CN103224611A - Modified alicyclic amine curing agent and preparation method thereof - Google Patents
Modified alicyclic amine curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN103224611A CN103224611A CN2013101794102A CN201310179410A CN103224611A CN 103224611 A CN103224611 A CN 103224611A CN 2013101794102 A CN2013101794102 A CN 2013101794102A CN 201310179410 A CN201310179410 A CN 201310179410A CN 103224611 A CN103224611 A CN 103224611A
- Authority
- CN
- China
- Prior art keywords
- parts
- preparation
- epoxy
- solidifying agent
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention relates to a modified alicyclic amine curing agent and a preparation method thereof. The modified alicyclic amine curing agent is a product which is prepared by reaction of 37-42 parts of 1,3-hexamethylene dimethylamine (1,3-BAC), 12-16 parts of epoxy resin and 41-51 parts of benzyl alcohol in parts by weight; and the viscosity of the product at 25 DEG C is 100-200mPa.S, the amine value is 340-450mgKOH/g, and the active hydrogen equivalent is 100-145g/eq. The preparation method comprises the following steps of: adding the epoxy resin and the benzyl alcohol to a reactor, and uniformly stirring for standby application; adding the 1,3-BAC to another reactor, heating to 60 DEG C, then dropwise adding the previous materials to the 1,3-BAC for reaction, finishing dropwise addition at 60-70 DEG C within 1 to 2 hours, continuously reacting for 1 hours at 60-70 DEG C, and cooling and discharging. The modified alicyclic amine curing agent has low heat release and good compatibility with the epoxy resin and is difficult in moisture absorption and whitening; and after the epoxy resin is cured by the curing agent, the epoxy resin has a smooth surface without water waves and high glossiness and the like.
Description
Technical field
The invention belongs to the composition epoxy resin technical field, be specifically related to aliphatic cyclic amine solidifying agent of a kind of modification and preparation method thereof, it is a kind of low viscosity that its feature replaces the IPDA preparation, and the aliphatic cyclic amine solidifying agent of this modification has solvent-free characteristics, can replace IPDA as solidifying agent.
Background technology
Resins, epoxy is a kind of important thermosetting resin, has that cohesive strength height, shrinking percentage are little, good performances such as excellent dielectric properties and resistance toheat, is widely used in electronics, sizing agent, coating, building, fields such as national defence.
Resins, epoxy is given Resins, epoxy paint and is had good performance, Resins, epoxy and solidifying agent must be carried out the molecule of cross-linked structure.Epoxy curing agent is of a great variety, diethylenetriamine commonly used, aliphatic polyamine and IPDA such as triethylene tetramine, alicyclic polyamines such as AEP.Above solidifying agent all has very high reactive behavior, low-viscosity, and chemical resistant properties is good, and dielectric properties are good, and are all normal temperature solidified; But this class solidifying agent is caused generally directly not using by following shortcoming, must use after the modification.Shortcoming is as follows:
1. the low proportioning difference of reactive hydrogen equivalent is big
2. thermal discharge is big
3. toxicity stimulates big
4. moisture absorption is big
5. height polarity can cause shrinkage cavity to solidified surface, defectives such as orange peel whiting
Isophorone diamine IPDA(chemical name: 3-aminomethyl-3,5,5-trimethylcyclohexyl amine) be a kind of low color (＜No. 1, Gardner's method=low viscosity, the aliphatic cyclic amine diamines that has better thermotolerance, weathering resistance than straight chain aliphatic polyamine, an amido is connected on the alicyclic ring by methyl, another directly is connected on the alicyclic ring, reduced the reactive behavior of amido, normal temperature is following and epoxy reaction is slow, generally obtain good water-fast stain, oil resistant face and chemical-resistant by modification, low-viscosity, the solvent-free high gloss solidifying agent of solidified under the normal temperature.It is good to have with the Resins, epoxy resin compatible, the characteristic that shrinking percentage is little, widespread use civil engineering and decorative coating.But IPDA price height, not anti-albefaction, cause modification after cost improve greatly.
