CN102603721A - Preparation method of triglycidyl isocyanurate - Google Patents
Preparation method of triglycidyl isocyanurate Download PDFInfo
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- CN102603721A CN102603721A CN2012100351884A CN201210035188A CN102603721A CN 102603721 A CN102603721 A CN 102603721A CN 2012100351884 A CN2012100351884 A CN 2012100351884A CN 201210035188 A CN201210035188 A CN 201210035188A CN 102603721 A CN102603721 A CN 102603721A
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Abstract
The invention relates to a preparation method of triglycidyl isocyanurate (I). The preparation method of triglycidyl isocyanurate is characterized by comprising the following steps: stirring triallyl isocyanurate in the presence of alcohol, acid carbonate and nitrile; adding 30% of hydrogen peroxide and stirring the mixture at 25-60 DEG C to keep the reaction for 6-10 hours, and then completing the reaction; performing aftertreatment on the reaction liquid to obtain the triglycidyl isocyanurate. The yield is more than 80.0%.
Description
Technical field
The present invention relates to a kind of preparation method of green of common powder paint solidifying agent, specifically is the preparation method of the green of triglycidyl isocyanurate, belongs to chemical production technical field.
Background technology
Cyanogen urea acid three-glycidyl ester, be called for short TGIC:
Cyanogen urea acid three-glycidyl ester is the solidifying agent of carboxyl-functional toner coating, and highly purified TGIC also has excellent electrical properties in high temperatures characteristics, can be used for making the electrical apparatus insulation material, printed wiring; Also can be used for veneer sheet and stabilizer for plastics.Because its good weatherability, thermostability is high, and mechanical property is superior, and its purposes very extensively.Though occurred the substitute of some TGIC systems in recent years on the market; Such as HAA system (CN100572472C), but substitute also is difficult to compare favourably with the TGIC system on the mechanical property of filming, weathering resistance at present, exists thick being coated with to be prone to produce pin hole; Xanthochromia is prone to problems such as dry linting easily.
The preparation method of cyanogen urea acid three-glycidyl ester (TGIC) at present commonly used generally adopt two step method (CN101367796B, CN101367796A, US3910908); [Ceng Guang is bright, three (epoxypropyl) chlorinated isocyanurates synthetic, thermosetting resin; 2003, (6): 12-14]; Preparation feedback is following:
Detailed process is following: (1) under the catalysis of quaternary ammonium salt, tricarbimide and epoxy chloropropane react 5～9h, the step midbody of winning with certain feed ratio under comparatively high temps; (2) drip caustic soda soln, ring closure reaction takes place, make TGIC.Though this method has technical maturity, the productive rate advantages of higher, this preparing method's reaction raw materials is held concurrently solvent epoxy chloropropane (ECH) need be excessive greatly, and belong to carcinogenic hazardous substance; The TGIC quality product of two step method has much room for improvement, and particularly epoxy residual quantity index is difficult to control, thereby has limited its purposes on electronic product.And adopt the cyanogen urea acid three-glycidyl ester (TGIC) of iso-cyanuric acid triallyl ester epoxidation preparation in the presence of ydrogen peroxide 50 not have chlorine residual, guaranteed the excellent electric performance of product.Less to the research report of this technology both at home and abroad at present, like Mu Chunming [applied chemistry, 2008 of HeFei University of Technology; 25 (9): 1090-1094] catalysis of employing manganese salt has been described, 50% hydrogen peroxide epoxidation iso-cyanuric acid triallyl ester (TAIC), productive rate 70%; But its product that obtains is a monocycle, dicyclo, trinucleated mixture [Mu Chunming; HeFei University of Technology's applied chemistry academic dissertation, 2008]; Preparation feedback is following:
The raw material iso-cyanuric acid triallyl ester (TAIC) that this method adopts is a kind of broad-spectrum fine chemical product, and just can manufacture latter stage in last century.The general following method of employing [Wang Fengyan, Shandong University's Master's thesis, 1999] preparation at present:
This method for preparing iso-cyanuric acid triallyl ester (TAIC) has raw material and generally is easy to get, advantages such as technical maturity, but seeing that the development of aftertreatment stripping technique; Then method [the Mu Chunming that adopt with propenyl chloride and isocyanuric acid direct reaction of present domestic factory more; HeFei University of Technology's applied chemistry academic dissertation, 2008] preparation, its technology is simple; Productive rate is high, and the preparation method is following:
USP (US3793321) equally also is to be feedstock production TGIC with iso-cyanuric acid triallyl ester (TAIC), is that 35% hydrogen peroxide-nitrile epoxidation systems prepares TGIC, yield 70% but it adopts.Its shortcoming is that this process using sodium hydroxide is controlled the pH value, and still exists some two keys not have complete epoxidation (US3793321) in the product.For yield and the purity that improves product, and reduce production costs, seek a kind of suitable large-scale industrialization production technique, the present invention adopts the preparation technology of a kind of new TGIC.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cyanogen urea acid three-glycidyl ester (I):
A kind of preparation method of cyanogen urea acid three-glycidyl ester; It is characterized in that may further comprise the steps: iso-cyanuric acid triallyl ester stirs in the presence of alcohol, acid carbonate and nitrile; Add 30% hydrogen peroxide in 25～60 ℃ of stirring reaction reaction 6～10h, reaction is finished; Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is greater than 80.0%.
