CN87100265A - Room curing and high temperature resistant high-strong toughness epoxy construction adhesive and preparation method - Google Patents
Room curing and high temperature resistant high-strong toughness epoxy construction adhesive and preparation method Download PDFInfo
- Publication number
- CN87100265A CN87100265A CN87100265.5A CN87100265A CN87100265A CN 87100265 A CN87100265 A CN 87100265A CN 87100265 A CN87100265 A CN 87100265A CN 87100265 A CN87100265 A CN 87100265A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- component
- weight
- preparation methods
- described preparation
- 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.)
- Expired - Lifetime
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention is room curing and high temperature resistant high-strong toughness epoxy construction adhesive and preparation method, the fragility of general epoxy adhesive and the shortcoming that room temperature (low temperature) is solidified the temperature tolerance difference have been overcome, its major technique feature is to be mixed with good toughness, high temperature resistant, curing system that reactive behavior is big with homemade solidifying agent and carboxyl butyronitrile modified epoxy in 1: 1～1: 12 ratio, make 200 ℃ of the tackiness agent ambient temperature curable heatproofs that make, but life-time service under 200 ℃, 250 ℃ still have intensity; Or-5 ℃ solidify 150 ℃ of heatproofs; Bonding strength reaches 18-300MPa; T type stripping strength reaches 39.2～66.67N/cm, has the performance of excellent oil resistant, water-fast, alkaline-resisting, acidproof, organic solvent-resistant, can bonding wet surface, and pasta and metal, plastics, pottery, hard rubber, timber etc.
Description
The present invention is room curing and high temperature resistant high-strong toughness epoxy construction adhesive and preparation method.
Since the seventies, countries in the world adhesives industries production and utilisation technology are round economizing the energy, and be nuisanceless, low cost, and high-performance etc. develop for target.Epoxy adhesive does not have the volatile matter effusion owing to have when curing, low-shrinkage, and chemical stability is good, and anti-environmental aging and excellent electric performance etc. are occupied critical role in synthetic adhesive.But because general existing property of epoxy adhesive is crisp and the shortcoming of temperature tolerance difference (resistant to elevated temperatures epoxy adhesive often need hot setting or curing system toxicity big etc.), thereby on using, be restricted.At present, the temperature resistant grade of the various high temperature resistant epoxy adhesives that abroad are developed into is generally below 180 ℃, and needs hot setting, uses inconvenience, and power consumption high (spy opens 77 32,929; The spy opens clear 59 221,381; The spy opens 78 13, and 648; Brit 1,484, and 797; US4,418,166).The U.S. has reported a kind of two component epoxy tackiness agent of high temperature resistant ambient temperature curable recently, but the life-time service temperature also has only 150 ℃ [Li Jinlin, chemical science and technology is dynamic, 46(1983)].Nineteen eighty-two Japan Cemendine company has reported a kind of self-vulcanizing of producing with carbamate or carboxyl butyronitrile modified epoxy and polyamide curing agent, 120～150 ℃ of heatproofs, T type stripping strength is the epoxy adhesive of 39.2N/cm, but should not use below 10 ℃ winter [Industrial materials (day), 30(2), 1982], (Li Gu, bonding two the annual meeting proceedings of China, 1984, P17).
The objective of the invention is to overcome the fragility of general epoxy glue and the shortcoming of self-vulcanizing temperature tolerance difference, be mixed with good toughness by a certain percentage with homemade solidifying agent and modified epoxy, high temperature resistant, the curing system that reactive behavior is big, making room temperature (low temperature) solidifies, also curable, high temperature resistant under-5 ℃, the epoxy construction adhesive of high-strong toughness.
The present invention implements like this: invent said epoxy adhesive in 12: 1～1: 1 ratio preparation cost when using with the homemade solidifying agent (B component) that contains amido, cyano group, phenyl and ehter bond with carboxyl butyronitrile modified epoxy (A component).
