylate adhesive is the same as that of experiment 1.
Comparative example 1:
main agent components:
methyl methacrylate 66.80% wt
14.00% wt. neoprene
ABS 14.00%Wt
WAX-156 0.50%Wt
WAX-145 0.50%Wt
BHT 0.10%Wt
Hydroquinone 0.10 wt%
Cumene hydroperoxide 4.00% wt
Curing agent component:
methyl methacrylate 66.10% wt
13.50% wt. neoprene
ABS 13.50%Wt
WAX-156 0.50%Wt
WAX-145 0.50%Wt
MEHQ 0.10%Wt
Phenothiazine 0.10% wt
N, N-dimethyl-p-toluidine 0.20% wt
Transition metal salt 0.50% wt
SR9051 5.00%Wt。
Example 1-example 3, comparative example 1 the low odor high performance two component acrylate glue performance test of the bonded metallic materials prepared.
The main agent component of the invention comprises the following raw materials in percentage by weight: (A) 20-60% wt of vinyl acrylic ester monomer; (B) 5-35% wt. elastomer; (C) 0.1-2% Wt of fully refined paraffin; (D) 1-10% WtCTBN modified epoxy resin; (E) 5 to 10% wt. of a polyurethane resin containing at least 1 vinyl end-capping; (F) 1-10% wt. reactive liquid nitrile rubber; (G) 0.01-5% wt stabilizer; (H) 1-8% wt peroxide initiator; the curing agent comprises the following raw materials in percentage by mass: (A) 20-60% wt of vinyl Shan Guan acrylate monomer; (B) 5-35% wt. elastomer; (C) 0.1-2% Wt of fully refined paraffin; (D) 1-10% WtCTBN modified epoxy resin; (E) 5 to 10% wt. of a polyurethane resin containing at least 1 vinyl end-capping; (F) 1-10% wt. reactive liquid nitrile rubber; (G) 0.01-5% wt stabilizer; (H) 1-10% wt promoter; (I) 0.01-2% wt. transition metal organic salt; (J) 1-5% wt. of auxiliary accelerator.
Wherein the vinyl Shan Guan acrylate monomer in the main agent component and the curing agent component can be any one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate, 2-phenoxyethyl methacrylate and tetrahydrofuran methacrylate; the elastomer can be MBS rubber elastomer or elastomer and can be any one or more of mixture of MBS rubber elastomer, nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene and SBS rubber elastomer; the fully refined paraffin can also be one or a mixture of WAX-120, WAX-145 and WAX-156; the reactive liquid nitrile rubber may also be one of 1300X33LC, 1300X43LC or mixtures thereof; the peroxide initiator may also be t-butyl hydroperoxide; the accelerator may also be an amine; the transition metal organic salt can also be any one or more of cobalt acetylacetonate, copper acetylacetonate, zinc acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate and titanium acetylacetonate; the auxiliary accelerator can also be one or a mixture of phosphate ester monomers and acrylic acid ester polyester adhesion promoters; the stabilizer of the main component can be any one or more of phenolic compounds, quinone compounds, oxalic acid, sodium salts and phenothiazine; the stabilizer of the curing agent component can also be one of phenolic compounds, quinone compounds or a mixture thereof.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A high-toughness high-strength low-odor acrylate adhesive is characterized in that: the main agent component and the curing agent component are prepared from the following components in parts by mass: 1 is prepared by mixing the components according to a proportion,
the main agent comprises the following raw materials in percentage by mass:
(A) 20 to 60 percent of vinyl acrylic ester monomer;
(B) 5-35% wt. elastomer;
(C) 0.1 to 2 percent of Wt total refined paraffin;
(D) 1-10% WtCTBN modified epoxy resin;
(E) 5 to 10% wt. of a polyurethane resin containing at least 1 vinyl end-capping;
(F) 1-10% wt. reactive liquid nitrile rubber;
(G) 0.01 to 5 percent of Wt stabilizer;
(H) 1 to 8 percent of Wt peroxide initiator;
the curing agent comprises the following raw materials in percentage by mass:
(A) 20 to 60 percent of Wt vinyl Shan Guan acrylic ester monomer;
(B) 5-35% wt. elastomer;
(C) 0.1 to 2 percent of Wt total refined paraffin;
(D) 1-10% WtCTBN modified epoxy resin;
(E) 5 to 10% wt. of a polyurethane resin containing at least 1 vinyl end-capping;
(F) 1-10% wt. reactive liquid nitrile rubber;
(G) 0.01 to 5 percent of Wt stabilizer;
(H) 1 to 10 percent of Wt accelerant;
(I) 0.01 to 2 percent of Wt transition metal organic salt;
(J) 1 to 5 percent of Wt auxiliary accelerator;
the vinyl acrylic ester monomer is one or a mixture of more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate, 2-phenoxyethyl methacrylate and tetrahydrofuran methacrylate; the elastomer is MBS rubber elastomer or the elastomer is mixture of MBS rubber elastomer and one or more of nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene and SBS rubber elastomer; the CTBN modified epoxy resin is o-cresol formaldehyde epoxy resin modified by CTBN; the polyurethane resin containing at least one vinyl end-capping is a polyurethane resin obtained by polymerizing a polyether polyol with a molecular weight of 3000 with isophorone diisocyanate and end-capping with a methacrylate monomer, and the peroxide initiator is any one of cumene hydroperoxide, tert-butyl hydroperoxide or a mixture thereof.
2. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the fully refined paraffin WAX is one or a mixture of WAX-120, WAX-145 and WAX-156.
3. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the reactive liquid nitrile rubber is one of 1300X33LC, 1300X43LC or a mixture thereof.
4. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the accelerator is an amine.
5. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the transition metal organic salt is any one or more of cobalt acetylacetonate, copper acetylacetonate, zinc acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate and titanium acetylacetonate.
6. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the auxiliary accelerator is one or a mixture of phosphate ester monomer and acrylic polyester adhesion promoter.
7. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the stabilizer of the main agent component is one or a mixture of more of phenolic compounds, quinone compounds, oxalic acid, sodium salts and phenothiazine.
8. The high toughness, high strength, low odor acrylate gum of claim 1 wherein: the stabilizer of the curing agent component is one or a mixture of phenolic compounds and quinone compounds.
9. A process for preparing the high toughness high strength low odor acrylate gum according to any one of claims 1-8, characterized in that: the method comprises the following steps:
(1) Modification of CTBN epoxy resin:
1. putting the o-cresol formaldehyde epoxy resin and liquid CTBN into a reaction bottle;
2. heating to 70-90deg.C, stirring for 30-60 min;
3. pouring triphenylphosphine into a reaction bottle;
4. heating to 110-125deg.C, stirring for 120-150 min;
5. observing the color during stirring, changing from dark brown to light yellow, stopping stirring and cooling;
(2) Modification of polyether polyol:
1. putting polyether polyol with molecular weight of 3000 into a reaction bottle, heating to 115-120 ℃, vacuum dehydrating for 2 hours, and cooling for standby;
2. putting IPDI into a reaction bottle, controlling the temperature to be 70-80 ℃, and stirring for 30 minutes;
3. putting dibutyl tin dilaurate into a reaction bottle, controlling the temperature to 75-80 ℃, and stirring for 90 minutes;
4. adding HEMA and LMA into a reaction bottle, controlling the temperature to 70-80 ℃, and stirring for 90 minutes;
5. putting the HQ into a reaction bottle, controlling the temperature to be 75-80 ℃, stirring for 90 minutes, stopping stirring and cooling;
(3) Main agent components: adding vinyl acrylic ester monomer and refined paraffin into a reaction kettle, heating to 70-74 ℃, adding elastomer and CTBN modified epoxy resin, stirring until complete dissolution, stopping heating, adding polyurethane resin at least containing 1 vinyl end cap and reactive liquid nitrile rubber, stirring until complete dissolution, adding stabilizer, stirring uniformly, cooling to below 30 ℃, adding peroxide initiator, stirring uniformly, and obtaining a main component;
(4) And (3) a curing agent component: adding vinyl acrylic ester monomer and refined paraffin into a reaction kettle, heating to 70-74 ℃, adding elastomer and CTBN modified epoxy resin, stirring until complete dissolution, stopping heating, adding polyurethane resin at least containing 1 vinyl end cap and reactive liquid nitrile rubber, stirring until complete dissolution, adding stabilizer, stirring uniformly, cooling to below 40 ℃, adding accelerator, transition metal salt and auxiliary accelerator, stirring uniformly, and obtaining curing agent component;
(5) The main component prepared in the step (3) and the curing agent prepared in the step (4) are mixed according to the mass portion of 1:1, mixing uniformly to obtain the low-odor acrylate adhesive with high toughness and high strength.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311176124.0A CN117186798A (en) | 2023-09-13 | 2023-09-13 | High-toughness high-strength low-odor acrylate adhesive and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311176124.0A CN117186798A (en) | 2023-09-13 | 2023-09-13 | High-toughness high-strength low-odor acrylate adhesive and preparation process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN117186798A true CN117186798A (en) | 2023-12-08 |
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|---|---|---|---|
| CN202311176124.0A Pending CN117186798A (en) | 2023-09-13 | 2023-09-13 | High-toughness high-strength low-odor acrylate adhesive and preparation process thereof |
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| Country | Link |
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| CN (1) | CN117186798A (en) |
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