CN102887868A - Preparation method of triallyl isocyanurate - Google Patents
Preparation method of triallyl isocyanurate Download PDFInfo
- Publication number
- CN102887868A CN102887868A CN2012103443981A CN201210344398A CN102887868A CN 102887868 A CN102887868 A CN 102887868A CN 2012103443981 A CN2012103443981 A CN 2012103443981A CN 201210344398 A CN201210344398 A CN 201210344398A CN 102887868 A CN102887868 A CN 102887868A
- Authority
- CN
- China
- Prior art keywords
- triallyl isocyanurate
- isocyanurate
- catalyst
- preparation
- solvent
- 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.)
- Granted
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the synthesis field of triallyl isocyanurate, and specifically provides a method for preparing triallyl isocyanurate by using a catalytic system. The isocyanurate and a catalyst are added into solvent. Chloropropene is dropwise added under the temperature of 70-105 DEG C for reaction. After reacting for 4-8 hours, the reactant is cooled to room temperature and filtered to remove solid phases. The filtrate subjected to solvent recovery is distilled under 113-115 DEG C/ 133.3Pa to obtain the triallyl isocyanurate product, wherein the catalyst is the catalytic system of a copper catalyst and a phase transfer catalyst. According to the invention, a solvent method is adopted, and no water is brought in the reaction solution, so that the raw material chloropropene cannot be hydrolysized, the excessive chloropropene can be recycled at the end of the reaction, and the triallyl isocyanurate product obtained by the reaction has good quality.
Description
Technical field
The present invention relates to the synthetic field of triallyl isocyanurate, a kind of method that adopts catalyst system to prepare triallyl isocyanurate specifically is provided.
Background technology
Triallyl isocyanurate (hereinafter to be referred as TAIC), formal name used at school 1,3,5-triallyl-guanamine, 4,6-triketone is a kind of high molecular monomer that contains the multi-functional olefinic of fragrant heterocycle that grew up in the 1980's, be a kind of broad-spectrum fine chemical product, it can cooperate the organo-peroxide such as DCP to be used for the crosslinked of the thermoplastic materials such as polyolefine, polyvinyl chloride, polyester, polymeric amide, ethylene-propylene rubber(EPR), silicon rubber; The triazine structure of its uniqueness can improve the anti-ventilation property of thermotolerance, physical strength and oil resistant of crosslinked products; It also can become transparent, hard, wear-resisting superpolymer with other polymerization of unsaturated monomers, as the carrier of liquid and gas chromatographic column; Product after it and the bromine addition is a kind of new polymers fire retardant.Character is very stable under the TAIC normal temperature, can at room temperature store for a long time, has efficient, nontoxic, the advantages such as cross-linking density is high, easy storage, easy transportation, is very widely novel high polymer material auxiliary agent of a kind of purposes.
Triallyl isocyanurate (TAIC) is mainly by three kinds of method preparations at present:
US Patent No. 3,322, in 761 the method, triallyl isocyanurate (TAIC) is by in the presence of catalyzer, and cyanuric acid, propenyl chloride and aqueous sodium hydroxide solution reaction generate.The shortcoming of the method is that hydrolysis and product have a larger impurity peaks by liquid phase analysis easily in that the raw material propenyl chloride is arranged under the water condition.
US Patent No. 4,196 in 289 the method, adopts alkali metal cyanate and propenyl chloride in solvent, the about 130 ℃ of lower reactions of temperature.Be characterized in same reaction, carrying out cyanate Cheng Huan and propenyl chloride substitution reaction, except can generating triallyl isocyanurate (TAIC) product, also may generate the not allyl cyanide acid esters of Cheng Huan, so various impurity are more in the product, the purification separation difficulty.
The preparation method of US Patent No. 2009/0312545A1 is that the Claisen of triallyl cyanurate (TAC) resets.Good product quality in the method, its raw material TAC comes from the reaction of Cynuric Chloride and vinyl carbinol, but at home only the preparation cost of TAC surpassed above-mentioned two kinds of methods, be not suitable for suitability for industrialized production.
