CN104072726A - Epoxy resin curing agent and modification method thereof - Google Patents
Epoxy resin curing agent and modification method thereof Download PDFInfo
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- CN104072726A CN104072726A CN201410247247.3A CN201410247247A CN104072726A CN 104072726 A CN104072726 A CN 104072726A CN 201410247247 A CN201410247247 A CN 201410247247A CN 104072726 A CN104072726 A CN 104072726A
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- ethylene glycol
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Abstract
The invention discloses an epoxy resin curing agent and a modification method thereof. The epoxy resin curing agent consists of the following components in parts by weight: 35-50 parts of menthane diamine, 10-20 parts of epoxy compound and 40-45 parts of ethylene glycol butyl ether, wherein the epoxy compound is a compound containing one or two glycidyl ether groups. The epoxy compound and excessive menthane diamine have an addition reaction to obtain an addition product of menthane diamine, so that the toxicity of the curing agent is reduced, the compatibility with an epoxy resin is improved, the anti-whitening performance of a product is improved, the curing agent of the epoxy resin is good in use security, and the quality and the quality stability of the cured epoxy resin are improved.
Description
Technical field
The present invention relates to a kind of used for epoxy resin modification diamine curing agent in the Meng, particularly a kind of epoxy resin solidifying agent and method of modifying thereof.
Background technology
Epoxy resin has experienced the evolution of over half a century since coming out, and its output is occupied critical role with being applied in thermosetting resin field.Epoxy resin has a series of good characteristics, as high in bonding strength, bonding wide, shrinking percentage is low, good stability, and physical strength is high, electrical property is good, good processability etc., in aerospace, electronic instrument, wind-power electricity generation, track traffic, civil engineering work, be used widely in the fields such as electric insulating material.Adopt epoxy resin can make numerous high-performance coatings, tackiness agent, moulding compound and fibre reinforced composites etc.
Epoxy resin is originally as thermoplastic linear structure, and after being heated, solid resin can soften melting.Become thickness state or liquid state; The liquid resin reduced viscosity that is heated.Only add solidifying agent, solidifying agent and epoxy resin are carried out to crosslinking reaction and form cancellated macromole, just can obtain practicality.The solidifying agent of epoxy resin is of a great variety, and conventional have aliphatic polyamine, alicyclic polyamine, aromatic polyamine, heterocyclic amine and an organic acid anhydride etc.Wherein the Meng, alkane diamines was a kind of alicyclic polyamine, and as solidifying agent, it has very high reactive behavior, can normal temperature and low-temperature curing, there is viscosity low, and the advantage such as chemical resistance is good, but it but has following weak point: while solidifying, thermal discharge is large; Active oxygen equivalent is very low, and weighing with resin formula must be accurately, and excessive or not enough meeting greatly affects performance; Easily moisture absorption whiting, affects ply adhesion; There is irritating property strongly, affect operator's health.
Summary of the invention
For addressing the above problem, epoxy resin solidifying agent disclosed by the invention and method of modifying thereof, by carrying out addition reaction with epoxy compounds and excessive alkane diamines in the Meng, obtain the affixture of alkane diamines in the Meng, thereby reduced the toxicity of solidifying agent, improved the consistency with epoxy resin, improved the performance of the anti-albefactions of epoxy resin goods, make the solidifying agent safety in utilization of epoxy resin better, the harm of reduction to operation user of service, quality and the quality stability of the epoxy resin after raising is solidified.
Epoxy resin solidifying agent disclosed by the invention, by alkane diamines in the Meng, epoxy compounds, ethylene glycol monobutyl ether forms, each constituent content (meter by weight) alkane diamines 34-50 weight part in the Meng, epoxy compounds 10-20 weight part, ethylene glycol monobutyl ether 40-45 weight part; Wherein epoxy compounds is the compound that contains one or two glycidyl ether.
