CN101338018B - Epoxy curing agent and method for preparing same - Google Patents
Epoxy curing agent and method for preparing same Download PDFInfo
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- CN101338018B CN101338018B CN2007100435573A CN200710043557A CN101338018B CN 101338018 B CN101338018 B CN 101338018B CN 2007100435573 A CN2007100435573 A CN 2007100435573A CN 200710043557 A CN200710043557 A CN 200710043557A CN 101338018 B CN101338018 B CN 101338018B
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Abstract
The invention discloses an epoxy resin curing agent and a preparation method thereof. Amine compounds and phenolic compounds react for 2 to 14 hours under the temperature of 30 DEG C to 120 DEG C, and then the epoxy resin curing agent is obtained. The curing agent of the invention has no generation of the three wastes during the preparation, and has excellent physical and mechanical strength, light color, low viscidity, good fluidity, stable property for long term storage and no precipitation and crystallization whether in hot summer or cold winter, and can solidify epoxy resin under the lower temperature (3 DEG C to 7 DEG C). Compared with the unmodified aliphatic amine and alicyclic amine, the epoxy resin curing agent has good miscibility with the epoxy resin, can totally satisfy the requirements of the coatings, the electrons, the decorations, the adhesives and the composites.
Description
Technical field
The present invention relates to a kind of solidifying agent, relate in particular to a kind of low temperature epoxy curing agent and preparation method thereof.
Background technology
Resins, epoxy itself is thermoplasticity line style structure, can not directly use.By adding solidifying agent, Resins, epoxy is cross-linked into the cancellated thermosetting resin of build from thread-like molecule, thereby has use value.This solidification process is to be finished by the addition reaction of epoxide group in the Resins, epoxy molecule and solidifying agent.The solidifying agent difference, the mechanism of addition reaction is also different with condition of cure.
Amine curing agent is most representative normal temperature (low temperature) solidifying agent, and the most frequently used amine curing agent has following several.
(1) liquid polyamide curing agent:
This solidifying agent is the condenses of dimer (fatty acid) yl and polyhydric aliphatic amine.The mixture of they and Resins, epoxy has long usage period and good bonding force, snappiness and water tolerance.Their shortcoming is bad with the intermiscibility of Resins, epoxy; Low-temperature curing is incomplete, sluggish when temperature is lower than 15 ℃ especially, even add 2,4,6-three (dimethyl amine methyl) phenol (DMP-30) still is difficult to obtain satisfied water tolerance, chemical resistant properties and physical mechanical strength as promotor.
(2) fatty amine curing agent: (class word deletion)
This solidifying agent is the affixture of polyhydric aliphatic amine and mono-functional epoxy compound or Resins, epoxy.Contain a certain amount of hydroxyl in the molecule and can promote reaction, quicken resin solidification, improve solidifying agent and dissolving resin, resin chemical resistant properties and physical mechanical strength after the curing are good.This solidifying agent can be at 10-25 ℃ of completely solidified Resins, epoxy.But the primary amine in the polyhydric aliphatic amine absorbs the albefaction (also cry sometimes and haze or sweating) that water in air part and carbonic acid gas form epoxy resin surface in the solidifying agent under low temperature and high relative humidity (below 5 ℃) condition, and curing speed is very slow.
(3) pnenolic aldehyde amine hardener:
Phenols, formaldehyde and organic amine can be used as epoxy curing agent by the alkali that Manny phase (Mannich) reaction makes, and claim the phenolic aldehyde amine curing agent again.Though this reaction has reduced the functionality of amine, reaction plays promoter action to epoxy-amine to be with weakly acidic phenolic hydroxyl group.Down the solidification of Mannich alkali is very rapid at low temperature (3～7 ℃), even 0 ℃ still have curing activity, and compared with the aliphatic amide that does not have modification, Mannich alkali is good with the compatibility of Resins, epoxy, and blush resistance and anti-water spots are better.But the thick liquid of normally pale brown look of this class solidifying agent or reddish-brown is not suitable for light color or colourless Resins, epoxy is used, as coating, and electronics, artwork Ornament, tackiness agent.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of epoxy curing agent and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
The preparation method of low temperature epoxy curing agent of the present invention comprises the steps:
With aminated compounds and phenolic compound, at 30-120 ℃, preferred 85 ℃, reacted 2-14 hour, preferred 8 hours, promptly obtain low temperature epoxy curing agent of the present invention;
The part by weight of aminated compounds and phenolic compound is:
Aminated compounds: phenolic compound=1～5: 1;