Summary of the invention
The problem that exists for solving above-mentioned prior art, the present invention aims to provide a kind of sodium isocyanurate that carries out and reacts the method for preparing triallyl isocyanurate with propenyl chloride in organic solvent under catalyst action.This preparation method has the product yield height, the characteristics of good product quality.
Particularly, the contriver provides following technical scheme:
A kind of preparation method of triallyl isocyanurate comprises:
Sodium isocyanurate and catalyzer are added in the solvent, react at 70～105 ℃ of lower propenyl chlorides that drip of temperature, react and be cooled to room temperature after 4～8 hours, remove by filter solid phase, filtrate behind the recovery solvent distills out the triallyl isocyanurate product under 113～115 ℃/133.3Pa, wherein: described catalyzer is the catalyst system of copper catalyst and phase-transfer catalyst.
As preferably, among the present invention, described solvent is aprotic polar solvent, is DMF, methyl-sulphoxide, N-methylacetamide or acetonitrile.
As preferably, among the present invention, described copper catalyst is copper powder or cuprous chloride, and consumption is the 0.1-2.0 % by weight based on sodium isocyanurate.
As preferably, among the present invention, described phase-transfer catalyst is triethylamine, Tributylamine or pyridine, and consumption is the 0.5-5.0 % by weight based on sodium isocyanurate.
Compared with prior art, the present invention also has the following advantages:
The present invention adopts solvent method to react, and does not bring moisture in the reaction solution into, so the raw material propenyl chloride can not be hydrolyzed, and the excess chlorine propylene can reclaim after reaction finishes, triallyl isocyanurate (TAIC) good product quality that reaction obtains.
The present invention adopts tertiary amine as phase-transfer catalyst, and product yield is high, and low price, suitability for industrialized production.
The product that the present invention synthesizes is analyzed by mass spectrum (MS), and molecular weight is 249, and structural formula coincide with the structural formula of composing triallyl isocyanurate in the storehouse, and its structural formula is:
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.Method among the following embodiment if no special instructions, is the ordinary method of this area.
Embodiment 1
Sodium isocyanurate 195g and 600g acetonitrile are added in the four-hole boiling flask with prolong, add simultaneously cuprous chloride 2g and triethylamine 8g, be warming up to 70-75 ℃, beginning slowly drips propenyl chloride 345g, time for adding 3.5-4 hour, after dripping, propenyl chloride maintains the temperature at 80-85 ℃ of lower reaction 4 hours.Suction filtration went out solid phase after reaction finished, and liquid phase distills out colourless transparent liquid triallyl isocyanurate product 205g after reclaiming whole solvents under 113～115 ℃/133.3Pa, and yield 82.16%(is in sodium isocyanurate), content 98. 12%(HPLC).
Embodiment 2
With sodium isocyanurate 195g and 500gN, in the four-hole boiling flask of dinethylformamide adding with prolong, add simultaneously cuprous chloride 2g and Tributylamine 8g, be warming up to 80-85 ℃, beginning slowly drips propenyl chloride 345g, time for adding 3-3.5 hour, after dripping, propenyl chloride maintains the temperature at 90-95 ℃ of lower reaction 3 hours.Suction filtration went out solid phase after reaction finished, under 113～115 ℃/133.3Pa, distill out colourless transparent liquid triallyl isocyanurate product 215g behind the whole solvents of liquid phase reclaim under reduced pressure, yield 86.17%(is in sodium isocyanurate), content 98. 46%(HPLC).
Embodiment 3
Sodium isocyanurate 195g and 500g methyl-sulphoxide are added in the four-hole boiling flask with prolong, add simultaneously copper powder 2g and triethylamine 8g, be warming up to 90-95 ℃, beginning slowly drips propenyl chloride 345g, time for adding 3-3.5 hour, after dripping, propenyl chloride maintains the temperature at 100-105 ℃ of lower reaction 3 hours.Suction filtration went out solid phase after reaction finished, under 113～115 ℃/133.3Pa, distill out colourless transparent liquid triallyl isocyanurate product 212g behind the whole solvents of liquid phase reclaim under reduced pressure, yield 84.97%(is in sodium isocyanurate), content 98. 71%(HPLC).
