CN100341969C - Fast-setting two-component epoxy adhesive and its preparing method - Google Patents
Fast-setting two-component epoxy adhesive and its preparing method Download PDFInfo
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- CN100341969C CN100341969C CNB2004100228103A CN200410022810A CN100341969C CN 100341969 C CN100341969 C CN 100341969C CN B2004100228103 A CNB2004100228103 A CN B2004100228103A CN 200410022810 A CN200410022810 A CN 200410022810A CN 100341969 C CN100341969 C CN 100341969C
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- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 239000002879 Lewis base Substances 0.000 claims abstract description 7
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000004902 Softening Agent Substances 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical group CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003585 thioureas Chemical class 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical group CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical group CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 239000003822 epoxy resin Substances 0.000 abstract 2
- 229920000647 polyepoxide Polymers 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 239000012745 toughening agent Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 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 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention discloses a fast solidifying bicomponent epoxy adhesive and a preparation method thereof. The adhesive comprises a component A and a component B, wherein the component A is composed of epoxy resin or modified epoxy resin and plasticizing agents or toughening agents, and the component B is composed of modified amine solidifying agents, compound accelerating agents and coupling agents. The present invention is characterized in that the modified amine solidifying agents of the component B are products prepared by the reaction of 20 to 40 wt% of aliphatic polyamine, 40 to 50 wt% of hydroxyl compound and 8 to 15 wt% of thiourea compound at the temperature of 70 to 120 DEG C, and the compound accelerating agents are products prepared by the reaction of 30 to 50 wt% of sulfhydryl compound and 50 to 70 wt% of lewis base at 40 to 80 DEG C; after the adhesive is uniformly mixed, gel time at room temperature is from 3 to 8 minutes, and pressure can reach more than 6.7Mpa after 30 minutes. The present invention has the advantages of simple and convenient technology, low product cost, favorable application performance, no waste water, no waste gas and no waste slag, and the production can be carried out under the condition of normal pressure.
Description
Technical field
The present invention relates to a kind of fast setting two component epoxy tackiness agent and preparation method.
Background technology
Epoxy adhesive generally is made up of two components of A, B, and the A component generally contains Resins, epoxy or modified epoxy, softening agent or toughner; The B component generally contains solidifying agent, promotor, coupling agent etc.The solidifying agent that existing self-vulcanizing two component epoxy tackiness agent uses is an aliphatic polyamine, form very simple, one to the several hrs primary solidification, reached working strength in 3～7 days, weak point is that solidifying agent is volatile, toxicity is big, A, B two component volume ratios are generally 8～9: 1, and impregnation is not easy to control, and curing speed is fast inadequately.CN87100265A discloses a kind of modified amine curing agent that is made by diamine, dihydroxyphenyl propane, vinyl cyanide, and has used imidazoles promotor, and the epoxy adhesive over-all properties of making is better, and at room temperature (25 ℃) solidify, 1～7 day set time.CN11970998A discloses a kind of amine condensation, aromatic amine, polymeric amide of using and has been solidifying agent, and does promotor with tertiary amine, 45 minutes summers of gel time of its epoxy adhesive, 1 hour winter; When solidification value was 30 ℃, be 2 hours set time.Chinese patent publication number 1289348 discloses thiol-cured epoxy composite, is major ingredient with two sulfydryls or many sulfhydryl compounds, has used P contained compound and tertiary amine catalyst simultaneously, and the primary solidification time is 15 minutes.
Summary of the invention
The object of the present invention is to provide a kind of raw material to be easy to get, the preparation method is easy, can under condition of normal pressure, carry out and three-waste free discharge, constant product quality, need only 3～8 minutes quick-setting epoxy adhesive and preparation method thereof at ambient temperature just.
Two component epoxy tackiness agent of the present invention comprises the A component of being made up of Resins, epoxy or modified epoxy, softening agent or toughner; B component by modified amine, compound accelerant, coupling agent constitute is characterized in that:
In the B component:
1. modified amine be by:
20～40 weight % aliphatic polyamines, 40～50 weight % oxy-compound, 8～15 weight % thioureas, described weight % total amount is 100%, the product that makes through 70～120 ℃ of reactions;
2. compound accelerant be by
30～50 weight % sulfhydryl compounds, 50～70 weight % Lewis bases, described weight % total amount is 100%, the product that makes through 40～80 ℃ of reactions;
Production method of the present invention may further comprise the steps:
(1) modified amine is synthetic
With 20～40 weight % aliphatic polyamines, 40～50 weight % oxy-compound, 8～15 weight % thioureas, described weight % total amount is 100%, add in the reactor of band temperature control system and agitator, under 70～120 ℃ of conditions, reacted 2～3 hours, make modified amine;
(2) compound accelerant is synthetic
In another reactor, drop into 30～50 weight % sulfhydryl compounds, 50～70 weight % Lewis bases, described weight % total amount is 100%, through 40～80 ℃ of reaction 1～1.5h, is cooled to 40 ℃ then, obtains compound accelerant;
(3) by modified amine: compound accelerant: the weight ratio of coupling agent is 60～80: 5～10: 1～3, earlier compound accelerant is added in the modified amine, and react 1.5～2.5h down at 50～70 ℃, add silane coupling agent again, be cooled to 40 ℃ of dischargings, promptly get component B;
(4) selecting oxirane value for use is 0.3～0.6 Resins, epoxy or modified epoxy, adds softening agent or toughner according to a conventional method and stirs and make the A component;
Volume ratio by A component and B component during use is 1～1.5: 1 mixes.
Also can add filler in the epoxy adhesive of the present invention, as titanium dioxide, kaolin, talcum powder etc., to improve its hardness, wear resistance.
The aliphatic polyamine that the present invention uses can be diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1, and various kinds of amine compounds such as 6-hexanediamine, trimethylammonium hexamethylene diamine also can use aromatic polyamine.The reactive hydrogen number is preferably 4～7.
It is dihydroxyphenyl propane, Bisphenol F, end hydroxy polyether, hydroxyl telechelic polyester that the present invention uses oxy-compound.
The thiourea that the present invention uses is a thiocarbamide.
The sulfhydryl compound that the present invention uses is that wherein to contain a sulfydryl and have a functional group at least be single sulfhydryl compound of carboxyl, as Thiovanic acid, thiohydracrylic acid, single sulfydryl oxysuccinic acid.
The Lewis base that the present invention uses is diethylamide, triethylamine, quadrol, trolamine.
The coupling agent that the present invention uses is that an end is amido or epoxy group(ing), and an end is the organo silane coupling agent of methoxy or ethoxy silane group, as r-(methacryloxy) propyl trimethoxy silicane, r-glycidoxypropyltrime,hoxysilane.
Tackiness agent of the present invention is after mixing, and gel time at room temperature is 3～8 minutes, reaches more than the 6.7MPa after 30 minutes.The used prices of raw and semifnished materials are lower, and production technique is easy, product cost is low, applicable performance is good.This production process is carried out three-waste free discharge under condition of normal pressure.
Embodiment
[embodiment 1]
In three-necked flask, add diethylenetriamine 30g, dihydroxyphenyl propane 40g, thiocarbamide 10.5g, reacted 2 hours down, obtain modified amine at 90 ℃.
In another three-necked flask, add quadrol 5g, drip thiohydracrylic acid 9.8g,, obtain compound accelerant in 50 ℃ of reactions 1.5 hours.
The temperature of modified amine is adjusted to 60 ℃, and the dropping compound accelerant also reacted 2 hours, was cooled to 40 ℃, added 1.4gr-(methacryloxy) propyl trimethoxy silicane, stirred 30 minutes, promptly obtained B component solidifying agent.
Get this solidifying agent 5g, E-44 Resins, epoxy 5g, mixing prepares sample immediately on cardboard, presses GB7124-86 " tackiness agent tensile shear strength measuring method (metal-metal) " and measures tensile shear strength.Different with GB7124-86 is that sample is parked under 30 ℃.
Test-results is gelation time 5 minutes, tensile shear strength 10.8MPa.
[embodiment 2]
In three-necked flask, add tetraethylene pentamine 25g, Bisphenol F 45g, thiocarbamide 14g, reacted 2.5 hours down, obtain modified amine at 75 ℃.
In another three-necked flask, add triethylamine 5g, drip thiohydracrylic acid 8g,, obtain compound accelerant in 60 ℃ of reactions 1.5 hours.
The temperature of modified amine is adjusted to 60 ℃, and the dropping compound accelerant also reacted 2.5 hours, was cooled to 40 ℃, added the 2.5gr-glycidoxypropyltrime,hoxysilane, stirred 30 minutes, promptly obtained B component solidifying agent.
Get this solidifying agent 5g, E-44 Resins, epoxy 5g, mixing prepares sample immediately on cardboard, presses GB7124-86 " tackiness agent tensile shear strength measuring method (metal-metal) " and measures tensile shear strength.Different with GB7124-86 is that sample is parked under 30 ℃.
Test-results is gelation time 6 minutes, tensile shear strength 8.4MPa.
[embodiment 3]
In three-necked flask, add trimethylammonium pregnancy diamines 35g, hydroxyl telechelic polyester 40g, thiocarbamide 9g, reacted 2.5 hours down, obtain modified amine at 75 ℃.
In another three-necked flask, add triethylamine 5g, drip thiohydracrylic acid 6g,, obtain compound accelerant in 60 ℃ of reactions 1.5 hours.
