CN108977087B - Anaerobic adhesive and preparation method thereof - Google Patents
Anaerobic adhesive and preparation method thereof Download PDFInfo
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- CN108977087B CN108977087B CN201810653132.2A CN201810653132A CN108977087B CN 108977087 B CN108977087 B CN 108977087B CN 201810653132 A CN201810653132 A CN 201810653132A CN 108977087 B CN108977087 B CN 108977087B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 63
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 47
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 21
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000002738 chelating agent Substances 0.000 claims abstract description 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical group CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical group CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 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 description 6
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 4
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UICBCXONCUFSOI-UHFFFAOYSA-N n'-phenylacetohydrazide Chemical compound CC(=O)NNC1=CC=CC=C1 UICBCXONCUFSOI-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZZAGLMPBQOKGGT-UHFFFAOYSA-N [4-[4-(4-prop-2-enoyloxybutoxy)benzoyl]oxyphenyl] 4-(4-prop-2-enoyloxybutoxy)benzoate Chemical compound C1=CC(OCCCCOC(=O)C=C)=CC=C1C(=O)OC(C=C1)=CC=C1OC(=O)C1=CC=C(OCCCCOC(=O)C=C)C=C1 ZZAGLMPBQOKGGT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012207 thread-locking agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an anaerobic adhesive and a preparation method thereof, wherein the anaerobic adhesive comprises the following components in parts by mass: 50-80 parts of epoxy acrylate oligomer; 5-25 parts of bismaleimide; 5-20 parts of an active diluent; 0.05-2 parts of a polymerization inhibitor; 0.02-1 part of metal chelating agent; 1-8 parts of an accelerator; 1-8 parts of an initiator; 0.5-6 parts of a filler; 0.05-1 part of dye. The anaerobic adhesive provided by the invention has excellent binding power and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an anaerobic adhesive and a preparation method thereof.
Background
The anaerobic adhesive is a composition with a series of anaerobic curing characteristics and can play a role in bonding, fixing and sealing, becomes an indispensable liquid tool in the mechanical industry, and has wide application in the industries of aerospace, military industry, automobiles, machinery, electronics, electricity and the like. When the adhesive is stored, the adhesive is not cured when contacting with air, and when the adhesive is used, the adhesive can be cured spontaneously under the action of metal ions after being isolated from air, so that the adhesive, the fixing or the sealing effect is achieved.
The traditional high-temperature-resistant structure anaerobic adhesive is mainly thread locking adhesive, and the thread adhesive is mainly used for thread sealing and locking, and has low bonding strength to a planar structure, poor flexibility and low impact strength. Although the bonding strength of the common anaerobic structural adhesive is good, the adhesive is not ideal in heat resistance, and is mainly characterized in that the bonding strength is greatly reduced under the working condition of 150 ℃ or above, so that the adhesive is difficult to meet the bonding requirements of industries such as metal machinery, electronics and electricity and the like under the high-temperature condition.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an anaerobic adhesive which has excellent binding power and high-temperature resistance.
The invention also aims to provide a preparation method of the anaerobic adhesive, and the anaerobic adhesive prepared by the preparation method has excellent binding power and high-temperature resistance.
One of the purposes of the invention is realized by adopting the following technical scheme:
the anaerobic adhesive comprises the following components in parts by weight:
50-80 parts of epoxy acrylate oligomer;
5-25 parts of bismaleimide;
5-20 parts of an active diluent;
0.05-2 parts of a polymerization inhibitor;
0.02-1 part of metal chelating agent;
1-8 parts of an accelerator;
1-8 parts of an initiator;
0.5-6 parts of a filler;
0.05-1 part of dye.
Further, the anaerobic adhesive comprises the following components in parts by weight:
60-70 parts of epoxy acrylate oligomer;
10-20 parts of bismaleimide;
10-15 parts of an active diluent;
0.1-1 part of polymerization inhibitor;
0.05-0.5 part of metal chelating agent;
2-5 parts of an accelerator;
2-5 parts of an initiator;
1-5 parts of a filler;
0.1-0.5 part of dye.