The method of modifying of epoxy resin solidifying agent disclosed by the invention, comprise the steps the first step: in the there-necked flask with whipping appts and thermometer, add the epoxy compounds of 1020 weight parts and the ethylene glycol monobutyl ether of 20-23 weight part, start stirring, by heating material to T
1℃ stand-by; Second step: in the four-hole bottle with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 20-22 weight part in the Meng of 34-50 weight part, start stirring, by heating material to T
2℃, the material of the first step gained is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 70-80 ℃, in 1-2 hour, dropwise; The 3rd step: continue at 70-80 ℃ of reaction 1-2 hour, cooling discharge.
A kind of improvement of the method for modifying of epoxy resin solidifying agent disclosed by the invention, 60 ℃≤T
1=T
2≤ 80 ℃.
Another of the method for modifying of epoxy resin solidifying agent disclosed by the invention improved, and during the 3rd step cooling discharge, cooling adopts programmed cooling, and cooling rate is 8-10 ℃/min.
Epoxy resin solidifying agent disclosed by the invention and method of modifying thereof, by carrying out addition reaction with epoxy compounds and excessive alkane diamines in the Meng, obtain the affixture of alkane diamines in the Meng, thereby reduced the toxicity of solidifying agent, improve the consistency of it and epoxy resin, improved the performance of the anti-albefactions of epoxy resin goods, made the solidifying agent safety in utilization of epoxy resin better, reduce the harm to operation user of service, improved quality and the quality stability of the epoxy resin after solidifying.Add ethylene glycol monobutyl ether to play as non-activated thinner and softening agent the low viscous effect of falling.Because it has aliphatic cyclic amine lighter color, tint retention is good, and the advantage that gloss is high is especially suitable for use as the solidifying agent of epoxies sizing agent and coating.And effectively overcome the shortcoming of alkane diamine curing agent in the Meng, there is viscosity low, lighter color, toxicity are low, without excitatory advantage, during with its cured epoxy resin, thermal discharge is little, serviceable time is long, is difficult for moisture absorption whiting, and goods glossiness is high, chemical resistant properties is good, simultaneously can be in envrionment temperature and low-temperature curing.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention, should understand following embodiment and only for the present invention is described, is not used in and limits the scope of the invention.
Epoxy resin solidifying agent disclosed by the invention, by alkane diamines in the Meng, epoxy compounds, ethylene glycol monobutyl ether forms, each constituent content (meter by weight) alkane diamines 34-50 weight part in the Meng, epoxy compounds 10-20 weight part, ethylene glycol monobutyl ether 40-45 weight part; Wherein epoxy compounds is the compound that contains one or two glycidyl ether.
The method of modifying of epoxy resin solidifying agent disclosed by the invention, comprise the steps the first step: in the there-necked flask with whipping appts and thermometer, add the epoxy compounds of 1020 weight parts and the ethylene glycol monobutyl ether of 20-23 weight part, start stirring, by heating material to T
1℃ stand-by; Second step: in the four-hole bottle with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 20-22 weight part in the Meng of 34-50 weight part, start stirring, by heating material to T
2℃, the material of the first step gained is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 70-80 ℃, in 1-2 hour, dropwise; The 3rd step: continue at 70-80 ℃ of reaction 1-2 hour, cooling discharge.
As a kind of preferred, 60 ℃≤T
1=T
2≤ 80 ℃.
As a kind of preferred, during the 3rd step cooling discharge, cooling adopts programmed cooling, and cooling rate is 8-10 ℃/min.
As a kind of preferably, described epoxy compounds is a kind of in bisphenol A-type Racemic glycidol ethers diepoxides E-51 or butylglycidyl ether or Bisphenol F type Racemic glycidol ethers diepoxides DER354 or neodecanoic acid glycidyl ester.
Embodiment 1
In the there-necked flask with whipping appts and thermometer, add the bisphenol A-type Racemic glycidol ethers diepoxides E-51 of 15 parts and the ethylene glycol monobutyl ether of 23 parts, start stirring, heating material to 70 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 20 parts in the Meng of 42 parts, start stirring, by heating material to 70 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 70 ~ 80 ℃, in 1 ~ 2 hour, dropwise.Continuation is at 70 ~ 80 ℃ of reactions 1 hour, cooling discharge.Products therefrom is light yellow clarifying liquid body, and its main performance index is: viscosity is 400 mPa.s (25 ℃), and amine value is 270 mgKOH/g.
