CN102887868B - Preparation method of triallyl isocyanurate - Google Patents
Preparation method of triallyl isocyanurate Download PDFInfo
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- CN102887868B CN102887868B CN201210344398.1A CN201210344398A CN102887868B CN 102887868 B CN102887868 B CN 102887868B CN 201210344398 A CN201210344398 A CN 201210344398A CN 102887868 B CN102887868 B CN 102887868B
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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 synthesis field of triallyl isocyanurate, a kind of method adopting catalyst system to prepare triallyl isocyanurate is specifically provided.
Background technology
Triallyl isocyanurate (hereinafter referred to as TAIC), formal name used at school 1,3,5-triallyl-guanamine, 4,6-triketone is the high molecular weight monomers of a kind of multi-functional olefinic containing fragrant heterocycle grown up in the 1980's, be a kind of broad-spectrum fine chemical product, it can coordinate the organo-peroxides such as DCP being cross-linked for 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 resistance to ventilation property of the thermotolerance of crosslinked products, physical strength and oil resistant; 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 bromine addition is a kind of new polymers fire retardant.Under TAIC normal temperature, character is very stable, can at room temperature store for a long time, and having the advantages such as efficient, nontoxic, cross-linking density is high, easy storage, easily transport, is a kind of purposes novel high polymer material auxiliary agent very widely.
Current triallyl isocyanurate (TAIC) is prepared mainly through three kinds of methods:
US Patent No. 3,322, in the method for 761, triallyl isocyanurate (TAIC) passes through in the presence of a catalyst, and the reaction of cyanuric acid, propenyl chloride and aqueous sodium hydroxide solution generates.The shortcoming of the method is having raw material propenyl chloride under water condition to be easily hydrolyzed and product has a larger impurity peaks by liquid phase analysis.
US Patent No. 4,196, in the method for 289, adopts alkali metal cyanate and propenyl chloride in a solvent, reacts at temperature about 130 DEG C.Be characterized in same reaction, carry out cyanate Cheng Huan and propenyl chloride substitution reaction, except can generating triallyl isocyanurate (TAIC) product, also may generate the allyl cyanide acid esters of non-Cheng Huan, therefore in product, various impurity is more, purification & isolation difficulty.
The preparation method of US Patent No. 2009/0312545A1 is the Claisen rearrangement of triallyl cyanurate (TAC).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 exceeded above-mentioned two kinds of methods, be not suitable for suitability for industrialized production.
Summary of the invention
For solving above-mentioned prior art Problems existing, the present invention aims to provide and a kind ofly under catalyst action, carries out sodium isocyanurate in organic solvent and propenyl chloride reacts the method preparing triallyl isocyanurate.It is high that this preparation method has product yield, the feature of good product quality.
Particularly, contriver provides following technical scheme:
A preparation method for triallyl isocyanurate, comprising:
Sodium isocyanurate and catalyzer are added in solvent, at temperature 70 ~ 105 DEG C, drip propenyl chloride react, react and be cooled to room temperature after 4 ~ 8 hours, cross and filter solid phase, filtrate after recycling design distills out triallyl isocyanurate product under 113 ~ 115 DEG C/133.3Pa, wherein: described catalyzer is the catalyst system of copper catalyst and phase-transfer catalyst.
As preferably, in the present invention, described solvent is aprotic polar solvent, is DMF, methyl-sulphoxide, N-methylacetamide or acetonitrile.
As preferably, in 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, in 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 reaction solution, and therefore raw material propenyl chloride can not be hydrolyzed, and excess chlorine propylene can reclaim after the completion of reaction, 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, and suitability for industrialized is produced.
The product of the present invention's synthesis is analyzed by mass spectrum (MS), and molecular weight is 249, and structural formula coincide with the structural formula of triallyl isocyanurate in spectrum storehouse, and its structural formula is:
Embodiment
Below in conjunction with embodiment, further illustrate content of the present invention.
