CN1143661A - Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive - Google Patents
Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive Download PDFInfo
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- CN1143661A CN1143661A CN 96115631 CN96115631A CN1143661A CN 1143661 A CN1143661 A CN 1143661A CN 96115631 CN96115631 CN 96115631 CN 96115631 A CN96115631 A CN 96115631A CN 1143661 A CN1143661 A CN 1143661A
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Abstract
A process for preparing polyurethane toughened epoxy resin adhesive is disclosed. In said adhesive, aromatic diamine such as diamino dimethio toluene is used as solidifying agent with solidifying temp. from ambient temp. to 60 deg.C and solidifying time of 10-48 hr. Said adhesive has shear strength (steel-steel) up to 29.8 MPa as compared with that of pure epoxy resin of 20.0 MPa and stripping strength (aluminium-steel) up to 6.0 kN/m as compared with that of polyester of 3.0 kN/m.
Description
It is toughness reinforcing component with urethane that the present invention proposes a kind of, the preparation method of the epoxyn of ambient cure.
The characteristics of Resins, epoxy are high-adhesive-strength, low flexibility; Hard section of urethane can provide shearing resistance, and soft section can provide impact strength and fatigue resistance.Both combine and can give tackiness agent with higher shearing resistance, stripping strength and wear resistance.But the curing of Resins, epoxy only just can obtain preferable performance when solidification value reaches more than 120 ℃.The solidification value of urethane also requires more than 80 ℃.In general, reduce solidification value and be difficult to obtain ideal epoxy resin-polyurethane material.In existing technology, representative is the patent [Eur.Pat.Appl., 0,240,183 (1987)] of U.S. palmer company 1987, and the core of this patent is that the polyether polyamine of researching and developing with Texao company is a solidifying agent.With the alkylphenol end-blocking, Resins, epoxy, end capped urethane are mixed with polyether polyamine curing agent urethane.Patent is claimed that above-mentioned system can be implemented under near room temperature 40 ℃ and is cured.
Through inventor herein's laboratory test results, the system that Palmer company proposes can not successfully be solidified at 40 ℃.Even quote 1 in addition, 5-diaza-bicyclo [4,3,0]-5-nonene and 1,5-diaza-bicyclo [5,4,0]-5-hendecene is as curing catalysts [U.S.P., 4,952,629 (1990)], the solidified effect is also bad, only the about alkylphenol of 60-70% deblocking from the urethane end group.Consider in the Palmer company technology and generally must under temperature more than 120 ℃, just better effects can be arranged by deblocking with the alkylphenol blocked polyurethane, even quote the deblocking catalyzer (as above-mentioned 1, the derivative of 5-diaza-bicyclo) effective, not only cost an arm and a leg, and reagent stability is poor, necessary freezing preservation (storing temp is below 4 ℃), unfavorable to technology popularization.
The objective of the invention is to overcome alkylphenol blocked polyurethane deblocking temperature height in the Palmer company technology, adopt that polyether polyamine curing agent is domestic can not be produced, and expensive shortcoming, explore a new curing system, so that can under lower temperature, be cured, and make the tackiness agent after the curing have good shearing resistance and stripping strength.
In order to realize above purpose, it is basal component that the present invention adopts with Resins, epoxy, and urethane is toughness reinforcing component, prepares tackiness agent by interpenetrating net polymer (IPN) synthetic method.Use the IPN synthetic method, synergistic effect appears in the shearing resistance and the stripping strength of expectation tackiness agent, when improving material resistance to impact shock and stripping strength, sacrifices the shearing resistance of tackiness agent as small as possible.The key of the art of this patent is to explore a suitable curing system, can realize the curing of IPN network at low temperatures, and prepares the tackiness agent with good shearing resistance and stripping strength over-all properties.
Through a large amount of exploitative experiments, find that the epoxy resin-polyurethane system adopts aromatic diamines, as diamino diformazan sulfenyl toluene (DADMT) etc. as solidifying agent, can the unison epoxy resins and the difference of urethane two component curing speeds, can guarantee that again tackiness agent is cured reaction in room temperature-60 ℃ scope.Resins, epoxy is with the resin (molecular weight 390 of the E-51 trade mark in this patent, oxirane value 0.48-0.54 mole/100 grams) be main, urethane is to form with the tolylene diisocyanate reaction for soft section with end hydroxy polyether polyvalent alcohol (polyethers 330, polyethers 210 or its mixture).Urethane accounts for 25-30% in two components, under such component, has promptly kept the high-adhesive-strength (steel-steel shearing resistance reaches 25-30MPa) of epoxyn, gives tackiness agent again with quite high toughness (steel-aluminium stripping strength reaches 5-6KN/m).Compare with existing technology, the present invention has following characteristics:
1. in the epoxy resin-polyurethane bicomponent system, need not carry out end-blocking to urethane.Like this, both can reduce the system solidification value, can reduce cost again.
