CN1803882A - Alpha, omega end amino polyether used as epoxy resin curing agent and method for preparing the same - Google Patents
Alpha, omega end amino polyether used as epoxy resin curing agent and method for preparing the same Download PDFInfo
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- CN1803882A CN1803882A CN 200510019877 CN200510019877A CN1803882A CN 1803882 A CN1803882 A CN 1803882A CN 200510019877 CN200510019877 CN 200510019877 CN 200510019877 A CN200510019877 A CN 200510019877A CN 1803882 A CN1803882 A CN 1803882A
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Abstract
The provided alpha, omega-end polyaminoether as the new curing agent for epoxy resins belongs to the compound with general formula as (1) (wherein, all m, x and y for integer, 10>=m>=2, 6>=x+y>=1 and n for repetitive unit of polyether chain segment)or the mixture with aromatic polyaminoether, contains substituents on ortho-, meta- or para-position of benzene ring, and has high strength and ductility and filling rate without toxin.
Description
Technical field
The present invention relates to a class α, omega-amino terminated polyether and preparation method thereof, and with its adhesive system of forming as epoxy curing agent.
Background technology
As everyone knows, epoxyn has advantages such as resistance to chemical attack, wear-resisting, electrical isolation and adhesiveproperties be good, is widely used in fields such as machinery, electronics, aerospace; But common epoxyn enbrittles greatly, poor toughness, stripping strength, cracking are answered defectives such as step-down and the filling capacity of anti-filler difference, and this has seriously hindered its further application and development.Document " Chemie " [1997,245 (4270): 125-137] and " Polymer Engineeringand Science " [1995,35 (18): 379] are come epoxy resin toughened by some amine curing agents of modification." Chinese tackiness agent " [2000,9 (5): 10] propose when the molecular structure of design epoxy curing agent, to introduce the certain rigid unit to improve adhering with epoxy resin intensity, and obtained having than high-adhesive-strength the amino urethane-epoxyn of certain flexible end.Europatent EP0517167A2 and Chinese invention patent 031252443, disclose respectively with the aromatic amine polyether compound as solidifying agent, can significantly improve the snappiness and the shock-resistant ability of epoxy resin cure product, but their very difficult curing at ambient temperature or set time are longer, thereby are unfavorable for large-area construction application and widely-used.
Summary of the invention
For comprehensive physicals such as sticking power, snappiness and the shock-resistant ability etc. that significantly improve the epoxide resin tackiness agent, improve the anti-filler ability of tackiness agent, and large-area construction and widely used ability are convenient in self-vulcanizing, the invention provides the α of a class, omega-amino terminated polyether and preparation method thereof as epoxy curing agent.Owing to contain phenyl ring rigid element and polyether soft segments in this material, contain the aliphatic amide functional group simultaneously, thereby α, the mixture of omega-amino terminated polyether or itself and aromatic amino-terminated polyether (being called for short AATPE) can be high-strength with the Resins, epoxy composition as solidifying agent, the tackiness agent of high-ductility, high packing ratio.And after this tackiness agent adds filler of different nature, can form the functional coating material that important application is arranged in fields such as electromagnetic compatibility and drag reductions.
α provided by the invention, omega-amino terminated polyether is characterized in that the said α of the present invention, the general formula of omega-amino terminated polyether is:
In the formula (1): m, x, y are integer, and 10 〉=m 〉=2,6 〉=x+y 〉=1; N is the repeating unit of polyether segment, its value between the molecular weight that makes polyether segment between 200 to 10000.Substituting group on the phenyl ring can lay respectively at ortho position, a position or the contraposition on the phenyl ring, also can be positioned at ortho position, a position or contraposition on the phenyl ring simultaneously.
Why the tackiness agent that said AATPE of the present invention and Resins, epoxy are formed has above-mentioned advantage, is that AATPE contains at ambient temperature, can react fast with the epoxide group in the Resins, epoxy molecular chain, forms the aliphatic amide reactive hydrogen of cross-linked network.Owing to exist rigid element and flexible polyether segment in the cross-linked network simultaneously, generate a kind of tight, loose two phase structure, improve the interface feature of polymkeric substance and filler, thereby the product after solidifying, even when the filler packing ratio is high, still have high bonding strength and excellent flexibility.