The present invention also can be according to the needs of purposes in A or B component, is preferably in to add mineral filler or thixotropic agent in the B component.
The said mineral filler of the present invention can be used porcelain powder, silicon powder, glass fibre, cast iron powder, molybdenumdisulphide, Tungsten carbide etc., thixotropic agent such as white carbon black etc., or organic and inorganic mixed fillers.Can add different fillers according to different purposes,, improve processing performance, improve bonding strength, wear resistance, acid resistance etc. to reduce cost.
Solidifying agent of the present invention can be with diamine 0～80%(weight) (the best is 23～51%), dihydroxyphenyl propane 0～30%(the best is 5～10%), vinyl cyanide 0～45%(the best is 10～27%), Resins, epoxy 0～45%(the best is 15～25%), glyoxaline compound 3～40%(the best is 5～15%), silane coupling agent 0.1～12%(the best is 1～6%) be preparation of raw material or synthetic producing.
The synthesis reaction temperature of solidifying agent of the present invention is 70～150 ℃, and the best is 90～120 ℃, vacuumizes down reaction 1～2 hour, and the entire reaction time is 3～6 hours altogether.
The present invention prepares solidifying agent under above-mentioned reaction conditions order of addition(of ingredients) is: the adding diamine is heated and is made to dissolving, stir and add dihydroxyphenyl propane, vinyl cyanide, Resins, epoxy, isothermal reaction 1～2 hour, vacuumizing down (overbottom pressure 10～30mmHg) reactions 1～2 hour, adding glyoxaline compound reaction 1～2 hour, adding then (preferably cooling back adding) silane coupling agent again.
Said glyoxaline compound can be used imidazoles, 2-ethyl-4-methylimidazole, glyoxal ethyline etc. in the solidifying agent of the present invention, and the best is a glyoxal ethyline; Silane coupling agent can be used γ-An Bingjisanyiyangjiguiwan, γ-epoxidation propoxy-triethoxyl silane, diethylenetriamine base propyl-triethoxysilicane, α-phenylamino Union carbide A-162 etc., and the best is a γ-An Bingjisanyiyangjiguiwan; Diamine can be used hexanediamine, mphenylenediamine, N, N-diamino-phenylbenzene-methane; Resins, epoxy can be used novolac epoxy, amino polyfunctional epoxy resin, bisphenol A epoxide resin etc.
(carboxyl-content is 1.2～10% with carboxy nitrile rubber in the present invention, the best is 4～10%) 5～30%(weight) with Resins, epoxy (as bisphenol A epoxide resin, novolac epoxy etc.) 70～95%, vacuumize at 120～170 ℃ that (overbottom pressure 10～30mmHg) reaction made modified epoxy in 1～2 hour.Through recording the gained resin is the graft block copolymer that contains epoxy group(ing), itrile group, ester group, hydroxyl, phenyl etc., and itrile group is given good oil resistant of resin and cementability, and phenyl is given thermotolerance.
Self-control synthetic solidifying agent contains a large amount of amidos, itrile group, phenyl and ehter bond, thereby give the high reactivity of tackiness agent, oil-proofness, snappiness, and learn tentatively that from differential thermal analysis this curing system has 2～3 exothermic peaks, at room temperature can solidify quickly and reach practical intensity, in use can also continue to solidify, along with improving another group, the use temperature grade reacts simultaneously, form the higher structure of temperature resistant grade, and reach practical intensity, prepared tackiness agent is solidified in room temperature (low temperature), also can solidify under-5 ℃, and have high temperature resistant and high-strong toughness.
The present invention is with solidifying agent (B component), modified epoxy (A component) or add filler according to the above ratio thorough mixing evenly after, glue is coated equably can be bonding on the adherend surface, and apply contact pressure, makes two adhesive faces reach excellent contact.