Further, the anaerobic adhesive comprises the following components in parts by weight:
65 parts of epoxy acrylate oligomer, 15 parts of bismaleimide, 10 parts of reactive diluent, 0.3 part of polymerization inhibitor, 0.05 part of metal chelating agent, 2 parts of accelerator, 2.3 parts of filler, 5 parts of initiator and 0.35 part of dye; or,
65 parts of epoxy acrylate oligomer, 15 parts of bismaleimide, 10 parts of reactive diluent, 0.3 part of polymerization inhibitor, 0.1 part of metal chelating agent, 3.2 parts of accelerator, 2 parts of filler, 4 parts of initiator and 0.4 part of dye; or,
65 parts of epoxy acrylate oligomer, 15 parts of bismaleimide, 10 parts of reactive diluent, 1 part of polymerization inhibitor, 0.5 part of metal chelating agent, 3 parts of accelerator, 3 parts of filler, 2 parts of initiator and 0.5 part of dye.
The epoxy acrylate is at least one of bisphenol a epoxy acrylate, bisphenol F epoxy acrylate, and novolac epoxy acrylate, and the reactive diluent is at least one of n-butyl glycidyl ether, polypropylene glycol diglycidyl ether, tert-butyl glycidyl ether, polyethylene glycol diglycidyl ether, and o-tolyl glycidyl ether.
Further, the polymerization inhibitor is at least one of hydroquinone, naphthoquinone, p-tert-butylphenol and p-methoxyphenol.
Further, the metal chelating agent is at least one of ethylenediaminetetraacetic acid tetrasodium salt and ethylenediaminetetraacetic acid disodium salt.
Further, the accelerant is at least one of o-phenylsulfonyl imide, acetyl phenylhydrazine, triethylamine, maleic acid, N-dimethyl-p-toluidine, N-diethyl-p-toluidine or o-benzoylsulfonyl imide; and/or the presence of a gas in the atmosphere,
the initiator is at least one of tert-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide or tert-butyl peroxybenzoate; and/or the filler is at least one of fumed silica, polytetrafluoroethylene powder, polyethylene powder and polymethyl methacrylate; and/or the dye is at least one of disperse red, disperse purple, oil blue and oil green.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the anaerobic adhesive comprises the following steps:
putting epoxy acrylate oligomer, bismaleimide, a reactive diluent, a polymerization inhibitor, a metal chelating agent, an accelerant and a filler into a reaction kettle according to the weight part ratio, and fully stirring at a first temperature until all the materials are dissolved; and cooling to a second temperature, adding the initiator and the dye into the reaction kettle according to the weight part ratio, and uniformly stirring to obtain a finished product, wherein the first temperature is 45-75 ℃, and the second temperature is 25-45 ℃.
Further, the first temperature is 55-65 ℃, and the second temperature is 35 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the anaerobic adhesive is prepared by adding a proper amount of epoxy acrylate oligomer, so that the characteristics of high bonding strength and good size stability of an adhesive layer of the epoxy acrylate are utilized, the high temperature resistance characteristic of the anaerobic adhesive is endowed, and the bonding force and the high temperature resistance of the anaerobic adhesive are greatly enhanced.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The anaerobic adhesive provided by the embodiment of the invention comprises the following components in parts by weight:
50-80 parts of epoxy acrylate oligomer;
5-25 parts of bismaleimide;
5-20 parts of an active diluent;
0.05-2 parts of a polymerization inhibitor;
0.02-1 part of metal chelating agent;
1-8 parts of an accelerator;
1-8 parts of an initiator;
0.5-6 parts of a filler;
0.05-1 part of dye.
Because the epoxy acrylate is prepared by the esterification reaction of epoxy and acrylic acid, the adhesive has high bonding strength, good adhesive force, high hardness and excellent chemical resistance. Cured epoxy acrylate coatings also exhibit these characteristics. The anaerobic adhesive is prepared by adding a proper amount of epoxy acrylate oligomer, so that the characteristics of high bonding strength and good size stability of an adhesive layer of the epoxy acrylate are utilized, the characteristics of high bonding strength and high temperature resistance of the anaerobic adhesive are endowed, and the bonding force and the high temperature resistance of the anaerobic adhesive are greatly enhanced.
As a preferred embodiment, the anaerobic adhesive comprises the following components in parts by mass: 60-70 parts of epoxy acrylate oligomer; 10-20 parts of bismaleimide; 10-15 parts of an active diluent; 0.1-1 part of polymerization inhibitor; 0.05-0.5 part of metal chelating agent; 2-5 parts of an accelerator; 2-5 parts of an initiator; 1-5 parts of a filler; 0.1-0.5 part of dye.