Preferred ratio is:
Aminated compounds: phenolic compound=1～3: 1;
Said aminated compounds comprises aliphatic amide or aliphatic cyclic amine;
Said aliphatic amide comprises aliphatic amide or its modifier;
Preferred aliphatic amide is quadrol, butanediamine, hexanediamine, the rare triamine of diethyl, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, diethylaminopropylamine, Monoethanolamine MEA BASF, diethanolamine, trolamine, m-xylene diamine, 593 solidifying agent or 5769 solidifying agent etc.;
The chemical name of said 593 solidifying agent is the affixture of diethylenetriamine and epoxy propane butyl ether, can adopt the product of Shanghai Resin Factory Co., Ltd.;
The chemical name of said 5769 solidifying agent is the affixture of triethylene tetramine and oxyethane, can adopt the product of Shanghai Resin Factory Co., Ltd.;
Said aliphatic cyclic amine comprises aliphatic cyclic amine or its modifier;
Preferred aliphatic cyclic amine is isophorone diamine, cyclohexanediamine, methyl ring pentamethylene diamine, 1,3 pair of (aminomethyl) hexanaphthene, 4, more than one in 4 '-diamino-dicyclohexyl methane, aminoethylpiperazine or 5618 solidifying agent;
The chemical name of 5618 solidifying agent is the affixture of isophorone diamine and Resins, epoxy, can adopt the product of Shanghai Resin Factory Co., Ltd.;
Said phenolic compound comprises phenol, dihydroxyphenyl propane, nonyl phenol or tert.-butyl phenol etc.;
Solidifying agent of the present invention can be at low temperature, and as 3-7 ℃, cured epoxy resin mixes solidifying agent of the present invention with Resins, epoxy, and general part by weight is: 100 parts of Resins, epoxy, 20～60 parts in solidifying agent.
Solidifying agent of the present invention, preparation process do not have the three wastes to produce, and have good physical mechanical strength, of light color, viscosity is low, good fluidity, standing storage stable performance, no matter heat and severe winter, not precipitation and crystalline polamer can be at low temperature (3-7 ℃) cured epoxy resins.With respect to unmodified aliphatic amide and aliphatic cyclic amine, good with the Resins, epoxy compatibility, can satisfy the needs of coating, electronics, ornaments, tackiness agent and matrix material fully.
Embodiment
Embodiment 1
Electric mixer is being housed, is adding isophorone diamine 170g, aminoethylpiperazine 60g in the there-necked flask of the 250ml of spherical condensating tube and thermometer, dihydroxyphenyl propane 70g starts agitator, begins to heat up, maintain the temperature at 90 ℃, reacted 6 hours, obtain the sticking shape liquid of water white transparency.
Adopt GB/T12007.1-1989 Resins, epoxy color measurenent method Gardner's colourity method and GB/T12007.4-1989 Resins, epoxy viscosity measurement standard to detect, the result is as follows:
Color and luster, (Gardner)≤2, viscosity, (25 ℃) mPa.s ,≤200, store stable performance after a year, not precipitation and crystalline polamer.
At low temperature (3-7 ℃) cured epoxy resin, the after fixing thing was hard in 24 hours, surface-brightening; Comparison is still soft, and there is greasy thing in the surface.
Embodiment 2
Electric mixer is being housed, is adding diethylenetriamine 120g in the there-necked flask of the 250ml of ball-type condenser and thermometer, dihydroxyphenyl propane 130g starts agitator, begins to heat up, and keeps 80 ℃ of temperature, reacts 4.5 hours, obtains the sticking shape liquid of light color.
Adopt GB/T12007.1-1989 Resins, epoxy color measurenent method Gardner's colourity method and GB/T12007.4-1989 Resins, epoxy viscosity measurement standard to detect, the result is as follows:
Color and luster, (Gardner)≤2, viscosity, (25 ℃) mPa.s ,≤350, store stable performance after a year, not precipitation and crystalline polamer.
At low temperature (3-7 ℃) cured epoxy resin, the after fixing thing was hard in 24 hours, surface-brightening; Comparison is still soft, and there is greasy thing in the surface.
Embodiment 3
Electric mixer is being housed, is adding aminoethylpiperazine 110g in the there-necked flask of the 250ml of ball-type condenser and thermometer, nonyl phenol 90g starts agitator, begins to heat up, and keeps 60 ℃ of temperature, reacts 3 hours, obtains light viscous liquid.
Adopt GB/T12007.1-1989 Resins, epoxy color measurenent method Gardner's colourity method and GB/T12007.4-1989 Resins, epoxy viscosity measurement standard to detect, the result is as follows:
Color and luster, (Gardner)≤2, viscosity, (25 ℃) mPa.s ,≤150, store stable performance after a year, not precipitation and crystalline polamer.
At low temperature (3-7 ℃) cured epoxy resin, the after fixing thing was hard in 24 hours, surface-brightening; Comparison is still soft, and there is greasy thing in the surface.
Claims (8)
1. the preparation method of low temperature epoxy curing agent comprises the steps: aminated compounds and phenolic compound, at 30-120 ℃, reacts 2-14 hour, promptly obtains epoxy curing agent;
The part by weight of aminated compounds and phenolic compound is:
Aminated compounds: phenolic compound=1～5: 1.
