CN117210179A - Single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance - Google Patents
Single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance Download PDFInfo
- Publication number
- CN117210179A CN117210179A CN202311097831.0A CN202311097831A CN117210179A CN 117210179 A CN117210179 A CN 117210179A CN 202311097831 A CN202311097831 A CN 202311097831A CN 117210179 A CN117210179 A CN 117210179A
- Authority
- CN
- China
- Prior art keywords
- parts
- structural adhesive
- epoxy
- thermosetting epoxy
- component thermosetting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 70
- 239000000853 adhesive Substances 0.000 title claims abstract description 52
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 52
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 39
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 229910021485 fumed silica Inorganic materials 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- -1 polydimethylsiloxane Polymers 0.000 claims description 10
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- VEIYJWQZNGASMA-UHFFFAOYSA-N cyclohex-3-en-1-ylmethanol Chemical compound OCC1CCC=CC1 VEIYJWQZNGASMA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000007769 metal material Substances 0.000 abstract description 4
- 238000010008 shearing Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 15
- 229910002012 Aerosil® Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-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 6
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance and a preparation method thereof, wherein the single-component thermosetting epoxy structural adhesive comprises the following components in parts by weight: 5 to 10 parts of self-synthesized anhydride-silane modified epoxy, 40 to 60 parts of epoxy resin, 4 to 6 parts of diluent, 2 to 4 parts of coupling agent, 2 to 4 parts of black paste, 45 to 55 parts of filler, 4 to 10 parts of curing agent and 2 to 6 parts of accelerator. The single-component thermosetting epoxy structural adhesive has excellent impact resistance, and can fully meet the strength requirement of structural bonding; the adhesive has excellent high-temperature shearing strength on metal materials, can meet the application requirements under high-temperature conditions, and ensures the reliability of bonding parts. Has excellent application prospect in the aspects of vehicle body structure adhesion, motor shell adhesion and the like.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a single-component thermosetting epoxy structural adhesive suitable for bonding a vehicle body structure and a motor shell. .
Background
As an important thermosetting polymer material, the epoxy resin has the characteristics of excellent adhesive force, low residual stress, high tensile strength and modulus, low shrinkage rate in the curing process, good chemical resistance and excellent mechanical and dielectric properties. Is widely applied to the fields of aerospace composite materials, high-strength adhesives, molding materials, biomedical systems, electronic packaging, coatings and the like. The cured epoxy resin has certain defects in practical application due to the inherent brittleness. For example: the high crosslinking density results in the disadvantages of poor crack propagation resistance, poor toughness, low fracture energy, low brittleness and impact resistance, etc. Therefore, optimizing and improving the epoxy resin and improving the toughness and the impact resistance of the epoxy resin is always an important subject of research by related researchers.
Thermosetting one-component epoxy adhesives have been used for quite some time in the field of vehicle body construction, which generally have good adhesion to metal substrates and excellent mechanical properties. But in some parts of the vehicle body structure that are prone to heat, for example: motors, gearboxes, etc. The thermosetting single-component epoxy structural adhesive is required to have excellent thermal stability and excellent shear strength under high temperature conditions, and the firmness and reliability of the bonding part are ensured, so that the risk coefficient is reduced and the personal safety is ensured. The thermosetting single-component epoxy structural adhesive generally has higher strength attenuation rate under high temperature conditions, and risks for bonding under high temperature conditions. Therefore, the development of the thermosetting single-component epoxy adhesive with excellent heat stability and low high-temperature strength attenuation rate is very important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of single-component thermosetting epoxy structural adhesive suitable for bonding a vehicle body structure and a motor shell, and the prepared product has excellent impact resistance, excellent shearing strength on a metal material under high temperature and excellent reliability, and can meet the requirements of structural bonding operation, reliability and strength.
The specific technical scheme is as follows:
the invention aims at providing a preparation method of a single-component thermosetting epoxy structural adhesive suitable for bonding a vehicle body structure and a motor shell, which is characterized by comprising the following components in parts by weight:
5 to 10 parts of self-synthesized anhydride-silane modified epoxy, 40 to 60 parts of epoxy resin, 4 to 6 parts of diluent, 2 to 4 parts of coupling agent, 2 to 4 parts of black paste, 45 to 55 parts of filler, 4 to 10 parts of curing agent and 2 to 6 parts of accelerator.