As a preferred embodiment, the anaerobic adhesive comprises the following components in parts by mass: 65 parts of epoxy acrylate oligomer, 15 parts of bismaleimide, 10 parts of reactive diluent, 0.3 part of polymerization inhibitor, 0.05 part of metal chelating agent, 2 parts of accelerator, 2.3 parts of filler, 5 parts of initiator and 0.35 part of dye; or,
65 parts of epoxy acrylate oligomer, 15 parts of bismaleimide, 10 parts of reactive diluent, 0.3 part of polymerization inhibitor, 0.1 part of metal chelating agent, 3.2 parts of accelerator, 2 parts of filler, 4 parts of initiator and 0.4 part of dye; or,
65 parts of epoxy acrylate oligomer, 15 parts of bismaleimide, 10 parts of reactive diluent, 1 part of polymerization inhibitor, 0.5 part of metal chelating agent, 3 parts of accelerator, 3 parts of filler, 2 parts of initiator and 0.5 part of dye.
In a preferred embodiment, the epoxy acrylate is at least one of bisphenol a type epoxy acrylate, bisphenol F type epoxy acrylate, and novolac type epoxy acrylate.
In a preferred embodiment, the reactive diluent is at least one of n-butyl glycidyl ether, polypropylene glycol diglycidyl ether, tert-butyl glycidyl ether, polyethylene glycol diglycidyl ether, and o-tolyl glycidyl ether. The active diluent has the main functions of adjusting the viscosity of the anaerobic adhesive, improving the toughness or rigidity of the anaerobic adhesive, improving the low-temperature resistance of the anaerobic adhesive, and not reducing the comprehensive performance of the product like other non-active diluents when participating in the reaction.
In a preferred embodiment, the polymerization inhibitor is at least one of hydroquinone, naphthoquinone, p-tert-butylphenol, and p-methoxyphenol. The storage period can be prolonged by adding the polymerization inhibitor. The polymerization inhibitor is used for preparing the anaerobic adhesive, so that the prepared anaerobic adhesive does not gel after being aged for 2-4 hours at 80 ℃, and the shelf life of the prepared anaerobic adhesive is two years at normal temperature.
The metal chelating agent is at least one of ethylene diamine tetraacetic acid tetrasodium salt and ethylene diamine tetraacetic acid disodium salt. The accelerant is at least one of o-phenylsulfonyl imide, acetyl phenylhydrazine, triethylamine, maleic acid, N-dimethyl-p-toluidine, N-diethyl-p-toluidine or o-benzoylsulfonyl imide. The initiator is at least one of tert-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide or tert-butyl peroxybenzoate. The initiator has the characteristic of small activity.
The filler is at least one of fumed silica, polytetrafluoroethylene powder, polyethylene powder and polymethyl methacrylate. The dye is at least one of disperse red, disperse purple, oil blue and oil green. The filler can fill gaps, the fumed silica and the polymethyl methacrylate are used as the filler to endow the anaerobic adhesive with thixotropy so as to prevent the anaerobic adhesive from lacking adhesive at a bonding part due to flowing of the anaerobic adhesive, wherein the polymethyl methacrylate has certain solubility in an acrylic monomer, the polymethyl methacrylate with different molecular weights can be selected to adjust the anaerobic adhesive viscosity, the larger the molecular weight is, the larger the anaerobic adhesive viscosity is, the smaller the molecular weight is, the lower the anaerobic adhesive viscosity is, and the anaerobic adhesive with thixotropy can be prepared. Meanwhile, the polytetrafluoroethylene powder and the polyethylene powder are used as fillers, so that the chemical corrosion resistance of the anaerobic adhesive can be improved, thread seizure is prevented, and the lubricating performance is improved.
The invention also provides a preparation method of the anaerobic adhesive, which comprises the following steps:
putting epoxy acrylate oligomer, bismaleimide, a reactive diluent, a polymerization inhibitor, a metal chelating agent, an accelerant and a filler into a reaction kettle according to the weight part ratio, and fully stirring at a first temperature until all the materials are dissolved; and cooling to a second temperature, adding the initiator and the dye into the reaction kettle according to the weight part ratio, and uniformly stirring to obtain a finished product, wherein the first temperature is 45-75 ℃, and the second temperature is 25-45 ℃.