Embodiment 4
With sodium isocyanurate 195g and 500gN, in the four-hole boiling flask of dinethylformamide adding with prolong, add simultaneously copper powder 3.0g and Tributylamine 6g, be warming up to 80-85 ℃ of beginning and slowly drip propenyl chloride 345g, time for adding 3-3.5 hour, after dripping, propenyl chloride maintains the temperature at 95-95 ℃ of lower reaction 3 hours.Suction filtration went out solid phase after reaction finished, under 113～115 ℃/133.3Pa, distill out colourless transparent liquid triallyl isocyanurate product 210g behind the whole solvents of liquid phase reclaim under reduced pressure, yield 84.17%(is in sodium isocyanurate), content 98. 54%(HPLC).
Embodiment 5
Sodium isocyanurate 195g and 500gN-methylacetamide are added in the four-hole boiling flask with prolong, add simultaneously cuprous chloride 3.0g and pyridine 6g, be warming up to 85-90 ℃ of beginning and slowly drip propenyl chloride 345g, time for adding 3-3.5 hour, after dripping, propenyl chloride maintains the temperature at 95-100 ℃ of lower reaction 2 hours.Suction filtration went out solid phase after reaction finished, under 113～115 ℃/133.3Pa, distill out colourless transparent liquid triallyl isocyanurate product 219g behind the whole solvents of liquid phase reclaim under reduced pressure, yield 87.78%(is in sodium isocyanurate), content 98.62%(HPLC).
At last, should be pointed out that above embodiment only is the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-described embodiment, and many distortion can also be arranged.Every all distortion of directly deriving or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (5)
1. the preparation method of a triallyl isocyanurate is characterized in that comprising:
Sodium isocyanurate and catalyzer are added in the solvent, react at the temperature 70-105 ℃ of lower propenyl chloride that drips, react and be cooled to room temperature after 4～8 hours, remove by filter solid phase, filtrate behind the recovery solvent distills out the triallyl isocyanurate product under 11 3～115 ℃/133.3Pa, wherein: described catalyzer is the catalyst system of copper catalyst and phase-transfer catalyst.
2. the preparation method of a kind of triallyl isocyanurate according to claim 1 is characterized in that, described solvent is aprotic polar solvent, is DMF, methyl-sulphoxide, N-methylacetamide or acetonitrile.
3. the preparation method of a kind of triallyl isocyanurate according to claim 1 is characterized in that, described copper catalyst is copper powder or cuprous chloride, and consumption is the 0.1-2.0 % by weight based on sodium isocyanurate.
4. the preparation method of a kind of triallyl isocyanurate according to claim 1 is characterized in that, described phase-transfer catalyst is triethylamine, Tributylamine or pyridine, and consumption is the 0.5-5.0 % by weight based on sodium isocyanurate.