Compared with prior art, the said epoxy adhesive of the present invention has overcome the fragility of general epoxy glue and the shortcoming that room temperature (low temperature) is solidified the temperature tolerance difference, and temperature tolerance, obdurability have all surpassed prior art, not only self-vulcanizing [25 ℃/(1～7 day) or 60 ℃/(30 minutes～4 hours)], and (5 ℃/4 days) also can solidify under-5 ℃.Bonding strength can reach 18～30MPa; Good toughness, T type stripping strength can reach 39.2～66.67N/cm; 150～200 ℃ of heatproofs, 250 ℃ still have intensity, can be at 150～200 ℃ of following life-time service;-5 ℃ solidify heatproof down and can reach 150 ℃; Performance with excellent oil resistant, water-fast, alkaline resistance properties and good acidproof, organic solvent-resistant; To wet surface, pasta and multiple materials such as metal, plastics, pottery, hard rubber, timber are all demonstrated good adhesiveproperties.
The technology of the present invention route is rationally feasible, and used starting material cheaply are easy to get, and cost is low, and output and quality is stable, and the no three wastes and environmental pollution are suitable for commercialization production.
Tackiness agent for example of the present invention is used for the reparation of " No. one, Chinese hydrokineter " exterior vacuum chamber; Tv flyback transformer magnetic core bonding; Pay the bonding of excitation electromotor permanent magnet; Brake facing bonding; High temperature resistant, high pressure, high-tension electric insulating sealant that submersible electric pump PTD device is required; The field repair of the valve seat cooling cylinder of high-pressure jet drilling slush pump; Bonding and the sealing of New Cementing sleeve pipe insert well cementation structure; The repairing of automobile, fuel tank, oil tank, water tank, water pot, natural gas line etc. and add the proper metal filler as the reparation of oil press column, oil cylinder etc.
Example one
Modified epoxy 92.05%(weight)
Glyoxal ethyline 7.36%(weight)
γ-An Bingjisanyiyangjiguiwan 0.59%(weight)
Modified epoxy is by liquid carboxyl butyronitrile 16.7%(weight), bisphenol-A epoxy E-51 83.3% adds in the reactor, and heat temperature raising stirs, and begins to vacuumize (overbottom pressure 10～30mmHg) isothermal reactions 2 hours and making when temperature rises to 130 ℃.Be mixed with tackiness agent in above-mentioned material ratio then.
Example two
Dihydroxyphenyl propane 7.2%(weight)
Vinyl cyanide 18.3%(weight)
Hexanediamine 36.6%(weight)
Epoxy 644 20.7%(weight)
Glyoxal ethyline 13.3%(weight)
γ-An Bingjisanyiyangjiguiwan 3.9%(weight)
In reactor, add the hexanediamine heating for dissolving, stir and add dihydroxyphenyl propane, vinyl cyanide, epoxy 644,100 ℃ of temperature of reaction, reacted 2 hours, vacuumizing (overbottom pressure 10mmHg) following reaction 2 hours again, cooling adds γ-An Bingjisanyiyangjiguiwan, makes solidifying agent, adds 1: 1 porcelain powder and example one synthetic modified epoxy again by being mixed with tackiness agent at 1: 2.
Claims (13)
1, a kind of room curing and high temperature resistant high-strong toughness epoxy construction adhesive, formulated when it is characterized in that using with the solidifying agent (B component) that contains amido, cyano group, phenyl and ehter bond in 12: 1～1: 1 ratio by carboxyl butyronitrile modified epoxy (A component).
2, tackiness agent according to claim 1 is characterized in that in A or B component, is preferably in to add mineral filler or thixotropic agent in the B component.
3, tackiness agent according to claim 1 and 2 is characterized in that the A component is liquid carboxyl butyronitrile modified epoxy, and carboxyl-content is 1.2～10% in the carboxy nitrile rubber, and the best is 4～10%.
4, the preparation method of tackiness agent according to claim 1, it is characterized in that weight) with diamine 0～80%(, dihydroxyphenyl propane 0～30%, vinyl cyanide 0～45%, Resins, epoxy 0～45%, glyoxaline compound 3～40%, silane coupling agent 0.1～12% is preparation of raw material or synthesizes and produce the B component, is mixed with tackiness agent with carboxyl butyronitrile modified epoxy (A component) or filler then.