In a preferred embodiment, the first temperature is 55 to 65 ℃ and the second temperature is 35 ℃.
Comparative example
The anaerobic adhesive in the embodiment comprises the following components in parts by weight:
51 parts of methacrylate, 43 parts of polyethylene glycol (200) diacrylate, 0.15 part of p-methoxyphenol, 0.05 part of ethylene diamine tetraacetic acid tetrasodium salt, 2.5 parts of triethylamine, 4.5 parts of cumene hydroperoxide and 0.5 part of disperse red.
Putting the methacrylate, the polyethylene glycol (200), the diacrylic acid, the triethylamine, the p-methoxyphenol and the ethylene diamine tetraacetic acid tetrasodium salt into a reaction kettle according to the mass part ratio, and fully stirring at 55-65 ℃ until the methacrylate, the polyethylene glycol (200), the diacrylic acid, the triethylamine, the p-methoxyphenol and the ethylene diamine tetraacetic acid tetrasodium salt are completely dissolved; cooling to 35 ℃, putting the cumene hydroperoxide and the disperse red into a reaction kettle according to the weight part ratio, and stirring uniformly to obtain a finished product.
Example 1
The anaerobic adhesive in the embodiment comprises the following components in parts by weight:
65 parts of bisphenol A epoxy acrylate, 15 parts of bismaleimide, 10 parts of n-butyl glycidyl ether, 0.3 part of p-methoxyphenol, 0.05 part of ethylene diamine tetraacetic acid tetrasodium salt, 2 parts of acetyl phenylhydrazine, 2.3 parts of fumed silica, 5 parts of tert-butyl hydroperoxide and 0.35 part of disperse violet.
Putting bisphenol A epoxy acrylate, bismaleimide, n-butyl glycidyl ether, p-methoxyphenol, ethylene diamine tetraacetic acid tetrasodium salt, acetyl phenylhydrazine and fumed silica into a reaction kettle according to the mass part ratio, and fully stirring at 55-65 ℃ until all components are dissolved; cooling to 35 ℃, putting the tert-butyl hydroperoxide and the disperse violet into the reaction kettle according to the weight part ratio, and stirring uniformly to obtain a finished product.
Example 2
The anaerobic adhesive in the embodiment comprises the following components in parts by weight:
65 parts of phenolic epoxy acrylate, 15 parts of bismaleimide, 10 parts of tert-butyl glycidyl ether, 0.3 part of hydroquinone, 0.1 part of ethylene diamine tetraacetic acid disodium salt, 3.2 parts of o-phthalimide, 2 parts of polymethyl methacrylate, 4 parts of cumene hydroperoxide, 0.2 part of disperse red and 0.2 part of disperse violet.
Putting novolac epoxy acrylate, bismaleimide, tert-butyl glycidyl ether, 0.3 part of hydroquinone, ethylene diamine tetraacetic acid disodium salt, o-phenylsulfonyl imide and polymethyl methacrylate into a reaction kettle according to the mass part ratio, and fully stirring at 55-65 ℃ until all the materials are dissolved; cooling to 35 ℃, putting the cumene hydroperoxide, the disperse red and the disperse violet into a reaction kettle according to the weight part ratio, and stirring uniformly to obtain a finished product.
Example 3
The anaerobic adhesive in the embodiment comprises the following components in parts by weight:
65 parts of bisphenol F epoxy acrylate, 15 parts of bismaleimide, 10 parts of o-tolyl glycidyl ether, 1 part of p-tert-butylphenol, 0.5 part of ethylene diamine tetraacetic acid tetrasodium salt, 3 parts of o-phenylsulfonyl imide, 3 parts of polytetrafluoroethylene powder, 2 parts of dicumyl peroxide and 0.5 part of oil blue.
Putting bisphenol F epoxy acrylate, bismaleimide, o-tolyl glycidyl ether, p-tert-butylphenol, ethylene diamine tetraacetic acid tetrasodium salt, o-phenylsulfonylimide and polytetrafluoroethylene powder into a reaction kettle according to the mass part ratio, and fully stirring at 55-65 ℃ until the materials are completely dissolved; and cooling to 35 ℃, adding dicumyl peroxide and oil blue into the reaction kettle according to the weight part ratio, and uniformly stirring to obtain a finished product.