In the present invention, if not refer in particular to, all parts, per-cent are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is conventional.Method in 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 cuprous chloride 2g and triethylamine 8g simultaneously, be warming up to 70-75 DEG C, start slowly to drip propenyl chloride 345g, time for adding 3.5-4 hour, reacts 4 hour at maintaining the temperature at 80-85 DEG C after propenyl chloride drips.Reaction terminates rear suction filtration and goes out solid phase, and under 113 ~ 115 DEG C/133.3Pa, distill out colourless transparent liquid triallyl isocyanurate product 205g after liquid phase reclaims whole solvent, yield 82.16%(is in sodium isocyanurate), content 98. 12%(HPLC).
embodiment 2
By sodium isocyanurate 195g and 500gN, dinethylformamide adds in the four-hole boiling flask with prolong, add cuprous chloride 2g and Tributylamine 8g simultaneously, be warming up to 80-85 DEG C, start slowly to drip propenyl chloride 345g, time for adding 3-3.5 hour, reacts 3 hour at maintaining the temperature at 90-95 DEG C after propenyl chloride drips.Reaction terminates rear suction filtration and goes out solid phase, under 113 ~ 115 DEG C/133.3Pa, colourless transparent liquid triallyl isocyanurate product 215g is distilled out after the whole solvent 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 copper powder 2g and triethylamine 8g simultaneously, be warming up to 90-95 DEG C, start slowly to drip propenyl chloride 345g, time for adding 3-3.5 hour, reacts 3 hour at maintaining the temperature at 100-105 DEG C after propenyl chloride drips.Reaction terminates rear suction filtration and goes out solid phase, under 113 ~ 115 DEG C/133.3Pa, colourless transparent liquid triallyl isocyanurate product 212g is distilled out after the whole solvent of liquid phase reclaim under reduced pressure, yield 84.97%(is in sodium isocyanurate), content 98. 71%(HPLC).
embodiment 4
By sodium isocyanurate 195g and 500gN, dinethylformamide adds in the four-hole boiling flask with prolong, add copper powder 3.0g and Tributylamine 6g simultaneously, be warming up to 80-85 DEG C to start slowly to drip propenyl chloride 345g, time for adding 3-3.5 hour, reacts 3 hour at maintaining the temperature at 95-95 DEG C after propenyl chloride drips.Reaction terminates rear suction filtration and goes out solid phase, under 113 ~ 115 DEG C/133.3Pa, colourless transparent liquid triallyl isocyanurate product 210g is distilled out after the whole solvent 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 cuprous chloride 3.0g and pyridine 6g simultaneously, be warming up to 85-90 DEG C to start slowly to drip propenyl chloride 345g, time for adding 3-3.5 hour, reacts 2 hour at maintaining the temperature at 95-100 DEG C after propenyl chloride drips.Reaction terminates rear suction filtration and goes out solid phase, under 113 ~ 115 DEG C/133.3Pa, colourless transparent liquid triallyl isocyanurate product 219g is distilled out after the whole solvent of liquid phase reclaim under reduced pressure, yield 87.78%(is in sodium isocyanurate), content 98.62%(HPLC).
Finally, it should be pointed out that above embodiment is only the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-described embodiment, can also have many distortion.Every all distortion of directly deriving from content disclosed by the invention or associating, all should think protection scope of the present invention.
Claims (1)
1. a preparation method for triallyl isocyanurate, is characterized in that comprising:
Sodium isocyanurate and catalyzer are added in solvent, at temperature 70-105 DEG C, drip propenyl chloride react, react and be cooled to room temperature after 4 ~ 8 hours, cross and filter solid phase, filtrate after recycling design distills out triallyl isocyanurate product under 11 3 ~ 115 DEG C/133.3Pa, wherein: described catalyzer is the catalyst system of copper catalyst and phase-transfer catalyst
Described solvent is aprotic polar solvent, is DMF, methyl-sulphoxide, N-methylacetamide or acetonitrile,
Described copper catalyst is copper powder or cuprous chloride, and consumption is the 0.1-2.0 % by weight based on sodium isocyanurate,
Described phase-transfer catalyst is triethylamine, Tributylamine or pyridine, and consumption is the 0.5-5.0 % by weight based on sodium isocyanurate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN108929283B (en) * | 2018-07-13 | 2021-12-14 | 安徽省化工研究院 | Synthesis method of high-purity crosslinking agent 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196289A (en) * | 1978-03-31 | 1980-04-01 | Nippon Kasei Chemical Co., Ltd. | Process for producing triallyl isocyanurate |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322761A (en) * | 1965-07-14 | 1967-05-30 | Allied Chem | Purification of triallyl isocyanurate |
| DE102006032167B4 (en) * | 2006-07-12 | 2014-11-27 | Evonik Degussa Gmbh | Process for the preparation of triallyl isocyanurate (TAIC) |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196289A (en) * | 1978-03-31 | 1980-04-01 | Nippon Kasei Chemical Co., Ltd. | Process for producing triallyl isocyanurate |
| 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 |
|---|
| 交联剂TAIC性质、用途及制备;梁伟强;《广西化工》;19901231(第2期);第20页第2-3点 * |
| 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》.2008,第9-15页. * |
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