CN102504205B - Preparation method for epoxy hardener resistant to boiling water boiling - Google Patents
Preparation method for epoxy hardener resistant to boiling water boiling Download PDFInfo
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- CN102504205B CN102504205B CN 201110354423 CN201110354423A CN102504205B CN 102504205 B CN102504205 B CN 102504205B CN 201110354423 CN201110354423 CN 201110354423 CN 201110354423 A CN201110354423 A CN 201110354423A CN 102504205 B CN102504205 B CN 102504205B
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Abstract
The invention relates to a preparation method for an epoxy hardener resistant to boiling water boiling. The hardener consists of an epoxy compound, a hydroxyl compound, an amine compound and an imidazole compound, wherein the epoxy compound is butyl glycidyl ether, phenmethyl glycidyl ether or 1,4-butanediol diglycidyl ether; the hydroxyl compound is phenylcarbinol, polyethylene glycol or glycerol; the amine compound is a mixture of m-xylenediamine and 3,3-dimethyl-4,4-diamino-dicyclohexyl methane; and the imidazole compound is 2-ethyl-4-methylimidazole or 2-methylimidazole. The hardener is mainly applied to occasion bonding which is resistant to a boiling water medium for a long time, and has the advantages of simple preparation process, easiness for controlling reaction conditions, environmental friendliness and small reduction rate of strength after boiling water boiling after being hardened and bonded with epoxy resin at the room temperature.
Description
Technical field
The present invention relates to epoxy hardener of a kind of anti-boiling water boiling and preparation method thereof.
Background technology
The solidifying agent that existing self-vulcanizing double-component epoxy adhesive uses has polymeric amide, aliphatic amide, aromatic amine, aliphatic cyclic amine and their modifier, it is coordinated bond after solidifying be placed in boiling water boiled 7 days with epoxy resin, bond is under the effect of water molecules, bond easily comes off, and the strength degradation rate is 10～100% not wait, and is difficult to prolonged application in resistant to boiling water bonding occasion.
Summary of the invention
For solving the deficiency of above-mentioned tackiness agent use properties, the purpose of this invention is to provide that a kind of technique is simple, easy control of reaction conditions, environmental protection, coordinate self-vulcanizing bonding with epoxy resin after, minimum epoxy hardener of strength degradation rate and preparation method thereof after boiling water boiling;
Solidifying agent of the present invention is with after epoxy resin coordinates, the bonding strength of self-vulcanizing is 20～25MPa, bonding strength after one month is 19.8～24.5MPa and through boiling water boiling, strength degradation is minimum, the solidifying agent production technique is simple, easy control of reaction conditions, environmental protection, production process is carried out three-waste free discharge under condition of normal pressure.
The objective of the invention is to realize in the following manner:
The epoxy hardener of a kind of anti-boiling water boiling of the present invention, by 10～20% epoxy compounds, 20～30% oxy-compound, 50～60% aminated compoundss, glyoxaline compound 1～3% hybrid reaction and get, the weight percentage sum of each component is 100%;
Production technique of the present invention is first aminated compounds to be added in there-necked flask, be warmed up to 70～80 ℃ and add glyoxaline compound, after stirring and dissolving is complete, be cooled to again 40 ℃, below 60 ℃, drip the mixture of oxy-compound and epoxy compounds, be warming up to again 80～100 ℃ after 5～6 hours, react cooling after 1～2 hour and get final product discharging;
The epoxy compounds that the present invention uses is to select butylglycidyl ether, benzyl glycidyl ether, BDDE or their mixture;
The oxy-compound that the present invention uses is phenylcarbinol, polyoxyethylene glycol, glycerol or their mixture;
The aminated compounds that the present invention uses is m-xylene diamine and 3,3-dimethyl-4, the mixture of 4-diamino-dicyclohexyl methyl hydride, and both weight ratios are 1:1～2;
The glyoxaline compound that the present invention uses is 2-ethyl-4-methylimidazole, glyoxal ethyline or their mixture.
EmbodimentThe embodiment of the present invention is as follows.
Example 1With 20 g m-xylene diamines, 32g3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride adds in there-necked flask, be warmed up to 70～80 ℃ and add 1.5g2-ethyl-4-methylimidazole, after stirring and dissolving is complete, then be cooled to 40 ℃, drip the mixture of 28g phenylcarbinol and 15g butylglycidyl ether, temperature is controlled at below 60 ℃, is warming up to 80～100 ℃ after 5～6 hours again, then reacts cooling after 1～2 hour and get final product discharging;
Get this solidifying agent 2g, E-44 epoxy resin 3g prepares sample after mixing, presses GB7124-86 " tackiness agent tensile shear strength measuring method (metal-metal) " and measures tensile shear strength;
It is 22MPa that its test-results is placed in the room temperature tensile shearing resistance, and the tensile shear strength through boiling water boiling after month is 21.7 MPa.