5, preparation method according to claim 4 is characterized in that synthesis reaction temperature is 70～150 ℃, and the best is 90～120 ℃, vacuumizes down reaction 1～2 hour, totally 3～6 hours entire reaction time.
6, according to claim 4 or 5 described preparation methods, adding diamine when it is characterized in that reacting earlier makes to dissolving, under agitation add dihydroxyphenyl propane, vinyl cyanide, Resins, epoxy, isothermal reaction 1～2 hour, vacuumize down (overbottom pressure 10～30mmHg) reactions 1～2 hour, add glyoxaline compound reaction 1～2 hour, add (preferably the cooling back adds) silane coupling agent.
7, according to claim 4,5 or 6 described preparation methods, it is characterized in that the Resins, epoxy in the B component is novolac epoxy, amino polyfunctional epoxy resin, bisphenol A epoxide resin, optimum content are 15～25%(weight).
8, according to claim 4,5 or 6 described preparation methods, it is characterized in that glyoxaline compound is an imidazoles, 2-ethyl-4 Methylimidazole, glyoxal ethyline, the best is a glyoxal ethyline, optimum content is 5～15%(weight).
9, according to claim 4,5 or 6 described preparation methods, it is characterized in that silane coupling agent is a γ-An Jibingjisanyiyangjiguiwan, γ-epoxidation propoxy-triethoxyl silane, diethylenetriamine base propyl-triethoxysilicane, α-phenylamino Union carbide A-162, the best is a γ-An Bingjisanyiyangjiguiwan, and optimum content is 1～6%(weight).
10, according to claim 4,5 or 6 described preparation methods, it is characterized in that diamine is hexanediamine, mphenylenediamine, N, N-diamino-phenylbenzene-methane, optimum content are 23～51%.(weight).
11, according to claim 4,5 or 6 described preparation methods, the optimum content that it is characterized in that dihydroxyphenyl propane is 5～10%(weight).
12, it is characterized in that according to claim 4,5 or 6 described preparation methods the optimum content of vinyl cyanide is 10～27%(weight).
13, according to claim 4,5 or 6 described preparation methods, it is characterized in that the A component is by carboxy nitrile rubber (carboxyl-content is 1.2～10%, and the best is 4～10%) 5～30%(weight) and Resins, epoxy 70～95% vacuumizes under 120～170 ℃, and (overbottom pressure 10～30mmHg) reactions were produced in 1～2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87100265 CN1015989B (en) | 1987-01-10 | 1987-01-10 | Room temp. solidified high-temperature-resisting high-strength tough epoxy construction adhesive and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87100265 CN1015989B (en) | 1987-01-10 | 1987-01-10 | Room temp. solidified high-temperature-resisting high-strength tough epoxy construction adhesive and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87100265A true CN87100265A (en) | 1988-07-20 |
| CN1015989B CN1015989B (en) | 1992-03-25 |
Family
ID=4812797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87100265 Expired CN1015989B (en) | 1987-01-10 | 1987-01-10 | Room temp. solidified high-temperature-resisting high-strength tough epoxy construction adhesive and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015989B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341969C (en) * | 2004-01-02 | 2007-10-10 | 湖南神力实业有限公司 | Fast-setting two-component epoxy adhesive and its preparing method |
| CN101818037A (en) * | 2009-02-27 | 2010-09-01 | 汉高（中国）投资有限公司 | Room-temperature curing epoxy structural adhesive composition and preparation method thereof |
| CN102250573A (en) * | 2011-05-05 | 2011-11-23 | 北京天山新材料技术股份有限公司 | High shear and high peel strength epoxy adhesive |