The self-synthesis anhydride-silane modified epoxy is prepared by combining the following raw materials in parts by weight: 190-200 parts of maleic anhydride, 220-235 parts of 3-cyclohexene-1-methanol, 560-600 parts of hydrogen-terminated polydimethylsiloxane, 0.001-0.002 part of K855033 KARSTEDT catalyst, 20-25 parts of 50% sodium hydroxide aqueous solution, 20-30 parts of epichlorohydrin and 315-350 parts of ethanol.
Further, the self-synthesized anhydride-silane modified epoxy is prepared by a three-step method, wherein the first step is as follows: and (3) carrying out esterification reaction on maleic anhydride and 3-cyclohexene-1-methanol to obtain an ester compound A containing double bonds and carboxylic acid groups.
The second step is: and (3) performing hydrosilylation reaction on the hydrogen-terminated polydimethylsiloxane and the ester compound A obtained in the first step to obtain a silane-modified ester compound B with a carboxylic acid group.
The third step is: and (3) reacting the ester compound B prepared in the second step with epichlorohydrin to prepare the anhydride-silane modified epoxy.
The beneficial effects of adopting the further scheme are as follows: on one hand, the epoxy group in the anhydride-silane modified epoxy can improve the compatibility between the anhydride-silane modified epoxy and the epoxy resin, so that the anhydride-silane modified epoxy can be better dispersed to form a uniform phase; on the other hand, the epoxy groups can participate in the reaction to form a three-dimensional network with the main epoxy resin, so that the degree of crosslinking of the system is improved, and the material is endowed with excellent mechanical strength. The cyclohexene structure of the self-synthesized anhydride-silane modified epoxy can endow the material with excellent high-temperature modulus and excellent thermal stability. In addition, the silicon-oxygen bond in the anhydride-silane modified epoxy structure has positive effect on enhancing the thermal stability of the material, and ensures the reliability of the material under the high-temperature condition. The introduction of the silicon-oxygen bond and the anhydride chain segment on the self-synthesized anhydride-silane modified epoxy skeleton improves the flexibility of the material. Meanwhile, the anhydride-silane modified epoxy has ether bond, which is beneficial to enhancing the flexibility of the material and improving the modulus and the shock resistance of the single-component epoxy structural adhesive.
The structural formula of the self-synthesized anhydride-silane modified epoxy is as follows:
the synthetic route of the self-synthesized anhydride-silane modified epoxy is as follows:
further, the epoxy resin is one or a mixture of more than two of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin. The bisphenol A type epoxy resin is preferably Epikote828 of Van, the bisphenol F type epoxy resin is preferably ceramic DER354, and the bisphenol S type epoxy resin is preferably Nanjing Yueixin YBBS-360.
The beneficial effects of adopting the further scheme are as follows: the epoxy resin of different types is selected to match, so that the performances of the single-component thermosetting epoxy structural adhesive, such as workability, tg point, bonding strength, tensile strength, modulus and the like, reach a balance point, and the single-component thermosetting epoxy structural adhesive has excellent comprehensive performance.
Further, the diluent is one or more of benzyl glycidyl ether, neopentyl glycol diglycidyl ether and butyl glycidyl ether.
The beneficial effects of adopting the further scheme are as follows: the viscosity and fluidity of the system are regulated to meet the requirements of different operativity, and meanwhile, the surface smoothness and flatness of the cured product are optimized.
Further, the coupling agent is a silane coupling agent, specifically, one or more than two of 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 3-diethylaminopropyl trimethoxy silane and 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane.
The beneficial effects of adopting the further scheme are as follows: the silane coupling agent is beneficial to improving the wettability of the single-component thermosetting epoxy structural adhesive to the base material and improving the compatibility between the resin and the filler; the wettability of the epoxy structural adhesive to the bonding material is improved, and the bonding strength is enhanced.
Further, the black paste is a premix of carbon black and epoxy resin, specifically, a premix of MA100 of Mitsubishi corporation of Japan and 840 of DIC corporation of Japan, and the ratio of MA100 to 840 is 2:8.
Further, the curing agent is a latent amine curing agent, preferably a dicyandiamide curing agent, preferably an OMICURE DDA 10 of Henschel.