α of the present invention, the preparation method of omega-amino terminated polyether, it is characterized in that following these steps to carry out: (1) is raw material with the sulfur oxychloride of 0.05mol end hydroxy polyether and 0.08～0.2mol, 0.15 the N of～1.5ml, dinethylformamide are catalyzer, in 40～80 ℃ of scopes, stirred 3～30 hours, obtain the chlorine terminated polyether; (2) be after the Tetrabutyl amonium bromide of the sodium hydroxide of mixture, 0.09～0.6mol of 0～2.0 hydroxy phenyl amine and hydroxy phenyl aliphatic amide and 0.19～1.9g mixes with the mol ratio of 0.08～0.15mol, add 0.05mol chlorine terminated polyether, and under 50～80 ℃, stirred 4～96 hours, then the extraction, filtering and impurity removing, and distillation removal solvent, promptly prepare the said formula of the present invention (1) material.Hydroxy phenyl aliphatic amide of the present invention can be used general formula (2) expression:
X is integer and 3 〉=x＞0 in the formula (2).
The α that uses of the present invention, omega-amino terminated polyether or α, the epoxyn system that the mixture of omega-amino terminated polyether and aromatic amino-terminated polyether (AATPE) is formed as solidifying agent is widely used, nontoxic, ambient temperature curable are even cured product still has characteristics such as high-strength and high ductility when the filler packing ratio is high.
Specific embodiments
Further illustrate content of the present invention below in conjunction with embodiment:
Embodiment 1: polyoxyethylene glycol 0.05mol and N, dinethylformamide (DMF) 0.6mL (0.01mol) are joined in the there-necked flask of 100mL, be warming up to 40 ℃ with oil bath while stirring, in 10min, drip 8mL (0.11mol) sulfur oxychloride then, continue reaction 6 hours at 80 ℃ afterwards.The SO that produces in the reaction process
2, HCl gas absorbs with alkali lye.Crude product is collected in the saturated common salt water washing of reaction solution cooling back, and dry and transfer to neutrality with Anhydrous potassium carbonate, filtration collection filtrate promptly obtains the end capped polyoxyethylene glycol of chlorine then.
In the there-necked flask of 250ml, after hydroxy benzylamine 0.1mol, NaOH 0.4mol and TBAB 0.84g at room temperature mixed, add the end capped polyoxyethylene glycol 0.05mol of chlorine.Simultaneously with oil bath with mixture heating up to 60 ℃, stirred 48 hours.After the reaction solution cooling, with about 50ml methylene dichloride organic compound is extracted, methylene dichloride is removed in distillation then, promptly obtains α, and ω-two (benzamido group) polyoxyethylene glycol is called for short 1-AATPE.
Embodiment 2: polyoxyethylene glycol 0.05mol and N, dinethylformamide (DMF) 0.15mL (0.0025mol) are joined in the there-necked flask of 100mL, be warming up to 40 ℃ with oil bath while stirring, in 8min, drip 5.8mL (0.08mol) sulfur oxychloride then, continue reaction 30 hours at 60 ℃ afterwards.The SO that produces in the reaction process
2, HCl gas absorbs with alkali lye.Crude product is collected in the saturated common salt water washing of reaction solution cooling back, and dry and transfer to neutrality with Anhydrous potassium carbonate, filtration collection filtrate promptly obtains the end capped polyoxyethylene glycol of chlorine then.
In the there-necked flask of 250ml, after hydroxy benzylamine 0.08mol, NaOH 0.09mol and TBAB 0.19g at room temperature mixed, add the end capped polyoxyethylene glycol 0.05mol of chlorine.Simultaneously with oil bath with mixture heating up to 50 ℃, stirred 4 hours.After the reaction solution cooling, with about 50ml methylene dichloride organic compound is extracted, methylene dichloride is removed in distillation then, promptly obtains α, and ω-two (benzamido group) polyoxyethylene glycol is called for short 1-AATPE.
Embodiment 3: polyoxyethylene glycol 0.05mol and N, dinethylformamide (DMF) 1.5mL (0.025mol) are joined in the there-necked flask of 100mL, be warming up to 40 ℃ with oil bath while stirring, in 15min, drip 14.5mL (0.2mol) sulfur oxychloride then, continue reaction 3 hours at 40 ℃ afterwards.The SO that produces in the reaction process
2, HCl gas absorbs with alkali lye.Crude product is collected in the saturated common salt water washing of reaction solution cooling back, and dry and transfer to neutrality with Anhydrous potassium carbonate, filtration collection filtrate promptly obtains the end capped polyoxyethylene glycol of chlorine then.