| CN101358121B (en) * | 2008-09-10 | 2012-05-09 | 武汉科技学院 | Preparation method of high temperature resistant epoxy adhesive capable of room temperature curing |
| CN103450835A (en) * | 2012-05-29 | 2013-12-18 | 浙江瑞翌新材料科技有限公司 | Epoxy resin adhesive and preparation method thereof |
| CN103540286A (en) * | 2013-11-01 | 2014-01-29 | 中国林业科学研究院林产化学工业研究所 | Machine brush-manufacturing adhesive and preparation method thereof |
| CN103865461A (en) * | 2014-04-08 | 2014-06-18 | 株洲时代新材料科技股份有限公司 | Adhesive |
| CN103897644A (en) * | 2014-03-27 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Preparation method of silicone-modified epoxy resin packaging adhesive |
| CN104212394A (en) * | 2014-09-11 | 2014-12-17 | 中国科学院长春应用化学研究所 | Room-temperature curing epoxy resin adhesive and preparation method thereof |
| CN106118505A (en) * | 2016-07-07 | 2016-11-16 | 阜南县铭钰柳木工艺品有限公司 | Bamboo cane high-temperature Resistance Adhesives and preparation method thereof used by bamboo weaving |
| CN111117541A (en) * | 2019-12-27 | 2020-05-08 | 海南农垦林产集团股份有限公司 | Finger joint glue blending method for processing glued beam |
| CN113943486A (en) * | 2021-10-26 | 2022-01-18 | 杭州博源电力设备有限公司 | Cable plugging material and preparation method thereof |
| CN115637125A (en) * | 2021-07-20 | 2023-01-24 | 中蓝晨光化工研究设计院有限公司 | Environment-friendly epoxy resin adhesive and preparation method thereof |
-
1987
- 1987-01-10 CN CN 87100265 patent/CN1015989B/en not_active Expired
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341969C (en) * | 2004-01-02 | 2007-10-10 | 湖南神力实业有限公司 | Fast-setting two-component epoxy adhesive and its preparing method |
| CN101358121B (en) * | 2008-09-10 | 2012-05-09 | 武汉科技学院 | Preparation method of high temperature resistant epoxy adhesive capable of room temperature curing |
| CN101818037A (en) * | 2009-02-27 | 2010-09-01 | 汉高（中国）投资有限公司 | Room-temperature curing epoxy structural adhesive composition and preparation method thereof |
| WO2010097051A1 (en) | 2009-02-27 | 2010-09-02 | 汉高（中国）投资有限公司 | Room-temperature curable epoxy structural adhesive composition and preparation method thereof |
| CN101818037B (en) * | 2009-02-27 | 2014-12-31 | 汉高（中国）投资有限公司 | Room-temperature curing epoxy structural adhesive composition and preparation method thereof |
| CN102250573A (en) * | 2011-05-05 | 2011-11-23 | 北京天山新材料技术股份有限公司 | High shear and high peel strength epoxy adhesive |
| CN102250573B (en) * | 2011-05-05 | 2013-01-23 | 北京天山新材料技术股份有限公司 | High shear and high peel strength epoxy adhesive |
| CN103450835A (en) * | 2012-05-29 | 2013-12-18 | 浙江瑞翌新材料科技有限公司 | Epoxy resin adhesive and preparation method thereof |
| CN103450835B (en) * | 2012-05-29 | 2015-07-08 | 浙江瑞翌新材料科技有限公司 | Epoxy resin adhesive and preparation method thereof |
| CN103540286A (en) * | 2013-11-01 | 2014-01-29 | 中国林业科学研究院林产化学工业研究所 | Machine brush-manufacturing adhesive and preparation method thereof |
| CN103540286B (en) * | 2013-11-01 | 2015-06-03 | 中国林业科学研究院林产化学工业研究所 | Machine brush-manufacturing adhesive and preparation method thereof |
| CN103897644A (en) * | 2014-03-27 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Preparation method of silicone-modified epoxy resin packaging adhesive |
| CN103865461A (en) * | 2014-04-08 | 2014-06-18 | 株洲时代新材料科技股份有限公司 | Adhesive |
| CN103865461B (en) * | 2014-04-08 | 2015-12-30 | 株洲时代新材料科技股份有限公司 | A kind of tackiness agent |
| CN104212394A (en) * | 2014-09-11 | 2014-12-17 | 中国科学院长春应用化学研究所 | Room-temperature curing epoxy resin adhesive and preparation method thereof |