Summary of the invention
It is low to the present invention seeks to invent a kind of cost, has that viscosity is low, a lighter color, low, the anti-albefaction of toxicity, anti-solvent wiping; Be used for epoxy resin cure, solidify smooth, smooth, the non-whitening in back; Especially can replace IPDA as modification aliphatic cyclic amine solidifying agent.
This modification aliphatic cyclic amine solidifying agent is by by 1, and 3-hexamethylene dimethylamine and Resins, epoxy carry out addition reaction and forms, 1, and its solidifying agent of 3-hexamethylene dimethylamine is because of molecular structure and IPDA solidifying agent and similar.
1,3-hexamethylene dimethylamine molecular formula is: C
8H
18N
2
In this solidifying agent-NH
2After carrying out addition reaction with the Resins, epoxy group, make that the solidifying agent after the modification has anti-xanthochromia, heat shock resistance, high strength, many good characteristics such as good toughness.Moisture resistance and processing property improve greatly simultaneously.
Resins, epoxy is as a kind of medium and 1, and 3-hexamethylene dimethylamine carries out addition reaction, reduces the unhindered amina of solidifying agent, makes 1, and 3-hexamethylene dimethylamine is active to be reduced.
Phenylcarbinol is regulated the viscosity of solidifying agent as a kind of non-activated thinner.
Technical scheme:
A kind of modification aliphatic cyclic amine solidifying agent, be to be 1 by weight meter raw material, 3-hexamethylene dimethylamine (1,3-BAC) 37 ~ 42 parts, 12 ~ 16 parts of Resins, epoxy, 42 ~ 51 parts of reacted products of phenylcarbinol, viscosity is that 100 ~ 200 mPa.s, amine value are that 340 ~ 450mgKOH/g, reactive hydrogen equivalent are 100 ~ 145g/eq in the time of its 25 ℃.
Wherein Resins, epoxy can be bisphenol-A liquid epoxy resin, and the epoxy equivalent (weight) of its standard (EEW) is 185 ~ 190g/eq.
A kind of preparation method of modification aliphatic cyclic amine solidifying agent is characterized in that realizing by the following step:
The first step: in band whipping appts reactor, be incorporated as 12 ~ 16 parts of Resins, epoxy, 42 ~ 51 parts of phenylcarbinols start agitator, and setting mixing speed is 100R/M(rev/min), material is heated to 60 ~ 70 ℃; It is stand-by that material is stirred;
Second step: in band whipping appts reactor, add 1,37 ~ 42 parts of startup agitators of 3-BAC, the setting mixing speed is 150R/M, and material is heated to 60 ℃; The first step gained material added by dropping funnel react, the control rate of addition makes temperature of reaction maintain 60 ~ 70 ℃ to carry out, dropwise in 1 ~ 2h;
The 3rd step: continuing is being under the 150R/M with the mixing speed, reacts 1 hour at 60 ~ 70 ℃, and cooling discharge then obtains the aliphatic cyclic amine solidifying agent of modification.
The reactor that the first step of the present invention, second step use has thermometer.
The present invention's second step material dropping is that constant voltage drips.
Modification aliphatic cyclic amine solidifying agent of the present invention passes through by 1, and 3-BAC and Resins, epoxy carry out addition reaction, thereby improve the operability of solidifying agent, with the anti-albefaction performance of epoxy resin-based paint; Because it is low that this solidifying agent has a viscosity, lighter color, high gloss, characteristics such as environmental protection are particularly suitable for the epoxide terrace of usefulness and the solidifying agent of ornaments polyester resin.Its main performance index:
Viscosity (25 ℃, mpa.s) 100 ~ 200
Amine value (mgKOH/g) 340 ~ 450
Reactive hydrogen equivalent (g/eq) 100 ~ 145
Hectogram standard epoxy (EEW=190 g/eq) consumption is 45 ~ 50 grams.