Preparation is undertaken by following chemical reaction:
The nitrile that the object of the invention also provides is selected from a kind of in cyanobenzene, 2-chlorobenzonitrile, acetonitrile, 4-hydroxybenzene acetonitrile, benzyl cyanide, vinyl cyanide or the isopropyl cyanide.
The acid carbonate that the object of the invention also provides is selected from a kind of in bicarbonate of ammonia, sodium hydrogencarbonate or the saleratus; The acid carbonate consumption is 50～60% of iso-cyanuric acid triallyl ester (TAIC) quality.
The alcohol that the object of the invention also provides is selected from methyl alcohol, ethanol, propyl alcohol or butanols; Pure and mild iso-cyanuric acid triallyl ester (TAIC) mol ratio is 60～65: 1.
The object of the invention also provides the consumption of 30% hydrogen peroxide, it is characterized in that 30% hydrogen peroxide and iso-cyanuric acid triallyl ester (TAIC) mol ratio is 3～6: 1.
The present invention compared with prior art has following advantage:
1) the objective of the invention is to select for use the acid carbonate solid as buffer reagent, both regulated the pH value, form the hydrocarbonate system with 30% hydrogen peroxide effect again; Hydrocarbonate system and ydrogen peroxide 50-dual oxygenizement of nitrile system makes three two key oxidations of iso-cyanuric acid triallyl ester (TAIC) complete;
2) preparation method of the present invention adopts the preparation method TGIC of 30% hydrogen peroxide as oxidation iso-cyanuric acid triallyl ester (TAIC), and environmental protection is than 50%, 35% ydrogen peroxide 50 safety and reliability, more economical; The acid carbonate buffer system is little to equipment corrosion;
3) preparing method's of the present invention cyanogen urea acid three-glycidyl ester purity is high, and of light color, article are of fine quality, and yield is greater than 80.0% (literature value 70%).
Embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1
The preparation of cyanogen urea acid three-glycidyl ester
Methyl alcohol (50ml), bicarbonate of ammonia (0.07mol), iso-cyanuric acid triallyl ester (0.03mol), vinyl cyanide (0.09mol) stirred 15 minutes; Add 30% hydrogen peroxide (0.1mol) in 25～60 ℃ of stirring reaction 2h; Add 30% hydrogen peroxide 5g, continue reaction 6～8h, reaction is finished.Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is 80.1%, and fusing point is 103～115 ℃;
1H NMR (400MHz, CDCl
3) δ: 2.70～2.86 (m, 6H, 3 * CH
2), 3.27～3.28 (m, 3H, 3 * CH), 4.07～4.16 (m, 6H, 3 * CH
2).
Embodiment 2
The preparation of cyanogen urea acid three-glycidyl ester
Ethanol (50ml), saleratus (0.05mol), iso-cyanuric acid triallyl ester (0.03mol), acetonitrile (0.09mol) stirred 15 minutes; Add 30% hydrogen peroxide (0.1mol) in 25～60 ℃ of stirring reaction 2h; Add 30% hydrogen peroxide 5g, continue reaction 6～10h, reaction is finished.Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is 82.1%, and fusing point is 103～115 ℃;
1H NMR (400MHz, CDCl
3) δ: 2.71～2.85 (m, 6H, 3 * CH
2), 3.27～3.28 (m, 3H, 3 * CH), 4.08～4.16 (m, 6H, 3 * CH
2).