| CN104212394B (en) * | 2014-09-11 | 2016-01-13 | 中国科学院长春应用化学研究所 | A kind of room temperature curing epoxy sizing agent and preparation method thereof |
| CN106118505A (en) * | 2016-07-07 | 2016-11-16 | 阜南县铭钰柳木工艺品有限公司 | Bamboo cane high-temperature Resistance Adhesives and preparation method thereof used by bamboo weaving |
| CN111117541A (en) * | 2019-12-27 | 2020-05-08 | 海南农垦林产集团股份有限公司 | Finger joint glue blending method for processing glued beam |
| CN115637125A (en) * | 2021-07-20 | 2023-01-24 | 中蓝晨光化工研究设计院有限公司 | Environment-friendly epoxy resin adhesive and preparation method thereof |
| CN115637125B (en) * | 2021-07-20 | 2023-09-12 | 中蓝晨光化工研究设计院有限公司 | Environment-friendly epoxy resin adhesive and preparation method thereof |
| CN113943486A (en) * | 2021-10-26 | 2022-01-18 | 杭州博源电力设备有限公司 | Cable plugging material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1015989B (en) | 1992-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555386B (en) | Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof | |
| CN87100265A (en) | Room curing and high temperature resistant high-strong toughness epoxy construction adhesive and preparation method | |
| CN103059304B (en) | Preparation and application of long-acting anticorrosion temperature-resistant coating | |
| CN110041869A (en) | A kind of modified epoxy injecting type anchoring adhesive and preparation method thereof | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| CN102533193A (en) | Bi-component epoxy resin construction adhesive and preparation method thereof | |
| CN101696263A (en) | Epoxy resin curing agent, method for preparing same and application thereof | |
| CN104356894A (en) | Preparation method of high-temperature-resistant organic silicon modified unsaturated polyester resin coating | |
| CN101508764B (en) | High-performance pnenolic aldehyde amine hardener for epoxy resin and preparation thereof | |
| CN111961191B (en) | Epoxy curing agent for joint king and preparation method thereof | |
| CN110229588B (en) | Graphene composite nano-alloy underwater heavy-duty coating and preparation method thereof | |
| CN106565636B (en) | Fluorine-containing polyfunctional epoxy resin and preparation method and application thereof | |
| CN106116260B (en) | A kind of granolith plank and preparation method thereof | |
| CN102875777A (en) | Novel epoxy hardener and preparation method thereof | |
| CN111777917A (en) | Preparation method of modified etched basalt scale/epoxy resin composite coating | |
| CN101457132A (en) | High toughness epoxy adhesive | |
| CN1156550C (en) | Single-component organic heat-conducting daub | |
| CN1030374C (en) | Fabrication of epoxy sealing head for fibrous membrane separator | |
| CN108588594B (en) | Electronic insulation packaging material and preparation method thereof | |
| CN115260959B (en) | Epoxy resin adhesive capable of being bonded for long time and preparation method thereof | |
| CN114774046B (en) | Normal-temperature curing adhesive and application method thereof | |
| CN1142215C (en) | Strong alkaline corrosion resistant material composition and firming agent | |
| CN113234207B (en) | Preparation method of acid-resistant solvent-free epoxy resin curing agent and application of curing agent | |
| CN109897166A (en) | A kind of water-soluble epoxy resin curing agent and preparation method thereof | |
| CN113480959B (en) | Building epoxy adhesive with waste rubber powder as filler and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| C14 | Grant of patent or utility model | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| C17 | Cessation of patent right |