Embodiment
The invention will be further described below in conjunction with specific examples
Embodiment 1
In the there-necked flask of belt stirrer and thermometer, add 51 parts of 12 parts of Resins, epoxy and phenylcarbinols.Start agitator, it is stand-by that material is stirred.In the four-hole boiling flask of band whipping appts, thermometer, constant pressure funnel, add 1,37 parts of startup agitators of 3-BAC are heated to 60 ℃ with material; The first step gained material added by dropping funnel react, the control rate of addition makes temperature of reaction maintain 60 ~ 70 ℃ to carry out, dropwise in 1 ~ 2h.Continuation is at 60 ~ 70 ℃ of reaction 1h, cooling discharge.Products obtained therefrom is
Color: colourless or light yellow transparent liquid
Viscosity (25 ℃, mPa.s) 125
Amine value (mgKOH/g) 365
Reactive hydrogen equivalent (g/eq) 145
Hectogram standard epoxy (EEW=190g/eq) hardener dose is 50 grams.
Allocate curing in proportion with above-mentioned example 1 gained solidifying agent and Resins, epoxy; Paint film color even, no albefaction, smooth smooth, hardness height, transparency height.
Embodiment 2
In the there-necked flask of belt stirrer and thermometer, add 42 parts of 16 parts of Resins, epoxy and phenylcarbinols.Start agitator, it is stand-by that material is stirred.In the four-hole boiling flask of band whipping appts, thermometer, constant pressure funnel, add 1,42 parts of startup agitators of 3-BAC are heated to 60 ℃ with material; The first step gained material added by dropping funnel react, the control rate of addition makes temperature of reaction maintain 60 ~ 70 ℃ to carry out, dropwise in 1 ~ 2h.Continuation is at 60 ~ 70 ℃ of reaction 1h, cooling discharge.Products obtained therefrom is
Color: colourless or light yellow transparent liquid
Viscosity (25 ℃, mPa.s) 137
Amine value (mgKOH/g) 415
Reactive hydrogen equivalent (g/eq) 115
Hectogram standard epoxy (EEW=190 g/eq) hardener dose is 55 grams.
Allocate curing in proportion with above-mentioned example 1 gained solidifying agent and Resins, epoxy; Paint film color even, no albefaction, smooth smooth, hardness height, transparency height.
Claims (6)
1. modification aliphatic cyclic amine solidifying agent, be to be 1 by weight meter raw material, 3-hexamethylene dimethylamine (1,3-BAC) 37 ~ 42 parts, 12 ~ 16 parts of Resins, epoxy, 42 ~ 51 parts of reacted products of phenylcarbinol, viscosity is that 100 ~ 200 mPa.s, amine value are that 340 ~ 450mgKOH/g, reactive hydrogen equivalent are 100 ~ 145g/eq in the time of its 25 ℃.
2. solidifying agent as claimed in claim 1 is characterized in that described Resins, epoxy is bisphenol-A liquid epoxy resin, and the epoxy equivalent (weight) of its standard is 185 ~ 190.
3. the preparation method of a modification aliphatic cyclic amine solidifying agent is characterized in that realizing by the following step:
The first step: in band whipping appts reactor, be incorporated as 12 ~ 16 parts of Resins, epoxy, 42 ~ 51 parts of phenylcarbinols start agitator, and setting mixing speed is 100 rev/mins, and material is heated to 60 ~ 70 ℃ material is stirred, and cools off stand-by;
Second step: in band whipping appts reactor, add 1,37 ~ 42 parts of startup agitators of 3-BAC, the setting mixing speed is 150R/M, and material is heated to 60 ℃; The first step gained material added by dropping funnel react, the control rate of addition makes temperature of reaction maintain 60 ~ 70 ℃ to carry out, dropwise in 1 ~ 2h;
The 3rd step: continuing is being 150 rev/mins with mixing speed, reacts 1 hour at 60 ~ 70 ℃, and cooling discharge then obtains the aliphatic cyclic amine solidifying agent of modification.
4. preparation method as claimed in claim 3 is characterized in that described the first step reactor has thermometer.
5. preparation method as claimed in claim 3 is characterized in that described second stage reactor has thermometer.