Embodiment 3
The preparation of cyanogen urea acid three-glycidyl ester
Ethanol (50ml), sodium hydrogencarbonate (0.05mol), iso-cyanuric acid triallyl ester (0.03mol), acetonitrile (0.09mol) stirred 15 minutes; Add 30% hydrogen peroxide (0.1mol) in 25～60 ℃ of stirring reaction 2h; Add 30% hydrogen peroxide 5g, continue reaction 9～10h, reaction is finished.Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is 81.2%, and fusing point is 103～115 ℃;
1H NMR (400MHz, CDCl
3) δ: 2.71～2.85 (m, 6H, 3 * CH
2), 3.27～3.28 (m, 3H, 3 * CH), 4.08～4.16 (m, 6H, 3 * CH
2).
Embodiment 4
The preparation of cyanogen urea acid three-glycidyl ester
Propyl alcohol (50ml), saleratus (0.05mol), iso-cyanuric acid triallyl ester (0.03mol), isopropyl cyanide (0.09mol) stirred 15 minutes; Add 30% hydrogen peroxide (0.1mol) in 25～60 ℃ of stirring reaction 2h; Add 30% hydrogen peroxide 5g, continue reaction 8～9h, reaction is finished.Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is 80.6%, and fusing point is 103～115 ℃;
1H NMR (400MHz, CDCl
3) δ: 2.71～2.85 (m, 6H, 3 * CH
2), 3.27～3.28 (m, 3H, 3 * CH), 4.08～4.16 (m, 6H, 3 * CH
2).
Embodiment 5
The preparation of cyanogen urea acid three-glycidyl ester
Methyl alcohol (50ml), saleratus (0.05mol), iso-cyanuric acid triallyl ester (0.03mol), 2-chlorobenzonitrile (0.09mol) stirred 15 minutes; Add 30% hydrogen peroxide (0.1mol) in 25～60 ℃ of stirring reaction 1.5h; Add 30% hydrogen peroxide 5g; Continue reaction 6～8h, reaction is finished.Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is 82.5%, and fusing point is 103～115 ℃;
1H NMR (400MHz, CDCl
3) δ: 2.71～2.85 (m, 6H, 3 * CH
2), 3.27～3.28 (m, 3H, 3 * CH), 4.08～4.16 (m, 6H, 3 * CH
2).
Claims (5)
1. the preparation method of the cyanogen urea shown in chemical structural formula I acid three-glycidyl ester:
The preparation method who it is characterized in that cyanogen urea acid three-glycidyl ester may further comprise the steps: iso-cyanuric acid triallyl ester stirs in the presence of alcohol, acid carbonate and nitrile, and the hydrogen peroxide of adding 30% is in 25～60 ℃ of stirring reactions reaction 6～10h, and reaction is finished; Reaction solution obtains cyanogen urea acid three-glycidyl ester through aftertreatment, and yield is greater than 80.0%; Preparation is undertaken by following chemical reaction:
2. the described nitrile of claim 1 is selected from a kind of in cyanobenzene, 2-chlorobenzonitrile, acetonitrile, 4-hydroxybenzene acetonitrile, benzyl cyanide, vinyl cyanide or the isopropyl cyanide.
3. the described acid carbonate of claim 1 is selected from a kind of in bicarbonate of ammonia, sodium hydrogencarbonate or the saleratus; The acid carbonate consumption is 50～60% of iso-cyanuric acid triallyl ester (TAIC) quality.
4. the described alcohol of claim 1 is selected from methyl alcohol, ethanol, propyl alcohol or butanols; Pure and mild iso-cyanuric acid triallyl ester (TAIC) mol ratio is 60～65: 1.
5. the consumption of described 30% hydrogen peroxide of claim 1 is characterized in that 30% hydrogen peroxide and iso-cyanuric acid triallyl ester (TAIC) mol ratio is 3～6: 1.