2. method according to claim 1 is characterized in that, temperature of reaction is 85 ℃, and the reaction times is 8 hours.
3. method according to claim 1 is characterized in that aminated compounds: phenolic compound=1～3: 1.
4. method according to claim 1 is characterized in that said aminated compounds comprises aliphatic amide or aliphatic cyclic amine.
5. method according to claim 4, it is characterized in that aliphatic amide is quadrol, butanediamine, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diethylaminopropylamine, Monoethanolamine MEA BASF, diethanolamine, trolamine, m-xylene diamine, 593 solidifying agent, 5769 solidifying agent or 784 solidifying agent.
6. method according to claim 4, it is characterized in that, said aliphatic cyclic amine is isophorone diamine, cyclohexanediamine, methyl ring pentamethylene diamine, 1,3 pair of (aminomethyl) hexanaphthene, 4, more than one in 4 '-diamino-dicyclohexyl methane, aminoethylpiperazine or 5618 solidifying agent.
7. method according to claim 4 is characterized in that said phenolic compound comprises phenol, dihydroxyphenyl propane, nonyl phenol or tert.-butyl phenol.
8. according to the epoxy curing agent of each described method preparation of claim 1～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2007100435573A CN101338018B (en) | 2007-07-06 | 2007-07-06 | Epoxy curing agent and method for preparing same |
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| CN2007100435573A CN101338018B (en) | 2007-07-06 | 2007-07-06 | Epoxy curing agent and method for preparing same |
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| CN101338018A CN101338018A (en) | 2009-01-07 |
| CN101338018B true CN101338018B (en) | 2010-09-08 |
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Families Citing this family (10)
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|---|---|---|---|---|
| TWI527839B (en) * | 2009-01-09 | 2016-04-01 | Nagase Chemtex Corp | A method for producing a thermosetting epoxy resin hardening material having transparency for visible light and a |
| JP5628891B2 (en) * | 2009-03-17 | 2014-11-19 | ダウ グローバル テクノロジーズ エルエルシー | Curable composition comprising cyclic diamine and cured product thereof |
| CN101985548B (en) * | 2010-06-30 | 2013-05-01 | 苏州贝得科技有限公司 | Refrigerating agent-resistant adhesive for high-voltage motor and preparation method thereof |
| CN104448244A (en) * | 2014-11-30 | 2015-03-25 | 桂林理工大学 | Preparation method of low-temperature epoxy resin curing agent |
| CN106883802A (en) * | 2015-12-16 | 2017-06-23 | 大亚(江苏)地板有限公司 | A kind of timber floor healant and application method |
| CN106675325A (en) * | 2016-12-10 | 2017-05-17 | 安徽卧龙泵阀股份有限公司 | Alkali-resistant resin coating for chemical pump |
| CN108727563B (en) * | 2017-04-19 | 2020-10-30 | 北京金汇利应用化工制品有限公司 | Epoxy curing agent |
| CN109897568B (en) * | 2019-03-11 | 2020-11-24 | 上海域金澜优实业有限公司 | Whitening-resistant curing agent for seam beautifying agent and preparation method thereof |
| CN114163390B (en) * | 2021-11-26 | 2024-03-08 | 江苏三木化工股份有限公司 | Piperazine epoxy resin curing agent and preparation method thereof |
| CN117363163A (en) * | 2023-10-26 | 2024-01-09 | 青岛中氟氟碳材料有限公司 | Preparation method and application of 200-DEG C-resistant heat-insulating coating applied to petrochemical pipeline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5107036A (en) * | 1989-10-25 | 1992-04-21 | Sumitomo Chemical Company, Limited | Curing agent for epoxy resin |
| CN1226568A (en) * | 1998-02-18 | 1999-08-25 | 中国科学院化学研究所 | Aromatic amine epoxy curing agent and preparation thereof |
| CN1460689A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Modified alicyclic amine solidifying agent and its preparation method |
| CN1560107A (en) * | 2004-02-24 | 2005-01-05 | 大连理工大学 | Solidifing agent of modified like epoxy resins by alcyl amine |
-
2007
- 2007-07-06 CN CN2007100435573A patent/CN101338018B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5107036A (en) * | 1989-10-25 | 1992-04-21 | Sumitomo Chemical Company, Limited | Curing agent for epoxy resin |
| CN1226568A (en) * | 1998-02-18 | 1999-08-25 | 中国科学院化学研究所 | Aromatic amine epoxy curing agent and preparation thereof |
| CN1460689A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Modified alicyclic amine solidifying agent and its preparation method |
| CN1560107A (en) * | 2004-02-24 | 2005-01-05 | 大连理工大学 | Solidifing agent of modified like epoxy resins by alcyl amine |
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| CN101338018A (en) | 2009-01-07 |
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