The accelerator is one or more than two of substituted urea or modified imidazole, preferably substituted urea accelerator, preferably OMICURE U-410M of Henschel.
The beneficial effects of adopting the further scheme are as follows: meets the requirements of the single-component thermosetting epoxy structural adhesive on the curing temperature and the curing speed required by structural bonding.
Further, the filler is one or more than two of talcum powder, kaolin, wollastonite, bentonite, silicon dioxide, calcium oxide, aluminum hydroxide, calcium carbonate, magnesium oxide and glass beads. Preferably, the filler is a compounded combination of calcium carbonate and fumed silica:
the calcium carbonate is heavy calcium carbonate with the particle size of 10-15 microns, preferably heavy calcium carbonate with the particle size of 10-15 microns in Nanning wooden forest mining industry.
Further, the fumed silica is hydrophobic fumed silica, preferably AEROSIL R202, AEROSIL R805 and AEROSIL R974 of qin-chang-dado company; TS-720 of cabot corporation.
The beneficial effects of adopting the further scheme are as follows: the introduction of heavy calcium carbonate can greatly reduce the production cost; and meanwhile, the modulus, tensile strength and hardness of the cured structural adhesive are enhanced, and the surface glossiness and wear resistance are improved.
The heavy calcium carbonate can be prevented from sedimentation in the system by introducing hydrophobic fumed silica; the ageing resistance of the cured structural adhesive is improved; the viscosity and the thixotropic property of the system are regulated to meet the requirement of process operability; the strength and ductility of the cured structural adhesive are positively promoted.
The beneficial effects of the invention are as follows: the single-component thermosetting epoxy structural adhesive has excellent impact resistance, excellent shearing strength on metal materials at high temperature and excellent reliability, and can meet the requirements of structural bonding operation, reliability and strength.
Description of the embodiments
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention.
Examples
The preparation method is suitable for the single-component thermosetting epoxy structural adhesive for bonding the vehicle body structure and the motor shell, and comprises the following steps:
(1) Maleic anhydride (196) g) is added into 3-cyclohexene-1-methanol (224-g) and stirred at 60 ℃ for 3 hours under the protection of nitrogen to prepare the ester compound A containing double bonds and carboxylic acid groups.
Under the protection of nitrogen, the ester compound A (420, g) is dehydrated for 30 minutes at 120 ℃, and then hydrogen-terminated poly (dimethylsiloxane) (580, g; average)M n 580), K855033 KARSTEDT catalyst (0.001 g;3000 ppm), at 100 ℃ for 4 hours, and collecting the silane-modified ester compound B with a carboxylic acid group by reduced pressure distillation.
The ester compound B (254 g) and epichlorohydrin (22 g) are mixed in N 2 Respectively adding the mixture into absolute ethyl alcohol (350 g) under the atmosphere, and raising the reaction temperature to 90 ℃; all of the 50% by mass aqueous sodium hydroxide solution (25. 25 g) was added dropwise to the above mixed solution over 2.5 hours, the reaction was stirred at 90 ℃ for 5 hours, followed by centrifugal washing with deionized water three times, removal of the remaining water by addition of anhydrous magnesium sulfate, removal of the solvent by rotary evaporation, and purification by vacuum distillation to obtain an anhydride-silane modified epoxy.
(2) At normal temperature, 10 parts of self-synthesized anhydride-silane modified epoxy obtained in the step (1), 828 parts of bisphenol A epoxy resin Epikote 40 parts, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate are put into a stirring kettle, stirred uniformly and vacuumized for defoaming; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, uniformly stirring, vacuumizing and defoaming to prepare the single-component thermosetting epoxy structural adhesive suitable for bonding of vehicle body structures and motor shells.
Examples
The preparation method is suitable for the single-component thermosetting epoxy structural adhesive for bonding the vehicle body structure and the motor shell, and comprises the following steps:
(1) As in example 1.
(2) At normal temperature, 5 parts of self-synthesized anhydride-silane modified epoxy obtained in the step (1), 828 parts of bisphenol A epoxy resin Epikote 45 parts, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate are put into a stirring kettle, stirred uniformly and vacuumized for defoaming; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, uniformly stirring, vacuumizing and defoaming to prepare the single-component thermosetting epoxy structural adhesive suitable for bonding of vehicle body structures and motor shells.