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| CN2012100351884A CN102603721A (en) | 2012-02-17 | 2012-02-17 | Preparation method of triglycidyl isocyanurate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014065239A1 (en) * | 2012-10-25 | 2014-05-01 | 日産化学工業株式会社 | Method for producing epoxy compound |
| CN106588896A (en) * | 2016-12-15 | 2017-04-26 | 湖南方锐达科技有限公司 | Method for preparing triglycidyl isocyanurate (TGIC) |
| CN112500399A (en) * | 2020-12-02 | 2021-03-16 | 黄山华惠科技有限公司 | Low-chlorine ECH-residue-free TGIC curing agent and preparation method thereof |
| CN114958156A (en) * | 2022-06-14 | 2022-08-30 | 深圳市华霖技术咨询服务有限公司 | Preparation method and application of coating curing agent |
| CN114989150A (en) * | 2022-03-21 | 2022-09-02 | 安徽工业大学 | Triglycidyl isocyanurate and preparation method and application thereof |
| CN115521296A (en) * | 2022-10-26 | 2022-12-27 | 东华大学 | Preparation method of epoxy compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793321A (en) * | 1970-07-02 | 1974-02-19 | Ciba Geigy Ag | Process for the manufacture of triglycidylisocyanurate |
-
2012
- 2012-02-17 CN CN2012100351884A patent/CN102603721A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793321A (en) * | 1970-07-02 | 1974-02-19 | Ciba Geigy Ag | Process for the manufacture of triglycidylisocyanurate |
Non-Patent Citations (1)
| Title |
|---|
| 慕春明: "基于异氰尿酸的异氰尿酸三缩水甘油酯和三(三溴苯氧基)异氰尿酸酯的合成研究", 《中国优秀硕士学位论文全文数据库》, 17 October 2008 (2008-10-17), pages 19 - 22 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014065239A1 (en) * | 2012-10-25 | 2014-05-01 | 日産化学工業株式会社 | Method for producing epoxy compound |
| KR20150070190A (en) * | 2012-10-25 | 2015-06-24 | 닛산 가가쿠 고교 가부시키 가이샤 | Method for producing epoxy compound |
| CN104797576A (en) * | 2012-10-25 | 2015-07-22 | 日产化学工业株式会社 | Method for producing epoxy compound |
| JPWO2014065239A1 (en) * | 2012-10-25 | 2016-09-08 | 日産化学工業株式会社 | Method for producing epoxy compound |
| US9464074B2 (en) | 2012-10-25 | 2016-10-11 | Nissan Chemical Industries, Ltd. | Method for producing epoxy compound |
| KR102126788B1 (en) * | 2012-10-25 | 2020-06-25 | 닛산 가가쿠 가부시키가이샤 | Method for producing epoxy compound |
| CN104797576B (en) * | 2012-10-25 | 2018-05-01 | 日产化学工业株式会社 | The manufacture method of epoxide |
| TWI643852B (en) * | 2012-10-25 | 2018-12-11 | 日商日產化學工業股份有限公司 | Production method for epoxy compound |
| CN106588896B (en) * | 2016-12-15 | 2019-01-04 | 湖南方锐达科技有限公司 | A kind of preparation method of isocyanuric acid three-glycidyl ester |
| CN106588896A (en) * | 2016-12-15 | 2017-04-26 | 湖南方锐达科技有限公司 | Method for preparing triglycidyl isocyanurate (TGIC) |
| CN112500399A (en) * | 2020-12-02 | 2021-03-16 | 黄山华惠科技有限公司 | Low-chlorine ECH-residue-free TGIC curing agent and preparation method thereof |
| CN112500399B (en) * | 2020-12-02 | 2024-03-12 | 黄山华惠科技有限公司 | Low-chlorine ECH-residue-free TGIC curing agent and preparation method thereof |
| CN114989150A (en) * | 2022-03-21 | 2022-09-02 | 安徽工业大学 | Triglycidyl isocyanurate and preparation method and application thereof |
| CN114989150B (en) * | 2022-03-21 | 2024-05-17 | 安徽工业大学 | Triglycidyl isocyanurate and preparation method and application thereof |
| CN114958156A (en) * | 2022-06-14 | 2022-08-30 | 深圳市华霖技术咨询服务有限公司 | Preparation method and application of coating curing agent |
| CN115521296A (en) * | 2022-10-26 | 2022-12-27 | 东华大学 | Preparation method of epoxy compound |
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Application publication date: 20120725 |