6. preparation method as claimed in claim 3 is characterized in that the described second step material dropping is that constant voltage drips.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101794102A CN103224611A (en) | 2013-05-15 | 2013-05-15 | Modified alicyclic amine curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101794102A CN103224611A (en) | 2013-05-15 | 2013-05-15 | Modified alicyclic amine curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103224611A true CN103224611A (en) | 2013-07-31 |
Family
ID=48835268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101794102A Pending CN103224611A (en) | 2013-05-15 | 2013-05-15 | Modified alicyclic amine curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103224611A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351580A (en) * | 2013-08-05 | 2013-10-16 | 安徽康瑞鑫电子科技有限公司 | Preparation method of epoxy resin pouring sealant |
| CN103361019A (en) * | 2013-08-05 | 2013-10-23 | 安徽康瑞鑫电子科技有限公司 | Epoxy resin pouring sealant |
| 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 |
| CN104072726A (en) * | 2014-06-06 | 2014-10-01 | 苏州之诺新材料科技有限公司 | Epoxy resin curing agent and modification method thereof |
| CN104356362A (en) * | 2014-11-23 | 2015-02-18 | 桂林理工大学 | Preparation method of modified alicyclic amine curing agent |
| CN107602819A (en) * | 2017-08-17 | 2018-01-19 | 湖北绿色家园材料技术股份有限公司 | A kind of low cost, high rigidity, the preparation method of high glaze epoxy stone material surface adhesive curing agent |
| CN107964088A (en) * | 2016-10-18 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent |
| CN108017776A (en) * | 2017-12-26 | 2018-05-11 | 湖南神力铃胶粘剂制造有限公司 | A kind of modified alicyclic ring amine hardener and preparation method thereof |
| CN108358509A (en) * | 2018-05-04 | 2018-08-03 | 厦门百安兴新材料有限公司 | A kind of epoxy color sand joint trimming agent and preparation method thereof |
| CN110240693A (en) * | 2019-07-10 | 2019-09-17 | 深圳市前海博扬研究院有限公司 | Polyamine curing agent and preparation method and composition epoxy resin |
| CN111748306A (en) * | 2020-06-17 | 2020-10-09 | 雅安市弘利展化工有限公司 | Curing agent for medical material pouring sealant and preparation method thereof |
| CN113150700A (en) * | 2021-03-25 | 2021-07-23 | 湖南神力铃胶粘剂制造有限公司 | Epoxy stone repair face adhesive with yellowing resistance, low viscosity and hydrophilic curing and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045809A (en) * | 2007-04-20 | 2007-10-03 | 常熟佳发化学有限责任公司 | Epoxy resin composite, and preparation method thereof and using method thereof |
| CN101798378A (en) * | 2009-02-05 | 2010-08-11 | 魏庆梅 | Transparent epoxy resin curing agent |
| CN102936478A (en) * | 2012-12-05 | 2013-02-20 | 湖南神力铃胶粘剂制造有限公司 | Elastic bicomponent normal-temperature cured epoxy resin adhesive and preparation method thereof |
-
2013
- 2013-05-15 CN CN2013101794102A patent/CN103224611A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045809A (en) * | 2007-04-20 | 2007-10-03 | 常熟佳发化学有限责任公司 | Epoxy resin composite, and preparation method thereof and using method thereof |
| CN101798378A (en) * | 2009-02-05 | 2010-08-11 | 魏庆梅 | Transparent epoxy resin curing agent |
| CN102936478A (en) * | 2012-12-05 | 2013-02-20 | 湖南神力铃胶粘剂制造有限公司 | Elastic bicomponent normal-temperature cured epoxy resin adhesive and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351580B (en) * | 2013-08-05 | 2015-06-17 | 安徽康瑞鑫电子科技有限公司 | Preparation method of epoxy resin pouring sealant |
| CN103361019A (en) * | 2013-08-05 | 2013-10-23 | 安徽康瑞鑫电子科技有限公司 | Epoxy resin pouring sealant |
| CN103351580A (en) * | 2013-08-05 | 2013-10-16 | 安徽康瑞鑫电子科技有限公司 | Preparation method of epoxy resin pouring sealant |
| CN103361019B (en) * | 2013-08-05 | 2015-02-04 | 安徽康瑞鑫电子科技有限公司 | Epoxy resin pouring sealant |