Examples
The preparation method is suitable for the single-component thermosetting epoxy structural adhesive for bonding the vehicle body structure and the motor shell, and comprises the following steps:
(1) As in example 1.
(2) At normal temperature, 10 parts of self-synthesized anhydride-silane modified epoxy obtained in the step (1), 20 parts of bisphenol A type epoxy resin Epikote828, 20 parts of bisphenol F type epoxy resin DER354, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate are added into a stirring kettle, stirred uniformly and vacuumized and defoamed; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, uniformly stirring, vacuumizing and defoaming to prepare the single-component thermosetting epoxy structural adhesive suitable for bonding of vehicle body structures and motor shells.
Examples
The preparation method is suitable for the single-component thermosetting epoxy structural adhesive for bonding the vehicle body structure and the motor shell, and comprises the following steps:
(1) As in example 1.
(2) At normal temperature, 5 parts of self-synthesized anhydride-silane modified epoxy obtained in the step (1), 22.5 parts of bisphenol A type epoxy resin Epikote828, 22.5 parts of bisphenol F type epoxy resin DER354, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate are put into a stirring kettle, stirred uniformly and vacuumized and defoamed; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, uniformly stirring, vacuumizing and defoaming to prepare the single-component thermosetting epoxy structural adhesive suitable for bonding of vehicle body structures and motor shells.
Examples
The preparation method is suitable for the single-component thermosetting epoxy structural adhesive for bonding the vehicle body structure and the motor shell, and comprises the following steps:
(1) As in example 1.
(2) At normal temperature, 10 parts of self-synthesized anhydride-silane modified epoxy obtained in the step (1), 354 parts of bisphenol F type epoxy resin DER 40 parts, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate are put into a stirring kettle, stirred uniformly and vacuumized for defoaming; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, uniformly stirring, vacuumizing and defoaming to prepare the single-component thermosetting epoxy structural adhesive suitable for bonding of vehicle body structures and motor shells.
Preparing epoxy structural adhesive:
50 parts of bisphenol A epoxy resin Epikote828, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-epoxypropoxy) propyl methyl diethoxysilane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate are put into a stirring kettle, stirred uniformly and vacuumized for defoaming; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, stirring uniformly, vacuumizing and defoaming to prepare the epoxy structural adhesive.
Preparing epoxy structural adhesive:
putting 25 parts of bisphenol A epoxy resin Epikote828, 25 parts of bisphenol F epoxy resin DER354, 4 parts of neopentyl glycol diglycidyl ether, 2 parts of 3- (2, 3-glycidoxy) propyl methyl diethoxysilane, 2 parts of black paste, 5 parts of AEROSIL R202 hydrophobic fumed silica and 40 parts of heavy calcium carbonate into a stirring kettle, stirring uniformly, and vacuumizing and defoaming; and then sequentially adding 5 parts of OMICURE DDA 10 and 2 parts of OMICURE U-410M into a stirring kettle, stirring uniformly, vacuumizing and defoaming to prepare the epoxy structural adhesive.
The performance of the one-component epoxy structural adhesives of the present invention of the above examples 1 to 5 and comparative examples 1 to 2 was tested by the following test.
The high temperature modulus of the cured one-component epoxy structural adhesive was evaluated by DMA (Q800, TA). A spline of specification 60mm×12mm×3mm was prepared, and the test was performed using a double cantilever measurement mode with a heating rate of 5 ℃/min from 25 ℃ to 250 ℃, with an oscillation frequency of 1Hz and an amplitude of 7.5 μm.
N 2 The sample was subjected to dynamic thermo-mechanical analysis (TMA) testing by a TA Instruments Q400-0537 analyzer at an air intake of 100 mL/min. The sample was contacted with the curved probe under a force of 0.20N and then heated from 0℃to 330℃at a rate of 5℃per minute. The force was adjusted by + -0.08N at a frequency of 0.10 Hz during the test cycle. The glass transition temperature (Tg) of the epoxy-amine network was thus measured and the data is the average of three independent runs.