2. application ipn technology, tackiness agent not only has high stripping strength, and shearing resistance also is that existing technology is unapproachable.
3. system synthesis technique of the present invention and to join all more existing technology of adhesive process simple.
Embodiments of the invention are as follows:
Example 1
Base polyurethane prepolymer for use as synthetic: add 100 parts of polyethers 330 in the reactor, heated and stirred, decompression dehydration is not till have bubble under 90 ℃, 10mmHg, be cooled to 50 ℃, add 15.4 parts of tolylene diisocyanates (TDI), slowly be warming up to 80 ℃, reacted 3-4 hour, NCO% is 3.0%
Tackiness agent preparation: 100 parts of E-51 Resins, epoxy, (669) 19 parts of ethylene glycol diglycidylethers, 2 parts of KH-560 coupling agents, 5 parts of aerosils, 6 parts of titanium dioxide, 19 parts of kaolin, 55 parts of base polyurethane prepolymer for use as, 65 parts of diamino diformazan sulfenyl toluene.
Condition of cure: in the time of 60 ℃ 10 hours 25 ℃ the time 48 hours
Example 2
The synthetic method of base polyurethane prepolymer for use as is with example 1, and filling a prescription is: 210100 parts of polyethers, and TDI35 part, NCO% is 6.2%
Tackiness agent preparation: 100 parts of E-51,20 parts of ethylene glycol diglycidylethers, 2 parts of KH-560,5 parts of aerosils, 6 parts of titanium dioxide, 20 parts of kaolin, 35 parts of base polyurethane prepolymer for use as, 27 parts of diamino diformazan sulfenyl toluene, 23 parts of mphenylenediamines.Tackiness agent curing under 60 ℃ reached following performance in 10 hours:
Shearing resistance 29.8MPa (steel-steel)
180 ° of stripping strength 6.0KN/m (aluminium-steel)
(11.0KN/m urethane-steel)
Claims (7)
1. a normal temp solidification polyurethane toughened epoxy resin adhesive is characterized in that with Resins, epoxy being main ingredient, is toughness reinforcing component with urethane, prepares by the interpenetrating(polymer)networks synthetic method.
2. according to the Resins, epoxy of indication in the claim 1, it can be bisphenol-A and epoxy chloropropane synthetic Resins, epoxy that its feature is levied in Resins, epoxy, or the α of aliphatic ether, the omega end epoxy compounds also can be the mixture of the epoxy compounds of above-mentioned two kinds of structures.
3. according to the urethane of claim 1 indication, it is characterized in that with tolylene diisocyanate (TDI) and diphenylmethanediisocyanate (MDI) be hard section, is the urethane of soft section preparation with polyester, polyethers, polybutadiene polyol.
4. according to the urethane of claim 3 indication, it is characterized in that urethane can be that urethane with a kind of chemical structure also can be the mixture of the urethane of different structure more than two kinds.
5. according to the interpenetrating(polymer)networks synthetic system of claim 1 indication, it is characterized in that with aromatic diamines as solidifying agent, comprising diamino diformazan sulfenyl toluene, diaminodiphenyl-methane, mphenylenediamine, diamino diethyl toluene etc., also can be their mixture.
6. curing system according to claim 5 is characterized in that the solidification value scope in room temperature to 60 ℃, and should be 48-10 hour set time mutually, and working life was greater than 60 minutes.