| 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 |
| CN104072726A (en) * | 2014-06-06 | 2014-10-01 | 苏州之诺新材料科技有限公司 | Epoxy resin curing agent and modification method thereof |
| CN104356362A (en) * | 2014-11-23 | 2015-02-18 | 桂林理工大学 | Preparation method of modified alicyclic amine curing agent |
| CN107964088A (en) * | 2016-10-18 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent |
| CN107602819A (en) * | 2017-08-17 | 2018-01-19 | 湖北绿色家园材料技术股份有限公司 | A kind of low cost, high rigidity, the preparation method of high glaze epoxy stone material surface adhesive curing agent |
| CN108017776A (en) * | 2017-12-26 | 2018-05-11 | 湖南神力铃胶粘剂制造有限公司 | A kind of modified alicyclic ring amine hardener and preparation method thereof |
| CN108358509A (en) * | 2018-05-04 | 2018-08-03 | 厦门百安兴新材料有限公司 | A kind of epoxy color sand joint trimming agent and preparation method thereof |
| CN108358509B (en) * | 2018-05-04 | 2021-06-01 | 厦门百安兴新材料有限公司 | Epoxy color sand crack beautifying agent and preparation method thereof |
| CN110240693A (en) * | 2019-07-10 | 2019-09-17 | 深圳市前海博扬研究院有限公司 | Polyamine curing agent and preparation method and composition epoxy resin |
| CN111748306A (en) * | 2020-06-17 | 2020-10-09 | 雅安市弘利展化工有限公司 | Curing agent for medical material pouring sealant and preparation method thereof |
| CN113150700A (en) * | 2021-03-25 | 2021-07-23 | 湖南神力铃胶粘剂制造有限公司 | Epoxy stone repair face adhesive with yellowing resistance, low viscosity and hydrophilic curing and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103224611A (en) | Modified alicyclic amine curing agent and preparation method thereof | |
| CN103224612B (en) | A kind of solvent-free self leveling epoxy resin curing agent and preparation method thereof | |
| CN107099021B (en) | Nitrogen-containing heterocycle epoxy hardener, composition and method | |
| CN103980463B (en) | A kind of epoxy resin solvent-free low-temperature solidified agent and preparation method thereof and application | |
| JP6177331B2 (en) | Curable composition based on epoxy resin without benzyl alcohol | |
| KR102129641B1 (en) | Ambient cure weatherable coatings | |
| CN112135855B (en) | Modified phenolic amine curing agent for epoxy resin composition and application thereof | |
| AU2017220532A1 (en) | Curing agent for low-emission epoxy resin compositions | |
| CN102782002A (en) | The use of linear triethylentetramine as curing agent for epoxy resins | |
| JPS6189219A (en) | Diethyltoluenediamine curing system and curable mixture containing the same | |
| JP2014524468A (en) | Cyclic carbonate monomers and polymers prepared therefrom | |
| CN103756610A (en) | Double-component yellowing resistance epoxy resin adhesive and preparation method thereof | |
| CN105331314A (en) | Weather-resistant epoxy glue as well as preparation method and applications thereof | |
| CN105229095A (en) | High solid content epoxypaint | |
| CN110382587B (en) | Method for preparing curing agent of low-emission epoxy resin composition | |
| CN101798378A (en) | Transparent epoxy resin curing agent | |
| CN110099944A (en) | Multiamide and amidoamines derived from hydroxy alkyl polyamines: the epoxy hardener having improved properties | |
| CN106939138B (en) | A kind of preparation method of antistripping oligomer waterborne epoxy coatings | |
| CN104718232A (en) | Adduct curing agents | |
| WO2014066450A2 (en) | Weatherable coatings | |
| CN105531317A (en) | Curable epoxy compositions | |
| TWI248448B (en) | Curing agent composition and curing epoxy resin composition | |
| CN101798379A (en) | Modified fatty amine curing agent | |
| CN115572235A (en) | Preparation method of cardanol aldehyde amine curing agent | |
| CN105793313A (en) | Epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130731 |