5. the preparation method of a kind of triallyl isocyanurate according to claim 1 is characterized in that, reacts at the temperature 70-105 ℃ of lower propenyl chloride that drips.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210344398.1A CN102887868B (en) | 2012-09-18 | 2012-09-18 | Preparation method of triallyl isocyanurate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210344398.1A CN102887868B (en) | 2012-09-18 | 2012-09-18 | Preparation method of triallyl isocyanurate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102887868A true CN102887868A (en) | 2013-01-23 |
| CN102887868B CN102887868B (en) | 2014-12-31 |
Family
ID=47531568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210344398.1A Active CN102887868B (en) | 2012-09-18 | 2012-09-18 | Preparation method of triallyl isocyanurate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102887868B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211651A (en) * | 2014-09-02 | 2014-12-17 | 江苏科利新材料有限公司 | Method for preparing high-quality cross-linking agent |
| CN106810505A (en) * | 2017-03-02 | 2017-06-09 | 江苏华星新材料科技股份有限公司 | The technique that a kind of isocyanuric acid prepares Triallyl isocyanurate |
| CN108623770A (en) * | 2017-03-22 | 2018-10-09 | 广元瑞峰新材料有限公司 | The production method of PVC crosslinking accelerators |
| CN108929283A (en) * | 2018-07-13 | 2018-12-04 | 安徽省化工研究院 | A kind of synthetic method of high-purity crosslinking agent triallyl isocyanurate |
| CN111253329A (en) * | 2020-04-14 | 2020-06-09 | 湖南方锐达科技有限公司 | Preparation process of triallyl isocyanurate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322761A (en) * | 1965-07-14 | 1967-05-30 | Allied Chem | Purification of triallyl isocyanurate |
| US4196289A (en) * | 1978-03-31 | 1980-04-01 | Nippon Kasei Chemical Co., Ltd. | Process for producing triallyl isocyanurate |
| CN101490019A (en) * | 2006-07-12 | 2009-07-22 | 赢创德固赛有限责任公司 | Process for preparing triallyl isocyanurate (TAIC) |
| WO2010137519A1 (en) * | 2009-05-25 | 2010-12-02 | 日本化成株式会社 | Method for storing triallyl isocyanurate |
| CN102448944A (en) * | 2009-05-25 | 2012-05-09 | 日本化成株式会社 | Triallylisocyanurate and process for production thereof |
-
2012
- 2012-09-18 CN CN201210344398.1A patent/CN102887868B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322761A (en) * | 1965-07-14 | 1967-05-30 | Allied Chem | Purification of triallyl isocyanurate |
| US4196289A (en) * | 1978-03-31 | 1980-04-01 | Nippon Kasei Chemical Co., Ltd. | Process for producing triallyl isocyanurate |
| CN101490019A (en) * | 2006-07-12 | 2009-07-22 | 赢创德固赛有限责任公司 | Process for preparing triallyl isocyanurate (TAIC) |
| WO2010137519A1 (en) * | 2009-05-25 | 2010-12-02 | 日本化成株式会社 | Method for storing triallyl isocyanurate |
| CN102448944A (en) * | 2009-05-25 | 2012-05-09 | 日本化成株式会社 | Triallylisocyanurate and process for production thereof |
Non-Patent Citations (2)
| 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", 《合肥工业大学硕士学位论文》, 1 December 2008 (2008-12-01), pages 9 - 15 * |
| 梁伟强: "交联剂TAIC性质、用途及制备", 《广西化工》, no. 2, 31 December 1990 (1990-12-31) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211651A (en) * | 2014-09-02 | 2014-12-17 | 江苏科利新材料有限公司 | Method for preparing high-quality cross-linking agent |
| CN106810505A (en) * | 2017-03-02 | 2017-06-09 | 江苏华星新材料科技股份有限公司 | The technique that a kind of isocyanuric acid prepares Triallyl isocyanurate |
| CN108623770A (en) * | 2017-03-22 | 2018-10-09 | 广元瑞峰新材料有限公司 | The production method of PVC crosslinking accelerators |
| CN108929283A (en) * | 2018-07-13 | 2018-12-04 | 安徽省化工研究院 | A kind of synthetic method of high-purity crosslinking agent triallyl isocyanurate |
| CN111253329A (en) * | 2020-04-14 | 2020-06-09 | 湖南方锐达科技有限公司 | Preparation process of triallyl isocyanurate |
| CN111253329B (en) * | 2020-04-14 | 2022-11-29 | 湖南方锐达科技有限公司 | Preparation process of triallyl isocyanurate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102887868B (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102887868B (en) | Preparation method of triallyl isocyanurate | |
| US7405330B2 (en) | Preparation of polytrimethylene ether glycol and copolymers thereof | |
