CN102924392A - One-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate - Google Patents
One-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate Download PDFInfo
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- CN102924392A CN102924392A CN2012104418898A CN201210441889A CN102924392A CN 102924392 A CN102924392 A CN 102924392A CN 2012104418898 A CN2012104418898 A CN 2012104418898A CN 201210441889 A CN201210441889 A CN 201210441889A CN 102924392 A CN102924392 A CN 102924392A
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- pentabromobenzyl
- acid ester
- isocyanuric acid
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Abstract
The invention discloses a one-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate. The method comprises the following steps of (1) adding cyanuric acid and alkali or salt of potassium or sodium into organic solvent, and enabling the mixture to react with stirring under the temperature of 0-100 DEG C until no bubbles is generated, wherein the mole ratio of cyanuric acid to alkali or salt of potassium or sodium is 1: (0.5-5); (2) adding five-bromine benzyl bromide into the reaction solution, and enabling the mixture to perform thermal reaction under the temperature of 100-150 DEG C until the reaction solution becomes white and white crystals are generated, wherein the mole ratio of the five-bromine benzyl bromide to the cyanuric acid is (3-10):1; and (3) cooling the reaction material to perform crystallization, and performing suction filtration, washing, suction filtration and purification on the precipitated crystals to obtain the 1,3,5-three (five-bromine benzyl) isocyanurate. By means of the one-pot method, process steps are simplified, product yield is high, production cost is reduced, environmental protection stress is relieved, and the product is high in purity, low in impurity content and high in yield.
Description
Technical field
The present invention relates to bromide fire retardant, be specifically related to a kind of 1,3, the preparation of 5-three (pentabromobenzyl) isocyanuric acid ester bromide fire retardant.
Background technology
1,3,5-three (pentabromobenzyl) isocyanuric acid ester is a kind of novel high-efficiency environment friendly bromide fire retardant.Its thermostability is better than most existing bromide fire retardants, its fusing point is higher than 340 ℃, mass loss is not higher than 2% in the time of 350 ℃, this is seldom in existing bromide fire retardant, can be widely used in all respects such as superpolymer synthetic materials, plastics, fiber, building materials, resin, especially fire-retardant as engineering plastics such as HIPS, PBT, ABS and polyolefine, can be used for simultaneously fire-retardant processing temperature and reach engineering plastics more than 300 ℃.The good light stability of this BACN and anti-uv-ray make it have excellent colour stability, particularly it has the advantage of extraordinary thermostability and unsuitable frosting, make it can recycling use, be conducive to environmental protection, this be that other fire retardant is incomparable.
At present, in the existing production technique of 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, adopt polystep reaction to prepare this product.Be specially and in the aqueous solution, prepare first trisodium cyanurate, extract crystal by concentrated mode, in solvent, add again pentabromobenzyl bromide and trisodium cyanurate and react and prepare 1,3,5-three (pentabromobenzyl) isocyanuric acid ester.Existing production technique not only processing step is complicated, poor working environment, and product yield and the content of preparation are inclined to one side, and low thermal stability is poor, and energy-output ratio is high, and follows the generation of the three wastes such as waste water, for environment has brought certain pollution.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiency of prior art existence, provide that a kind of processing step is simplified, production cost is low, product yield is high, good product quality, one kettle way that three-waste pollution is few prepare 1, the method of 3,5-three (pentabromobenzyl) isocyanuric acid ester.
For solving the problems of the technologies described above, technical scheme of the present invention is:
One kettle way prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, may further comprise the steps:
(1) with the alkali of cyanuric acid and potassium or sodium or salt according to the mol ratio of 1:0.5～5, join in the organic solvent, under the whipped state, be 0～100 ℃ in temperature and react, until without bubble formation.
(2) mol ratio of adding and cyanuric acid is the pentabromobenzyl bromide of 3～10:1 in above-mentioned reaction solution, and 100～150 ℃ of insulation reaction, until reaction soln is white, and the adularescent crystallization occurs.
(3) with the reaction mass crystallisation by cooling, the crystal of separating out carried out re-refining behind suction filtration, washing and the suction filtration obtains product 1,3,5-three (pentabromobenzyl) isocyanuric acid ester.
Preferably, the alkali of described potassium or sodium or salt comprise yellow soda ash, sodium bicarbonate, salt of wormwood, potassium hydroxide or sodium hydroxide.
As further preferred, the alkali of described potassium or sodium or salt are yellow soda ash.
Preferably, described organic solvent comprises one or more in toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, the ethylene glycol ethyl ether.
As further preferred, described organic solvent is ethylene glycol monomethyl ether.
Preferably, in the step (1), the alkali of described cyanuric acid and potassium or sodium or the mol ratio of salt are 1:0.8～1.2.
Preferably, in the step (1), described temperature of reaction is 50～70 ℃.