In the there-necked flask of 250ml, after hydroxy benzylamine 0.15mol, NaOH 0.6mol and TBAB1.9g at room temperature mixed, add the end capped polyoxyethylene glycol 0.05mol of chlorine.Simultaneously with oil bath with mixture heating up to 80 ℃, stirred 96 hours.After the reaction solution cooling, with about 50ml methylene dichloride organic compound is extracted, methylene dichloride is removed in distillation then, promptly obtains α, and ω-two (benzamido group) polyoxyethylene glycol is called for short 1-AATPE
Embodiment 4: with embodiment 1, replace the end capped polyoxyethylene glycol of chlorine with the end capped polypropylene glycol of chlorine, mixture substituted hydroxy benzylamine with hydroxy benzylamine and hydroxy phenyl Isopropylamine, after stirring 24 hours under 80 ℃, cooling, and with about 50ml dichloromethane extraction, distill then and remove methylene dichloride, promptly obtain two amino-terminated polypropylene glycols, be called for short 2-AATPE.
Embodiment 5: with embodiment 1, with hydroxyanilines substituted hydroxy benzylamine, obtain α, omega end aromatic amine polyoxyethylene glycol is called for short 1-BATPE.
Embodiment 6: bisphenol A type epoxy resin E-44 and 1-AATPE are mixed according to 1: 0.6 mass ratio, form the E-44/1-AATPE tackiness agent, 30 ℃ of curing of room temperature then are according to their mechanical property of GB test.Snappiness＜3mm; Shock strength＞50Kg.cm; Sticking power＞40MPa; Stripping strength＞85N/cm.
Embodiment 7: bisphenol A type epoxy resin E-44,1-AATPE and 1-BATPE are mixed according to 1: 0.4: 0.5 mass ratio, form tackiness agent, 30 ℃ of curing of room temperature then are according to their mechanical property of GB test.Snappiness＜2mm; Shock strength＞50Kg.cm; Sticking power＞40MPa; Stripping strength＞85N/cm.
Embodiment 8: Resins, epoxy and 2-AATPE and the tetrahydrofuran (THF) mass ratio according to 1: 0.2: 0.5 is mixed, form tackiness agent, 30 ℃ of curing of room temperature then are according to their mechanical property of GB test.Snappiness＜1mm; Shock strength＞50Kg.cm; Sticking power＞40MPa; Stripping strength＞85N/cm.
Claims (3)
1, a kind of α as epoxy curing agent, omega-amino terminated polyether is characterized in that containing phenyl ring rigid element and polyether soft segments in the molecule, and contains the aliphatic amide functional group, and available general formula (1) expression:
In the formula (1): m, x, y are integer, and 10 〉=m 〉=2,6 〉=x+y 〉=1; N is the repeating unit of polyether segment, its value between the molecular weight that makes polyether segment between 200 to 10000; Substituting group on the phenyl ring can lay respectively at ortho position, a position or the contraposition on the phenyl ring, or is positioned at ortho position, a position or contraposition on the phenyl ring simultaneously.
2, a kind of α as epoxy curing agent, the preparation method of omega-amino terminated polyether, it is characterized in that described α, omega-amino terminated polyether follows these steps to be prepared: (1) is raw material with the sulfur oxychloride of 0.05mol end hydroxy polyether and 0.08～0.2mol, 0.15 the N of～1.5ml, dinethylformamide are catalyzer, in 40～80 ℃ of scopes, stirred 3～30 hours, obtain the chlorine terminated polyether; (2) be after the Tetrabutyl amonium bromide of the sodium hydroxide of mixture, 0.09～0.6mol of 0～2.0 hydroxy phenyl amine and hydroxy phenyl aliphatic amide and 0.19～1.9g mixes with the mol ratio of 0.08～0.15mol, add 0.05mol chlorine terminated polyether, and under 50～80 ℃, stirred 4～96 hours, then the extraction, filtering and impurity removing, and distillation removal solvent, promptly prepare the said formula of the present invention (1) material.