Embodiment 2
In the there-necked flask with whipping appts and thermometer, add the butylglycidyl ether of 20 parts and the ethylene glycol monobutyl ether of 20 parts, start stirring, heating material to 70 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 23 parts in the Meng of 37 parts, start stirring, by heating material to 70 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 7080 ℃, in 12 hours, dropwise.Continuation is at 7080 ℃ of reactions 1 hour, cooling discharge.Products therefrom is achromaticity and clarification liquid, and viscosity is 36 mPa.s (25 ℃), and amine value is 420 mgKOH/g.
Embodiment 3
In the there-necked flask with whipping appts and thermometer, add the Bisphenol F type Racemic glycidol ethers diepoxides DER354 of 15 parts and the ethylene glycol monobutyl ether of 23 parts, start stirring, heating material to 70 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 20 parts in the Meng of 42 parts, start stirring, by heating material to 70 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 70 ~ 80 ℃, in 1 ~ 2 hour, dropwise.Continuation is at 70 ~ 80 ℃ of reactions 1 hour, cooling discharge.Products therefrom is light yellow clarifying liquid body, and its main performance index is: viscosity is 230 mPa.s (25 ℃), and amine value is 282 mgKOH/g.
Embodiment 4
In the there-necked flask with whipping appts and thermometer, add the neodecanoic acid glycidyl ester of 20 parts and the ethylene glycol monobutyl ether of 20 parts, start stirring, heating material to 70 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 23 parts in the Meng of 37 parts, start stirring, by heating material to 70 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 7080 ℃, in 12 hours, dropwise.Continuation is at 7080 ℃ of reactions 1 hour, cooling discharge.Products therefrom is achromaticity and clarification liquid, and viscosity is 67 mPa.s (25 ℃), and amine value is 350 mgKOH/g.
Embodiment 5
In the there-necked flask with whipping appts and thermometer, add the bisphenol A-type glycidyl ester class diepoxides E-51 of 16 parts and the ethylene glycol monobutyl ether of 23 parts, start stirring, heating material to 72 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 21 parts in the Meng of 40 parts, start stirring, by heating material to 72 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 70 ℃, in 1.6 hours, dropwise.Continuation is at 74 ℃ of reactions 1 hour, cooling discharge.Products therefrom is light yellow clarifying liquid body, and its main performance index is: viscosity is 430 mPa.s (25 ℃), and amine value is 250 mgKOH/g.
Embodiment 6
In the there-necked flask with whipping appts and thermometer, add the bisphenol A-type glycidyl ester class diepoxides E-51 of 18 parts and the ethylene glycol monobutyl ether of 21 parts, start stirring, heating material to 76 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 20 parts in the Meng of 36 parts, start stirring, by heating material to 76 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 80 ℃, in 1 hour, dropwise.Continuation is at 70 ℃ of reactions 2 hours, cooling discharge.Products therefrom is light yellow clarifying liquid body, and its main performance index is: viscosity is 480 mPa.s (25 ℃), and amine value is 235 mgKOH/g.
Embodiment 7
In the there-necked flask with whipping appts and thermometer, add the bisphenol A-type glycidyl ester class diepoxides E-51 of 20 parts and the ethylene glycol monobutyl ether of 20 parts, start stirring, heating material to 80 is ℃ stand-by.In four-hole bottle at another with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 21 parts in the Meng of 34 parts, start stirring, by heating material to 80 ℃.Then the material in aforementioned there-necked flask is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 78 ℃, in 1.4 hours, dropwise.Continuation is at 74 ℃ of reactions 1.5 hours, cooling discharge.Products therefrom is light yellow clarifying liquid body, and its main performance index is: viscosity is 505 mPa.s (25 ℃), and amine value is 205 mgKOH/g.