Preferably, the mol ratio of described pentabromobenzyl bromide and cyanuric acid is 3～5:1.
Preferably, in the step (2), temperature of reaction is 110～120 ℃.
Preferably, described making with extra care is that the material behind washing and the suction filtration is added in the organic solvent, carries out agitator treating 1～3 hour at 50～60 ℃.
Preferably, described organic solvent comprises one or more in toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, the ethylene glycol ethyl ether.
As further preferred, the organic solvent in described organic solvent and the step (1) is same or with several organic solvents.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
The present invention adopts one kettle way to prepare 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, first the alkali of cyanuric acid and potassium or sodium or salt are reacted in organic solvent and obtain cyanurate, in reaction solution, add again the pentabromobenzyl bromine reaction, with the reaction mass crystallisation by cooling and through washing and the refining product 1,3,5-three (pentabromobenzyl) isocyanuric acid ester of obtaining.Polystep reaction with prior art is compared, processing step of the present invention is simplified, product yield is high, and production energy consumption reduces, and greatly reduces three waste discharge, energy consumption and cost for wastewater treatment that the cyanurate crystal extracts have been reduced, reduced production cost, alleviated environmental protection pressure, and product purity is high, foreign matter content is low, and yield is high.Product yield of the present invention reaches more than 95%, and purity reaches more than 99%, Effective Raise quality and the thermostability of product.
The present invention is identical a kind of organic solvent or identical several organic solvents when adopting to product purification the time and preparing with cyanurate, the easier recycling of solvent.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
Stir down, cyanuric acid and yellow soda ash according to the mol ratio of 1:1, are joined in the organic solvent, under the whipped state, being 50 ℃ in temperature reacts, until without bubble formation.
After reaction is finished, reaction solution is warming up to 120 ℃, adding is the pentabromobenzyl bromide of 3:1 with the mol ratio of cyanuric acid, and insulation reaction is until reaction soln is white, and the adularescent suspension crystallization occurs.
With the reaction mass crystallisation by cooling, the crystal of separating out is carried out suction filtration, the solid behind the suction filtration washes with water, and adopt again organic solvent to make with extra care behind the suction filtration and obtain product 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, the yield of product is 95.3%, purity is 99.2%.
Embodiment 2
Stir down, cyanuric acid and sodium bicarbonate according to the mol ratio of 1:4, are joined in the organic solvent toluene, under the whipped state, being 30 ℃ in temperature reacts, until without bubble formation.
After reaction is finished, reaction solution is warming up to 100 ℃, adding is the pentabromobenzyl bromide of 8:1 with the mol ratio of cyanuric acid, and insulation reaction is until reaction soln is white, and the adularescent suspension crystallization occurs.
With the reaction mass crystallisation by cooling, the crystal of separating out is carried out suction filtration, solid behind the suction filtration washes with water, adopt again organic solvent toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, the refining product 1 that obtains of ethylene glycol ethyl ether behind the suction filtration, 3,5-three (pentabromobenzyl) isocyanuric acid ester, the yield of product is 95.1%, purity is 99.0%.
Embodiment 3
Stir down, cyanuric acid and salt of wormwood according to the mol ratio of 1:0.8, are joined in the organic solvent dimethyl formamide, under the whipped state, being 80 ℃ in temperature reacts, until without bubble formation.
After reaction is finished, reaction solution is warming up to 10 ℃, adding is the pentabromobenzyl bromide of 4:1 with the mol ratio of cyanuric acid, and insulation reaction is until reaction soln is white, and the adularescent suspension crystallization occurs.
With the reaction mass crystallisation by cooling, the crystal of separating out is carried out suction filtration, solid behind the suction filtration washes with water, put into the organic solvent dimethyl formamide behind the suction filtration, be 50 ℃ in temperature and carried out agitator treating 3 hours, the refining product 1 that obtains, 3,5-three (pentabromobenzyl) isocyanuric acid ester, the yield of product is 95.45%, purity is 99.29%.
Embodiment 4
Stir down, cyanuric acid and potassium hydroxide according to the mol ratio of 1:2, are joined in the organic solvent ethylene glycol monomethyl ether, under the whipped state, being 80 ℃ in temperature reacts, until without bubble formation.
After reaction is finished, reaction solution is warming up to 110 ℃, adding is the pentabromobenzyl bromide of 5:1 with the mol ratio of cyanuric acid, and insulation reaction is until reaction soln is white, and the adularescent suspension crystallization occurs.
With the reaction mass crystallisation by cooling, the crystal of separating out is carried out suction filtration, solid behind the suction filtration washes with water, put into the organic solvent ethylene glycol monomethyl ether behind the suction filtration, be 60 ℃ in temperature and carried out agitator treating 1 hour, the refining product 1 that obtains, 3,5-three (pentabromobenzyl) isocyanuric acid ester, the yield of product is 95.65%, purity is 99.35%.