3, α according to claim 2, the preparation method of omega-amino terminated polyether is characterized in that the mixture of described hydroxy phenyl amine and hydroxy phenyl aliphatic amide can be used general formula (2) expression:
In the formula (2): x is an integer, and 3 〉=x 〉=0.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851330A (en) * | 2010-05-28 | 2010-10-06 | 佛山市康泰威新材料有限公司 | Alpha, omega-amino terminated polyether compound with phenolic hydroxyl group, preparation method thereof and epoxy resin adhesive containing the same |
| CN102002158A (en) * | 2010-11-10 | 2011-04-06 | 扬州晨化科技集团有限公司 | Preparation method of alkyl amino terminated polyether |
| CN102161857A (en) * | 2010-12-28 | 2011-08-24 | 中国海洋石油总公司 | Curing agent used for anti-corrosion paint of epoxy resin and preparation method thereof |
| CN102617830A (en) * | 2012-03-27 | 2012-08-01 | 广东新劲刚超硬材料有限公司 | Room temperature curing water-based epoxy hardener and preparation method thereof |
| CN102816289A (en) * | 2012-08-14 | 2012-12-12 | 北方涂料工业研究设计院 | Preparation method for epoxy pouring sealant with characteristics of low viscosity, high elongation rate, and high strength |
| CN103342809A (en) * | 2013-07-04 | 2013-10-09 | 中国石油化工股份有限公司 | Synthesis method of aromatic amine-terminated polyether |
| CN106866435A (en) * | 2017-03-01 | 2017-06-20 | 无锡阿科力科技股份有限公司 | A kind of polyetheramine containing caged scaffold and preparation method thereof |
| CN113121814A (en) * | 2019-12-31 | 2021-07-16 | 惠州盛世达科技有限公司 | Polyether amine modification method |
| CN114395219A (en) * | 2022-01-17 | 2022-04-26 | 南通中集能源装备有限公司 | Hydrogen storage bottle, liquid epoxy resin system wound by wet method and preparation method thereof |
| CN115595087A (en) * | 2022-12-15 | 2023-01-13 | 苏州高泰电子技术股份有限公司（Cn） | Latent reactive adhesive film based on polyurethane and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267471C (en) * | 2003-08-08 | 2006-08-02 | 武汉理工大学 | Terminal aromatic amino base polyether compound, its preparation method and use in adhesive agent |
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2005
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851330B (en) * | 2010-05-28 | 2013-01-09 | 佛山市康泰威新材料有限公司 | Alpha, omega-amino terminated polyether compound with phenolic hydroxyl group, preparation method thereof and epoxy resin adhesive containing the same |
| CN101851330A (en) * | 2010-05-28 | 2010-10-06 | 佛山市康泰威新材料有限公司 | Alpha, omega-amino terminated polyether compound with phenolic hydroxyl group, preparation method thereof and epoxy resin adhesive containing the same |
| CN102002158A (en) * | 2010-11-10 | 2011-04-06 | 扬州晨化科技集团有限公司 | Preparation method of alkyl amino terminated polyether |
| CN102002158B (en) * | 2010-11-10 | 2012-05-09 | 扬州晨化科技集团有限公司 | Preparation method of alkyl amino terminated polyether |
| CN102161857A (en) * | 2010-12-28 | 2011-08-24 | 中国海洋石油总公司 | Curing agent used for anti-corrosion paint of epoxy resin and preparation method thereof |
| CN102161857B (en) * | 2010-12-28 | 2012-09-19 | 中国海洋石油总公司 | Curing agent used for anti-corrosion paint of epoxy resin and preparation method thereof |
| CN102617830A (en) * | 2012-03-27 | 2012-08-01 | 广东新劲刚超硬材料有限公司 | Room temperature curing water-based epoxy hardener and preparation method thereof |
| CN102816289A (en) * | 2012-08-14 | 2012-12-12 | 北方涂料工业研究设计院 | Preparation method for epoxy pouring sealant with characteristics of low viscosity, high elongation rate, and high strength |
| CN103342809A (en) * | 2013-07-04 | 2013-10-09 | 中国石油化工股份有限公司 | Synthesis method of aromatic amine-terminated polyether |
| CN103342809B (en) * | 2013-07-04 | 2015-10-28 | 中国石油化工股份有限公司 | The synthetic method of aromatic series Amino Terminated polyether(ATPE) |
| CN106866435A (en) * | 2017-03-01 | 2017-06-20 | 无锡阿科力科技股份有限公司 | A kind of polyetheramine containing caged scaffold and preparation method thereof |
| CN113121814A (en) * | 2019-12-31 | 2021-07-16 | 惠州盛世达科技有限公司 | Polyether amine modification method |
| CN114395219A (en) * | 2022-01-17 | 2022-04-26 | 南通中集能源装备有限公司 | Hydrogen storage bottle, liquid epoxy resin system wound by wet method and preparation method thereof |
| CN115595087A (en) * | 2022-12-15 | 2023-01-13 | 苏州高泰电子技术股份有限公司（Cn） | Latent reactive adhesive film based on polyurethane and preparation method thereof |
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