Tensile shear strength measurements followed the ASTM D1002-10 test standard, the tensile shear strength was measured using the following dimensions: bonding area (10 mm. Times.20 mm), glue layer thickness (0.2. 0.2 mm), curing process (20 min/150 ℃), test temperature (25 ℃ and 150 ℃), test speed (10 mm/min).
Test 4K 1C Testing
K 1C Testing was determined by the single edge notched bending technique of a universal testing machine using a 3 point bending jig at 10mm/min according to ASTM D5045 test standard -1 Is a cross-head speed test sample.
The results of tests 1 to 4 are shown in Table 1.
Table 1 comparison of test performances of examples 1 to 5 and comparative examples 1 to 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Modulus at 150 ℃ (MPa) | 113 | 134 | 105 | 127 | 101 | 166 | 157 |
| Tg(℃) | 121 | 132 | 118 | 129 | 115 | 148 | 143 |
| Shear Strength at 25 ℃ (MPa) | 29.7 | 25.9 | 30.4 | 26.8 | 32.3 | 23.8 | 24.6 |
| Shear Strength at 150 ℃ (MPa) | 13.9 | 9.4 | 14.6 | 10.1 | 15.7 | 4.87 | 5.01 |
| K 1C （MPa m 1/2 ） | 5.4 | 3.9 | 6.6 | 4.7 | 7.3 | 1.7 | 1.9 |
As can be seen from the data in table 1, the single-component thermosetting epoxy structural adhesive of the invention has excellent toughness and modulus, so that the material has excellent impact resistance, and can fully meet the strength requirement of structural bonding; the adhesive has excellent high-temperature shearing strength on metal materials, can meet the application requirements under high-temperature conditions, and ensures the reliability of bonding parts. Has excellent application prospect in the aspects of vehicle body structure adhesion, motor shell adhesion and the like.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance is characterized by comprising the following components in parts by weight:
5 to 10 parts of self-synthesized anhydride-silane modified epoxy, 40 to 60 parts of epoxy resin, 4 to 6 parts of diluent, 2 to 4 parts of coupling agent, 2 to 4 parts of black paste, 45 to 55 parts of filler, 4 to 10 parts of curing agent and 2 to 6 parts of accelerator.
2. The single-component thermosetting epoxy structural adhesive according to claim 1, wherein the self-synthesized anhydride-silane modified epoxy is prepared by combining the following raw materials in parts by weight: 190-200 parts of maleic anhydride, 220-235 parts of 3-cyclohexene-1-methanol, 560-600 parts of hydrogen-terminated polydimethylsiloxane, 0.001-0.002 part of K855033 KARSTEDT catalyst, 20-25 parts of 50% sodium hydroxide aqueous solution, 20-30 parts of epichlorohydrin and 315-350 parts of ethanol.
3. The one-part thermosetting epoxy structural adhesive of claim 1 or 2, wherein the self-synthesizing anhydride-silane modified epoxy has the structural formula:
4. the one-part thermosetting epoxy structural adhesive of claim 1 or 2, wherein the synthetic route of the self-synthesizing anhydride-silane modified epoxy is:
5. the single-component thermosetting epoxy structural adhesive according to claim 1, wherein the epoxy resin is one or a mixture of more than two of bisphenol a epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin.
6. The single-component thermosetting epoxy structural adhesive according to claim 1, wherein the diluent is one or a mixture of more than two of benzyl glycidyl ether, neopentyl glycol diglycidyl ether and butyl glycidyl ether; the coupling agent is a silane coupling agent, and is specifically one or more than two of 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 3-diethylaminopropyl trimethoxy silane and 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the black paste is a premix of carbon black and epoxy resin; the curing agent is a latent amine curing agent; the accelerator is one or more than two of substituted urea or modified imidazole.
7. The single-component thermosetting epoxy structural adhesive according to claim 1, wherein the filler is one or a mixture of more than two of talcum powder, kaolin, wollastonite, bentonite, silicon dioxide, calcium oxide, aluminum hydroxide, calcium carbonate, magnesium oxide and glass beads.
8. The one-part thermosetting epoxy structural adhesive of claim 7, wherein the filler is preferably a compounded combination of calcium carbonate and fumed silica; the calcium carbonate is heavy calcium carbonate with the particle size of 10-15 microns; the fumed silica is hydrophobic fumed silica.