The breaking moment was tested according to standard GB 18747.1-2002. The test results are shown in Table 1.
TABLE 1
Table 1 shows the performance parameters of the anaerobic glue in comparative example, example 1, example 2 and example 3. As can be seen from table 1, the breaking moment and the high temperature resistance of the anaerobic adhesive prepared by adding bisphenol a type epoxy acrylate, bisphenol F type epoxy acrylate and phenol type epoxy acrylate are significantly improved, and thus, the anaerobic adhesive prepared by using bisphenol a type epoxy acrylate, bisphenol F type epoxy acrylate and phenol type epoxy acrylate has high bonding strength, good dimensional stability of the adhesive layer, and significantly enhanced high temperature resistance. In addition, the phenolic epoxy acrylate is polyfunctional glycidyl ether epoxy acrylate, can provide 2.5 times more crosslinking points than bisphenol A epoxy acrylate, can form a three-dimensional structure with high crosslinking degree, and a cured product is rich in phenolic skeleton and shows excellent thermal stability and mechanical strength, so that the anaerobic adhesive prepared from the phenolic epoxy acrylate has more excellent medium resistance, temperature resistance and mechanical property than the anaerobic adhesive prepared from the bisphenol A epoxy acrylate and the bisphenol F epoxy acrylate.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (1)
1. The anaerobic adhesive is characterized by comprising the following components in parts by mass:
65 parts of bisphenol F type epoxy acrylate; 15 parts of bismaleimide; 10 parts of a reactive diluent; 1 part of polymerization inhibitor; 0.5 part of metal chelating agent; 3 parts of an accelerant; 2 parts of an initiator; 3 parts of a filler; 0.5 part of dye;
wherein the reactive diluent is o-tolyl glycidyl ether; the metal chelating agent is ethylene diamine tetraacetic acid tetrasodium salt; the polymerization inhibitor is p-tert-butylphenol; the accelerant is o-phenylsulfonylimide; the initiator is dicumyl peroxide; the filler is polytetrafluoroethylene powder; the dye is oil blue;
the preparation method of the anaerobic adhesive comprises the following steps:
putting bisphenol F type epoxy acrylate, bismaleimide, a reactive diluent, a polymerization inhibitor, a metal chelating agent, an accelerant and a filler into a reaction kettle according to the weight part ratio, and fully stirring at a first temperature until all components are dissolved; cooling to a second temperature, adding the initiator and the dye into the reaction kettle according to the weight part ratio, and uniformly stirring to obtain a finished product, wherein the first temperature is 55-65 ℃, and the second temperature is 35 ℃; the anaerobic adhesive does not gel after being aged for 2-4 hours at 80 ℃.
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| CN101735734B (en) * | 2008-11-04 | 2012-05-16 | 广东恒大新材料科技有限公司 | Anaerobic adhesive initiator composition and anaerobic adhesive containing initiator |
| CN101705071A (en) * | 2009-10-08 | 2010-05-12 | 广东三和化工科技有限公司 | High-temperature-resistant structure anaerobic adhesive |
| CN103194158B (en) * | 2013-04-26 | 2015-05-13 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant anaerobic borosilicate resin hybrid acrylate adhesive and preparation method thereof |
| CN103525356B (en) * | 2013-10-23 | 2015-04-15 | 南宁珀源化工有限公司 | Fixing glue for cutting sapphire |
| GB2531717B (en) * | 2014-10-24 | 2016-10-05 | Henkel IP & Holding GmbH | Anaerobic curable compositions |
| CN104356963A (en) * | 2014-11-19 | 2015-02-18 | 南京艾布纳密封技术有限公司 | High-temperature resistant thread-locking anaerobic adhesive and preparation method thereof |
| JP6504351B2 (en) * | 2015-04-16 | 2019-04-24 | 株式会社スリーボンド | Anaerobically curable composition |
| CN105670552A (en) * | 2016-01-26 | 2016-06-15 | 上海都伟光伏科技有限公司 | One-component acrylate structure adhesive with ageing resistance and high-temperature resistance and preparation method of acrylate structure adhesive |
| CN106189881B (en) * | 2016-08-04 | 2019-04-05 | 广东三和化工科技有限公司 | A kind of flame-proof environmental protection anaerobic adhesive and preparation method |
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