The temperature of modified amine is adjusted to 60 ℃, and the dropping compound accelerant also reacted 2.5 hours, was cooled to 40 ℃, added the 2.5gr-glycidoxypropyltrime,hoxysilane, stirred 30 minutes, promptly obtained B component solidifying agent.
Get this solidifying agent 5g, E-44 Resins, epoxy 5g, mixing prepares sample immediately on cardboard, presses GB7124-86 " tackiness agent tensile shear strength measuring method (metal-metal) " and measures tensile shear strength.Different with GB7124-86 is that sample is parked under 30 ℃.Test-results is gelation time 8 minutes.Tensile shear strength is 9.6MPa.
Claims (8)
1, a kind of epoxy adhesive comprises by Resins, epoxy or modified epoxy, the A component that softening agent or toughner are formed; B component by modified amine curing agent, compound accelerant, coupling agent constitute is characterized in that in the B component
1. modified amine curing agent be by:
20～40 weight % aliphatic polyamines, 40～50 weight % oxy-compound, 8～15 weight % thioureas, described weight % total amount is 100%, the product that makes through 70～120 ℃ of reactions;
2. compound accelerant be by
30～50 weight % sulfhydryl compounds, 50～70 weight % Lewis bases, described weight % total amount is 100%, the product that makes through 40～80 ℃ of reactions;
3. coupling agent is by silane coupling agent;
The volume ratio of A component and B component is 1～1.5: 1.
2, epoxy adhesive according to claim 1 is characterized in that the aliphatic polyamine in the modified amine curing agent is diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1,6-hexanediamine, trimethylammonium hexamethylene diamine.
3, epoxy adhesive according to claim 2 is characterized in that described aliphatic polyamine reactive hydrogen number is 4～7.
4, epoxy adhesive according to claim 1 is characterized in that the oxy-compound in the modified amine curing agent is dihydroxyphenyl propane, Bisphenol F, end hydroxy polyether, hydroxyl telechelic polyester.
5, epoxy adhesive according to claim 1 is characterized in that sulfhydryl compound in the compound accelerant is that wherein to contain a sulfydryl and have a functional group at least be single sulfhydryl compound of carboxyl.
6, epoxy adhesive according to claim 1 is characterized in that the Lewis base in the compound accelerant is diethylamide, triethylamine, quadrol, trolamine.
7, epoxy adhesive according to claim 1 is characterized in that coupling agent is that an end is amido or epoxy group(ing), and an end is the organo silane coupling agent of methoxy or ethoxy silane group.
8, a kind of preparation method of epoxy adhesive as claimed in claim 1 is characterized in that may further comprise the steps:
(1) modified amine curing agent is synthetic
With 20～40 weight % aliphatic polyamines, 40～50 weight % oxy-compound, 8～15 weight % thioureas, described weight % total amount is 100%, add in the reactor of band temperature control system and agitator, under 70～120 ℃ of conditions, reacted 2～3 hours, make modified amine;
(2) compound accelerant is synthetic
In another reactor, drop into 30～50 weight % sulfhydryl compounds, 50～70 weight % Lewis bases, described weight % total amount is 100%, reacts 1～1.5h down at 40～80 ℃, is cooled to 40 ℃ then, obtains compound accelerant;
(3) by modified amine: compound accelerant: the weight % ratio of coupling agent is 60～80: 5～10: 1～3, earlier compound accelerant is added in the modified amine, and react 1.5～2.5h down at 50～70 ℃, add silane coupling agent again, be cooled to 40 ℃ of dischargings, promptly get component B;
(4) selecting oxirane value for use is 0.3～0.6 Resins, epoxy or modified epoxy, adds softening agent or toughner according to a conventional method and stirs and make the A component;
(5) be to mix at 1～1.5: 1 by volume with the A component that makes and B component, promptly make epoxy adhesive product of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100228103A CN100341969C (en) | 2004-01-02 | 2004-01-02 | Fast-setting two-component epoxy adhesive and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100228103A CN100341969C (en) | 2004-01-02 | 2004-01-02 | Fast-setting two-component epoxy adhesive and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1640979A CN1640979A (en) | 2005-07-20 |
| CN100341969C true CN100341969C (en) | 2007-10-10 |
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| CNB2004100228103A Expired - Fee Related CN100341969C (en) | 2004-01-02 | 2004-01-02 | Fast-setting two-component epoxy adhesive and its preparing method |
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| CN109517558B (en) * | 2018-10-30 | 2022-04-08 | 成都飞机工业（集团）有限责任公司 | Preparation method of fast-curing wave-absorbing edge sealing adhesive |
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| CN1640979A (en) | 2005-07-20 |
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