9. A method for preparing the single-component thermosetting epoxy structural adhesive according to any one of claims 1 to 8, comprising the steps of:
(1) Under the protection of nitrogen, maleic anhydride and 3-cyclohexene-1-methanol react for 3 hours at 60 ℃ to prepare an ester compound A containing double bonds and carboxylic acid groups;
(2) Dehydrating the ester compound A obtained in the step (1) at 60 ℃ for 30 minutes under the protection of nitrogen, and then adding an averageM n Hydrogen end capped polydimethyl siloxane of 580, K855033 KARSTEDT catalyst of 3000ppm, react for 4 hours at 100 ℃, get the ester compound B with carboxylic acid group modified by silicane through reduced pressure distillation;
(3) Mixing the ester compound B obtained in the step (2), epichlorohydrin and ethanol under the protection of nitrogen, dropwise adding a sodium hydroxide aqueous solution into the mixture, heating the mixture to 90 ℃, stirring for 5 hours, then centrifugally washing with deionized water for three times, adding anhydrous magnesium sulfate to remove residual water, removing the solvent through rotary evaporation, and carrying out vacuum distillation and purification to obtain the self-synthesized anhydride-silane modified epoxy;
(4) Putting the self-synthesized anhydride-silane modified epoxy, epoxy resin, diluent, coupling agent, black paste and filler obtained in the step (3) into a stirring kettle, stirring uniformly, and vacuumizing and defoaming; and then putting the curing agent and the accelerator into the stirring kettle together, stirring uniformly, vacuumizing and defoaming to obtain the single-component thermosetting epoxy structural adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311097831.0A CN117210179A (en) | 2023-08-29 | 2023-08-29 | Single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311097831.0A CN117210179A (en) | 2023-08-29 | 2023-08-29 | Single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117210179A true CN117210179A (en) | 2023-12-12 |
Family
ID=89036180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311097831.0A Pending CN117210179A (en) | 2023-08-29 | 2023-08-29 | Single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117210179A (en) |
-
2023
- 2023-08-29 CN CN202311097831.0A patent/CN117210179A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6888257B2 (en) | Interface adhesive | |
| CN102977557B (en) | A kind of room temperature curing epoxy composition and method of making the same | |
| CN108892929B (en) | Toughened and reinforced epoxy resin composition | |
| CN102827566A (en) | Single-component high/low-temperature-resistant epoxy resin composition | |
| JPH04275383A (en) | High-performance epoxy adhesive | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| WO2013097197A1 (en) | Functional silane-compatibilized epoxy compositions for insulation applications | |
| CN117210179A (en) | Single-component thermosetting epoxy structural adhesive with excellent high temperature resistance and impact resistance | |
| JPH07196770A (en) | Epoxy resin, epoxy resin composition and its cured product | |
| CN109439246B (en) | Two-component epoxy structural adhesive and preparation method thereof | |
| CN110577789A (en) | Silane hybrid low-gross calorific-value solvent-free epoxy resin composition | |
| CN111944467A (en) | Nuclear-grade epoxy pouring sealant, preparation method and application | |
| KR102377780B1 (en) | Toughened epoxy adhesive composition | |
| JP7282011B2 (en) | Curable composition and cured product | |
| CN114058306A (en) | Underfill adhesive and preparation method and application thereof | |
| CN112877017A (en) | Low-curing-shrinkage heat-conducting epoxy pouring sealant and preparation method thereof | |
| CN118291071B (en) | Epoxy heat-conducting structural adhesive capable of realizing rapid positioning and curing at room temperature and preparation method thereof | |
| CN117551273B (en) | Functional auxiliary agent for underfill, preparation method and application thereof | |
| CN114149776B (en) | Internal toughening type epoxy structural adhesive and preparation method thereof | |
| EP1448694B1 (en) | Curable organic resin composition | |
| CN118240518B (en) | Epoxy resin composition for adhesive, preparation method of epoxy resin composition and adhesive | |
| WO2024224303A1 (en) | A modified curing agent component and a process for preparing the same | |
| JP6852622B2 (en) | Thermosetting epoxy resin composition | |
| CN114989759A (en) | Low-shrinkage, high-toughness and low-stress modified epoxy resin and preparation method thereof | |
| JP2015131915A (en) | Two-liquid type epoxy resin composition and method of producing case mold type capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |