CN101735081B - Alicyclic modified amine and preparation method thereof - Google Patents
Alicyclic modified amine and preparation method thereof Download PDFInfo
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- CN101735081B CN101735081B CN 200910312485 CN200910312485A CN101735081B CN 101735081 B CN101735081 B CN 101735081B CN 200910312485 CN200910312485 CN 200910312485 CN 200910312485 A CN200910312485 A CN 200910312485A CN 101735081 B CN101735081 B CN 101735081B
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- polyamine
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- amine
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Abstract
The invention discloses alicyclic modified amine and a preparation method thereof. The alicyclic modified amine is polyamine containing cyclohexyl, which is synthesized through the reaction of epoxy cyclohexane and polyamine serving as raw materials. The preparation method for the alicyclic modified amine is characterized in that the molar ratio of the epoxy cyclohexane to the polyamine serving as the raw materials is 1-1.2: 1, the reaction temperature is between 80 and 170 DEG C, and the reaction time is 4 to 10 hours. An epoxy resin product obtained from a double-component epoxy system cured by the alicyclic modified amine has the advantages of good mechanical property, low contractibility rate, thermal shock resistance, good ultraviolet resistance and room temperature curing performance, stable heat discharge during curing and better surface brightness.
Description
Technical field
The present invention relates to a kind of alicyclic modified amine and preparation method thereof, the especially bright a kind of polyamine that contains cyclohexyl and preparation method thereof that relates to.
Background technology
At present, as the polyamine monomer of epoxy curing agent, because toxicity is large, high volatility seldom is directly used in cured epoxy resin, and the chemical reaction that carries out being correlated with re-uses after increasing molecular weight more, and this behavior often is called the modification of solidifying agent in the art.It is the method for modifying of commonly using that application epoxy compounds and polyamine react, and the epoxide of current normal operation is the Racemic glycidol ethers products such as oxyethane, propylene oxide or butylglycidyl ether.Such as the disclosed epoxy curing agent that uses amine methyl cyclopentamine and glycidyl ether to carry out modification as raw material of CN200410021304.2.The CN96193565.0 report provides a kind of composition, said composition comprises (a) a kind of cycloaliphatic epoxy resin and (b) solidifying agent of significant quantity, should (b) solidifying agent comprises the modifier of a kind of cyclic aliphatic two or polyglycidyl ether and a kind of norbornane diamines.
Summary of the invention
The object of the present invention is to provide a kind of alicyclic modified amine and preparation method thereof, the two-component epoxy system that adopts this alicyclic modified amine to solidify has good mechanical property, and low-shrinkage, cold-hot impact; And good ultra-violet resistance energy and self-vulcanizing performance are arranged, and the solidification process heat release is steady; And preferably surface brightness is arranged.
Purpose of the present invention is achieved by the following technical programs:
The present invention's alicyclic modified amine is the polyamine that contains cyclohexyl that is synthesized by raw material epoxy cyclohexane and polyamine reaction.
The present invention's alicyclic modified amine preparation method is: the mol ratio of raw material epoxy cyclohexane and polyamine is 1～1.2: 1, and temperature of reaction is 80～170 ℃, and the reaction times is 4～10h.
The mol ratio of preferred epoxy cyclohexane and polyamine is 1 ~ 1.05: 1, and preferable reaction temperature is 100～130 ℃, and the preferred reaction time is 6～8h.
Described polyamine is one or more the mixture in fat polyamine or the alicyclic ring polyamine.
Described fat polyamine is the ethyleneamines series product, and chemical general formula is: NH
2CH
2-(CH
2NHCH
2)
n-CH
2NH
2, n is 0,1,2,3,4,5 or 6, such as quadrol, diethylenetriamine, polyethylene polyamine etc., or trimethylene amine series product, chemical general formula is: NH
2(C
2H
4)-[CH
2NH (C
2H
4)]
n-CH
2NH
2, n is 0,1,2,3,4,5 or 6, such as propylene diamine, two propylene triamines etc.
Described alicyclic ring polyamine is alicyclic diamine, such as ring pentamethylene diamine, cyclohexanediamine etc.
Adopt the two-component epoxy system of the present invention's alicyclic modified amine curing, the Resins, epoxy product that obtains has good mechanical property, and cold-hot impacts; Good ultra-violet resistance and self-vulcanizing performance are arranged, and the solidification process heat release is steady; And preferably surface brightness arranged.
Embodiment
Below in conjunction with embodiment the present invention is done progressive explanation.
Embodiment 1
Get the quadrol 60.0g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 98g 99% (w/w) under 90 ℃, and reinforced process temperature is controlled at about 80 ℃.Add complete rear continuation reaction 8h.Namely get the polyamine product that contains cyclohexyl.
Product appearance is white crystals; Molecular weight is 158; Zero pour is＞75 ℃; Amine value 550mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 6 months.
Embodiment 2
Get the quadrol 60.0g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 103g 99% (w/w) under 120 ℃, and reinforced process temperature is controlled at about 120 ℃.Add complete rear continuation reaction 4h.Namely get the polyamine product that contains cyclohexyl.