| WO2018062563A1 (en) | Bisfuran dihalide, method for producing bisfuran dihalide, and method for producing bisfuran diacid, bisfuran diol or bisfuran diamine using bisfuran dihalide | |
| WO2015091494A1 (en) | Five-membered cyclic biscarbonates bearing amide linkages, their preparation and their uses for the preparation of polymers | |
| US10702859B2 (en) | Method for preparing ligand for polyketone polymerization catalyst | |
| TWI535707B (en) | Triisopropyl triisocyanate, triallyl cyanurate and production method of triallyl isothiocyanate | |
| US20100081837A1 (en) | Process for production of powder of cage silsesquioxane compound | |
| CN102365254B (en) | Method for producing alcohol compound | |
| US9562004B2 (en) | 2, 2′-bis (4-hydroxyphenyl) alkyl azides and process for the preparation thereof | |
| WO2011142259A1 (en) | Method for producing aliphatic polycarbonate | |
| JP4301785B2 (en) | Tricyclopentadiene diepoxide | |
| KR101773460B1 (en) | Method for improving properties of glycidyl esters of carboxylic acids | |
| CN103539754B (en) | A kind of 4-replaces the cyclisation method of-2-oxazolidone | |
| CN105669579A (en) | Method for preparing triallyl cyanurate | |
| JP2011195637A (en) | Polycarbonate composition | |
| CN114555576A (en) | Method for producing perfluoro (2, 4-dimethyl-2-fluoroformyl-1, 3-dioxolane) | |
| JP2021102583A (en) | Method for producing alkoxymethyl=alkynyl=ether compound having terminal triple bond | |
| JP2019127442A (en) | Method for producing alicyclic carbonate | |
| JPS58208285A (en) | Production of 2,3-dihydro-2,2-dimethylbenzofuran- 7-ol | |
| JPH03101673A (en) | Synthesis of 3,3',5,5',6,6'-hexafluoro-4,4'-biphthalic anhydride, and 3,3',5,5',6,6'-hexafluoro-4,4'-biphthalic anhydride and its intermediate | |
| KR20200099546A (en) | Method of making diol | |
| JPH0489449A (en) | Production of 4,4'-octafluorobibenzonitrile, 4,4'-octafluorobibenzamide and 4,4'-octafluorobibenzoic acid and 4,4'-octafluorobibenzamide | |
| CN108929283B (en) | Synthesis method of high-purity crosslinking agent triallyl isocyanurate | |
| JP2011236189A (en) | Method for synthesizing disubstituted isocyanuric acid compound | |
| JPH0585995A (en) | Fluorine-containing diaminobenzene compound and fluorine-containing aromatic diamine compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU KELI NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: HANGZHOU KELI CHEMICAL CO., LTD. Effective date: 20140917 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 311228 HANGZHOU, ZHEJIANG PROVINCE TO: 224555 YANCHENG, JIANGSU PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20140917 Address after: 224555, Yancheng City Binhai Economic Development Zone, Jiangsu Province, coastal industrial park, north of Zhongshan Road Province Applicant after: JIANGSU KELI NEW MATERIAL CO., LTD. Address before: 311228, Zhejiang, Hangzhou Xiaoshan Linjiang Industrial Park, a farm Applicant before: Hangzhou Keli Chemical Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HANGZHOU KELI CHEMICAL CO., LTD. Free format text: FORMER OWNER: JIANGSU KELI NEW MATERIAL CO., LTD. Effective date: 20141229 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 224555 YANCHENG, JIANGSU PROVINCE TO: 311228 HANGZHOU, ZHEJIANG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20141229 Address after: 311228, Zhejiang, Hangzhou Xiaoshan Linjiang Industrial Park, a farm Patentee after: Hangzhou Keli Chemical Co., Ltd. Address before: 224555, Yancheng City Binhai Economic Development Zone, Jiangsu Province, coastal industrial park, north of Zhongshan Road Province Patentee before: JIANGSU KELI NEW MATERIAL CO., LTD. |
|
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU KELI NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: HANGZHOU KELI CHEMICAL CO., LTD. Effective date: 20150416 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 311228 HANGZHOU, ZHEJIANG PROVINCE TO: 224555 YANCHENG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150416 Address after: 224555, Yancheng City Binhai Economic Development Zone, Jiangsu Province, coastal industrial park, north of Zhongshan Road Province Patentee after: JIANGSU KELI NEW MATERIAL CO., LTD. Address before: 311228, Zhejiang, Hangzhou Xiaoshan Linjiang Industrial Park, a farm Patentee before: Hangzhou Keli Chemical Co., Ltd. |