7. Resins, epoxy according to claim 1 and urethane two components is characterized in that the weight of urethane accounts for the 15-35% of resin total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115631 CN1143661A (en) | 1996-01-17 | 1996-01-17 | Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115631 CN1143661A (en) | 1996-01-17 | 1996-01-17 | Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1143661A true CN1143661A (en) | 1997-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96115631 Pending CN1143661A (en) | 1996-01-17 | 1996-01-17 | Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091129C (en) * | 1997-07-21 | 2002-09-18 | 贾剑珉 | High-strength flexible structure adhesive |
| CN1295290C (en) * | 2005-06-25 | 2007-01-17 | 西南科技大学 | Process for preparing epoxy adhesive capable of curing at room temperature for special assembly |
| CN1304516C (en) * | 2005-12-23 | 2007-03-14 | 中冶集团建筑研究总院 | Adhesive for slow-binding prestress reinforcement |
| CN101679579B (en) * | 2007-06-20 | 2012-05-30 | 陶氏环球技术公司 | Crash durable epoxy adhesives with very low sensitivity to temperature variations |
| CN105176476A (en) * | 2015-09-30 | 2015-12-23 | 安徽省思维新型建材有限公司 | One-component polyurethane and epoxy adhesive with normal-temperature moisture curing capacity and preparation method of one-component polyurethane and epoxy adhesive |
| CN106146802A (en) * | 2016-08-19 | 2016-11-23 | 武汉工程大学 | Compound 2 ghiourea group 3,5 2 (methyl mercapto) 4 amino toluene is in the application of epoxy-resin systems |
| CN106905904A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | Digestion resistant adhesive and preparation method thereof |
| CN110499132A (en) * | 2019-08-08 | 2019-11-26 | 上海航天化工应用研究所 | A kind of solar heat protection binding function integrated composite and its preparation method and application |
| CN113338176A (en) * | 2021-06-03 | 2021-09-03 | 上海承亥桥隧工程集团有限公司 | Method for repairing hinge joint of uninterrupted traffic hollow slab bridge |
| CN114752333A (en) * | 2022-04-11 | 2022-07-15 | 中国航发北京航空材料研究院 | Normal-temperature-cured high-strength high-toughness high-temperature-resistant epoxy structure adhesive and preparation method thereof |
| CN115851222A (en) * | 2022-11-16 | 2023-03-28 | 烟台德邦科技股份有限公司 | Flexible copper foil base material bonding material and preparation method thereof |
-
1996
- 1996-01-17 CN CN 96115631 patent/CN1143661A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091129C (en) * | 1997-07-21 | 2002-09-18 | 贾剑珉 | High-strength flexible structure adhesive |
| CN1295290C (en) * | 2005-06-25 | 2007-01-17 | 西南科技大学 | Process for preparing epoxy adhesive capable of curing at room temperature for special assembly |
| CN1304516C (en) * | 2005-12-23 | 2007-03-14 | 中冶集团建筑研究总院 | Adhesive for slow-binding prestress reinforcement |
| CN101679579B (en) * | 2007-06-20 | 2012-05-30 | 陶氏环球技术公司 | Crash durable epoxy adhesives with very low sensitivity to temperature variations |
| CN105176476A (en) * | 2015-09-30 | 2015-12-23 | 安徽省思维新型建材有限公司 | One-component polyurethane and epoxy adhesive with normal-temperature moisture curing capacity and preparation method of one-component polyurethane and epoxy adhesive |
| CN106905904A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | Digestion resistant adhesive and preparation method thereof |
| CN106146802A (en) * | 2016-08-19 | 2016-11-23 | 武汉工程大学 | Compound 2 ghiourea group 3,5 2 (methyl mercapto) 4 amino toluene is in the application of epoxy-resin systems |
| CN106146802B (en) * | 2016-08-19 | 2019-05-03 | 武汉工程大学 | Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems |
| CN110499132A (en) * | 2019-08-08 | 2019-11-26 | 上海航天化工应用研究所 | A kind of solar heat protection binding function integrated composite and its preparation method and application |
| CN110499132B (en) * | 2019-08-08 | 2022-03-04 | 上海航天化工应用研究所 | Heat-proof bonding function integrated composite material and preparation method and application thereof |
| CN113338176A (en) * | 2021-06-03 | 2021-09-03 | 上海承亥桥隧工程集团有限公司 | Method for repairing hinge joint of uninterrupted traffic hollow slab bridge |
| CN114752333A (en) * | 2022-04-11 | 2022-07-15 | 中国航发北京航空材料研究院 | Normal-temperature-cured high-strength high-toughness high-temperature-resistant epoxy structure adhesive and preparation method thereof |
| CN114752333B (en) * | 2022-04-11 | 2024-02-13 | 中国航发北京航空材料研究院 | Normal-temperature-cured high-strength high-toughness high-temperature-resistant epoxy structural adhesive and preparation method thereof |
| CN115851222A (en) * | 2022-11-16 | 2023-03-28 | 烟台德邦科技股份有限公司 | Flexible copper foil base material bonding material and preparation method thereof |
| CN115851222B (en) * | 2022-11-16 | 2024-04-02 | 烟台德邦科技股份有限公司 | Soft copper foil substrate bonding material and preparation method thereof |
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