Product appearance is the yellow-white crystallization; Molecular weight is 158; Zero pour is＞75 ℃; Amine value 550mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 6 months.
Embodiment 3
Get the diethylenetriamine 103.0g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 98.0g 99% (w/w) under 90 ℃, and reinforced process temperature is controlled at about 90 ℃.Add complete rear continuation reaction 9h.Namely get the polyamine product that contains cyclohexyl.
Product appearance is yellow or white congealed solid; Molecular weight is 201; Zero pour is＞70 ℃; Amine value 600～650mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 6 months.
Embodiment 4
Get the diethylenetriamine 103.0g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 98.0g 99% (w/w) under 140 ℃, and reinforced process temperature is controlled at about 140 ℃.Add complete rear continuation reaction 6h.Namely get the slightly dark polyamine product that contains cyclohexyl of color.
Product appearance is yellow or white congealed solid; Molecular weight is 201; Zero pour is＞70 ℃; Amine value 600～650mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 12 months.
Embodiment 5
Get the propylene diamine 74.0g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 98.0g 99% (w/w) under 110 ℃, and reinforced process temperature is controlled at about 110 ℃.Add complete rear continuation reaction 6h.Namely get the polyamine product that contains cyclohexyl.
Product appearance is yellow or white xln; Molecular weight is 172; Zero pour is＞60 ℃; Amine value 550～600mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 6 months.
Embodiment 6
Get the ring pentamethylene diamine 98.0g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 98.0g 99% (w/w) under 130 ℃, and reinforced process temperature is controlled at about 130 ℃.Add complete rear continuation reaction 5h.Namely get the polyamine product that contains cyclohexyl.
Product appearance is yellow congealed solid; Molecular weight is 196; Zero pour is＞75 ℃; Amine value 600mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 6 months.
Embodiment 7
Get quadrol 30.0g, propylene diamine 22.2g, the diethylenetriamine 20.6g of content 99% (w/w), drop in the 250ml reactor.Logical nitrogen is also opened and is stirred, and splashes into the epoxy cyclohexane of 105.0g 99% (w/w) under 130 ℃, and reinforced process temperature is controlled at about 170 ℃.Add complete rear continuation reaction 4h.Namely get the polyamine product that contains cyclohexyl.
Product appearance is yellow or white congealed solid; Zero pour is＞70 ℃; Amine value 550～600mgKOH/g; Good with each based epoxy resin, polyetheramine, modified amine intermiscibility; Toxicity is lower than fat polyamine, aromatic amine and aliphatic cyclic amine; Store and stablized in 6 months.
Application Example:
Claims (2)
1. alicyclic modified amine is characterized in that: be by one or more the synthetic polyamine epoxy hardener that contains cyclohexyl of mixture reaction in raw material epoxy cyclohexane and quadrol, diethylenetriamine, propylene diamine, the ring pentamethylene diamine;
The mol ratio of the mixture of one or more of described raw material epoxy cyclohexane and described quadrol, diethylenetriamine, propylene diamine, ring pentamethylene diamine is 1 ~ 1.2:1, and temperature of reaction is 80 ~ 170 ℃, and the reaction times is 4 ~ 10h.
2. alicyclic modified amine according to claim 1, it is characterized in that: the mol ratio of the mixture of one or more of epoxy cyclohexane and described quadrol, diethylenetriamine, propylene diamine, ring pentamethylene diamine is 1 ~ 1.05:1, temperature of reaction is 100 ~ 130 ℃, and the reaction times is 6 ~ 8h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910312485 CN101735081B (en) | 2009-12-29 | 2009-12-29 | Alicyclic modified amine and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910312485 CN101735081B (en) | 2009-12-29 | 2009-12-29 | Alicyclic modified amine and preparation method thereof |
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| CN101735081A CN101735081A (en) | 2010-06-16 |
| CN101735081B true CN101735081B (en) | 2013-04-17 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3255035B1 (en) * | 2016-06-10 | 2018-09-19 | Evonik Degussa GmbH | 2- (3,3,5-trimethylcyclohexyl) propane-1,3-diamine, a method for their preparation and use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183109A (en) * | 1995-04-28 | 1998-05-27 | 国际壳牌研究有限公司 | Epoxy resin composition |
-
2009
- 2009-12-29 CN CN 200910312485 patent/CN101735081B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183109A (en) * | 1995-04-28 | 1998-05-27 | 国际壳牌研究有限公司 | Epoxy resin composition |
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| CN101735081A (en) | 2010-06-16 |
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Address after: 414000 room 217, No. 111, yingpanling Road, Yueyang Economic and Technological Development Zone, Yueyang City, Hunan Province Patentee after: Changde Xincai Technology Co.,Ltd. Address before: Room 209, 111 Yingpanling Road, Yueyang Economic and Technological Development Zone, Hunan 414000 Patentee before: Yueyang Changde Environmental Technology Co.,Ltd. |
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