Example 2With 20 g m-xylene diamines, 35g3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride adds in there-necked flask, be warmed up to 70～80 ℃ and add the 2g2-Methylimidazole, after stirring and dissolving is complete, then be cooled to 40 ℃, drip the mixture of 24g polyoxyethylene glycol and 13 g benzyl glycidyl ethers, temperature is controlled at below 60 ℃, is warming up to 80～100 ℃ after 5～6 hours again, reacts cooling after 1～2 hour and gets final product discharging;
Get this solidifying agent 2g, E-44 epoxy resin 3g prepares sample after mixing, presses GB7124-86 " tackiness agent tensile shear strength measuring method (metal-metal) " and measures tensile shear strength;
It is 23MPa that its test-results is placed in the room temperature tensile shearing resistance, and the tensile shear strength through boiling water boiling after month is 22,3 MPa.
Claims (5)
1. the preparation method of the epoxy hardener of an anti-boiling water boiling it is characterized in that by 10～20% epoxy compounds, 20～30% oxy-compound, 50～60% aminated compoundss, glyoxaline compound 1～3% hybrid reaction and getting in accordance with the following methods:
First aminated compounds is added in there-necked flask, be warmed up to 70～80 ℃ and add glyoxaline compound, after stirring and dissolving is complete, be cooled to again 40 ℃, below 60 ℃, drip the mixture of oxy-compound and epoxy compounds, be warming up to again 80～100 ℃ after 5～6 hours, react cooling discharging after 1～2 hour;
The weight percentage sum of each component is 100%.
2. the preparation method of the epoxy hardener of anti-boiling water boiling as claimed in claim 1, is characterized in that epoxy compounds is to select butylglycidyl ether, benzyl glycidyl ether, BDDE or their mixture.
3. the preparation method of the epoxy hardener of anti-boiling water boiling as claimed in claim 1, is characterized in that oxy-compound is phenylcarbinol, polyoxyethylene glycol, glycerol or their mixture.
4. the preparation method of the epoxy hardener of anti-boiling water boiling as claimed in claim 1, is characterized in that aminated compounds is m-xylene diamine and 3,3-dimethyl-4, the mixture of 4-diamino-dicyclohexyl methyl hydride, and both weight ratios are 1:1～2.
5. the preparation method of the epoxy hardener of anti-boiling water boiling as claimed in claim 1, is characterized in that glyoxaline compound is 2-ethyl-4-methylimidazole, glyoxal ethyline or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110354423 CN102504205B (en) | 2011-11-10 | 2011-11-10 | Preparation method for epoxy hardener resistant to boiling water boiling |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110354423 CN102504205B (en) | 2011-11-10 | 2011-11-10 | Preparation method for epoxy hardener resistant to boiling water boiling |
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| Publication Number | Publication Date |
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| CN102504205A CN102504205A (en) | 2012-06-20 |
| CN102504205B true CN102504205B (en) | 2013-06-19 |
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| CN 201110354423 Active CN102504205B (en) | 2011-11-10 | 2011-11-10 | Preparation method for epoxy hardener resistant to boiling water boiling |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151530A (en) * | 2014-08-19 | 2014-11-19 | 湖南神力铃胶粘剂制造有限公司 | Yellowing-resistance epoxy curing agent and preparation method thereof |
| RU2760687C2 (en) | 2017-06-09 | 2021-11-29 | Хексион Инк. | Epoxy resin systems for composites |
| CN110551275B (en) * | 2019-09-05 | 2022-04-12 | 中昊(大连)化工研究设计院有限公司 | Flexible imidazole epoxy adduct curing agent and preparation method thereof |
| CN110577635A (en) * | 2019-09-23 | 2019-12-17 | 固德电材系统（苏州）股份有限公司 | Preparation method and application of water-based epoxy resin curing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508825A (en) * | 2009-03-30 | 2009-08-19 | 汕头市骏码凯撒有限公司 | Epoxy resin embedding glue and method for producing the same |
| CN100582161C (en) * | 2007-04-20 | 2010-01-20 | 常熟佳发化学有限责任公司 | Epoxy resin composition and using method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100582161C (en) * | 2007-04-20 | 2010-01-20 | 常熟佳发化学有限责任公司 | Epoxy resin composition and using method thereof |
| CN101508825A (en) * | 2009-03-30 | 2009-08-19 | 汕头市骏码凯撒有限公司 | Epoxy resin embedding glue and method for producing the same |
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| CN102504205A (en) | 2012-06-20 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method for epoxy hardener resistant to boiling water boiling Effective date of registration: 20170504 Granted publication date: 20130619 Pledgee: Bank of Changsha Limited by Share Ltd. Liuyang branch Pledgor: Hunan Magpow Adhesive Manufacture Co.,Ltd. Registration number: 2017430000026 |
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Date of cancellation: 20210621 Granted publication date: 20130619 Pledgee: Bank of Changsha Limited by Share Ltd. Liuyang branch Pledgor: Hunan Magpow Adhesive Manufacture Co.,Ltd. Registration number: 2017430000026 |
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Denomination of invention: Preparation of a boiling resistant epoxy curing agent Effective date of registration: 20210624 Granted publication date: 20130619 Pledgee: Bank of Changsha Limited by Share Ltd. Liuyang branch Pledgor: Hunan Magpow Adhesive Manufacture Co.,Ltd. Registration number: Y2021430000022 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20130619 Pledgee: Bank of Changsha Limited by Share Ltd. Liuyang branch Pledgor: Hunan Magpow Adhesive Manufacture Co.,Ltd. Registration number: Y2021430000022 |