Epoxy resin solidifying agent disclosed by the invention and method of modifying thereof, by carrying out addition reaction with epoxy compounds and excessive alkane diamines in the Meng, obtain the affixture of alkane diamines in the Meng, thereby reduced the toxicity of solidifying agent, improve the consistency with epoxy resin, improved the performance of the anti-albefactions of epoxy resin goods, made the solidifying agent safety in utilization of epoxy resin better, the harm of reduction to operation user of service, quality and the quality stability of the epoxy resin after raising is solidified.Add ethylene glycol monobutyl ether to play as non-activated thinner and softening agent the low viscous effect of falling.Because it has aliphatic cyclic amine lighter color, tint retention is good, and the advantage that gloss is high is especially suitable for use as the solidifying agent of epoxies sizing agent and coating.With the Meng alkane diamine curing agent compare, there is viscosity low, lighter color, toxicity are low, without excitatory advantage, during with its cured epoxy resin, thermal discharge is little, and the serviceable time is long, is difficult for moisture absorption whiting, goods glossiness is high, and chemical resistant properties is good, simultaneously can be in envrionment temperature and low-temperature curing.
The disclosed technique means of the present invention program is not limited only to the disclosed technique means of above-mentioned technique means, also comprises the technical scheme being comprised of above technical characterictic arbitrary combination.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (4)
1. an epoxy resin solidifying agent, it is characterized in that: described epoxy resin solidifying agent is by alkane diamines in the Meng, epoxy compounds, ethylene glycol monobutyl ether forms, each constituent content (meter by weight) alkane diamines 34-50 weight part in the Meng, epoxy compounds 10-20 weight part, ethylene glycol monobutyl ether 40-45 weight part; Wherein epoxy compounds is the compound that contains one or two glycidyl ether.
2. the method for modifying of an epoxy resin solidifying agent, it is characterized in that: comprise the steps the first step: in the there-necked flask with whipping appts and thermometer, add the epoxy compounds of 10 20 weight parts and the ethylene glycol monobutyl ether of 20-23 weight part, start stirring, by heating material to T
1℃ stand-by; Second step: in the four-hole bottle with whipping appts, thermometer and constant pressure funnel, add the alkane diamines and the ethylene glycol monobutyl ether of 20-22 weight part in the Meng of 34-50 weight part, start stirring, by heating material to T
2℃, the material of the first step gained is dripped into and reacted by constant pressure funnel, control rate of addition reaction is carried out at 70-80 ℃, in 1-2 hour, dropwise; The 3rd step: continue at 70-80 ℃ of reaction 1-2 hour, cooling discharge.
3. the method for modifying of epoxy resin solidifying agent according to claim 2, is characterized in that: 60 ℃≤T
1=T
2≤ 80 ℃.
4. the method for modifying of epoxy resin solidifying agent according to claim 2, is characterized in that: during the 3rd step cooling discharge, cooling adopts programmed cooling, and cooling rate is 8-10 ℃/min.
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| CN201410247247.3A CN104072726A (en) | 2014-06-06 | 2014-06-06 | Epoxy resin curing agent and modification method thereof |
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| CN201410247247.3A CN104072726A (en) | 2014-06-06 | 2014-06-06 | Epoxy resin curing agent and modification method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348489A (en) * | 2015-12-16 | 2016-02-24 | 太仓康盛化工有限公司 | Self-emulsified epoxy resin curing agent |
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| CN102898624A (en) * | 2012-10-29 | 2013-01-30 | 上海维度化工科技有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN103224611A (en) * | 2013-05-15 | 2013-07-31 | 程梦喜 | Modified alicyclic amine curing agent and preparation method thereof |
| CN103554438A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Preparation method of modified epoxy hardener for reducing bleaching |
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2014
- 2014-06-06 CN CN201410247247.3A patent/CN104072726A/en active Pending
Patent Citations (4)
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| 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 |
| CN102898624A (en) * | 2012-10-29 | 2013-01-30 | 上海维度化工科技有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN103224611A (en) * | 2013-05-15 | 2013-07-31 | 程梦喜 | Modified alicyclic amine curing agent and preparation method thereof |
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| CN105348489A (en) * | 2015-12-16 | 2016-02-24 | 太仓康盛化工有限公司 | Self-emulsified epoxy resin curing agent |
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