Embodiment 5
Stir down, cyanuric acid and sodium hydroxide according to the mol ratio of 1:5, are joined in the organic solvent ethylene glycol ethyl ether, under the whipped state, being 90 ℃ in temperature reacts, until without bubble formation.
After reaction is finished, reaction solution is warming up to 130 ℃, adding is the pentabromobenzyl bromide of 4:1 with the mol ratio of cyanuric acid, and insulation reaction is until reaction soln is white, and the adularescent suspension crystallization occurs.
With the reaction mass crystallisation by cooling, the crystal of separating out is carried out suction filtration, solid behind the suction filtration washes with water, put into the organic solvent ethylene glycol ethyl ether behind the suction filtration, be 55 ℃ in temperature and carried out agitator treating 2 hours, the refining product 1 that obtains, 3,5-three (pentabromobenzyl) isocyanuric acid ester, the yield of product is 95.32%, purity is 99.15%.
Embodiment 6
Stir down, cyanuric acid and yellow soda ash according to the mol ratio of 1:1, are joined in the organic solvent N,N-DIMETHYLACETAMIDE, under the whipped state, being 70 ℃ in temperature reacts, until without bubble formation.
After reaction is finished, reaction solution is warming up to 115 ℃, adding is the pentabromobenzyl bromide of 3.5:1 with the mol ratio of cyanuric acid, and insulation reaction is until reaction soln is white, and the adularescent suspension crystallization occurs.
With the reaction mass crystallisation by cooling, the crystal of separating out is carried out suction filtration, solid behind the suction filtration washes with water, put into the organic solvent N,N-DIMETHYLACETAMIDE behind the suction filtration, be 52 ℃ in temperature and carried out agitator treating 1.5 hours, the refining product 1 that obtains, 3,5-three (pentabromobenzyl) isocyanuric acid ester, the yield of product is 95.55%, purity is 99.33%.
Claims (10)
1. one kettle way prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that may further comprise the steps:
(1) with the alkali of cyanuric acid and potassium or sodium or salt according to the mol ratio of 1:0.5～5, join in the organic solvent, under the whipped state, be 0～100 ℃ in temperature and react, until without bubble formation;
(2) mol ratio of adding and cyanuric acid is the pentabromobenzyl bromide of 3～10:1 in above-mentioned reaction solution, and 100～150 ℃ of insulation reaction, until reaction soln is white, and the adularescent crystallization occurs;
(3) with the reaction mass crystallisation by cooling, with the crystal of separating out washing and refining after obtain product 1,3,5-three (pentabromobenzyl) isocyanuric acid ester.
2. one kettle way as claimed in claim 1 prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: the alkali of described potassium or sodium or salt comprise yellow soda ash, sodium bicarbonate, salt of wormwood, potassium hydroxide or sodium hydroxide.
3. one kettle way as claimed in claim 1 prepares 1,3, the method of 5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: described organic solvent comprises one or more in toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, the ethylene glycol ethyl ether.
4. one kettle way as claimed in claim 1 prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: in the step (1), the alkali of described cyanuric acid and potassium or sodium or the mol ratio of salt are 1:0.8～1.2.
5. one kettle way as claimed in claim 1 prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: in the step (1), described temperature of reaction is 50～70 ℃.
6. one kettle way as claimed in claim 1 prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: the mol ratio of described pentabromobenzyl bromide and cyanuric acid is 3～5:1.
7. one kettle way as claimed in claim 1 prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: in the step (2), temperature of reaction is 110～120 ℃.
8. prepare 1 such as the described one kettle way of the arbitrary claim of claim 1 to 7,3, the method of 5-three (pentabromobenzyl) isocyanuric acid ester is characterized in that: described making with extra care is that the material behind washing and the suction filtration is added in the organic solvent, carries out agitator treating 1～3 hour at 50～60 ℃.
9. one kettle way as claimed in claim 8 prepares 1,3, the method of 5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: described organic solvent comprises one or more in toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, the ethylene glycol ethyl ether.
10. one kettle way as claimed in claim 9 prepares the method for 1,3,5-three (pentabromobenzyl) isocyanuric acid ester, it is characterized in that: the organic solvent in described organic solvent and the step (1) is same or with several organic solvents.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104418898A CN102924392A (en) | 2012-11-07 | 2012-11-07 | One-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate |
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| CN2012104418898A CN102924392A (en) | 2012-11-07 | 2012-11-07 | One-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420932A (en) * | 2013-08-26 | 2013-12-04 | 天津利安隆新材料股份有限公司 | Method for preparing 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate |
| CN113683576A (en) * | 2021-08-24 | 2021-11-23 | 珠海宏昌电子材料有限公司 | Isocyanurate, preparation method thereof and application thereof in high-frequency and high-speed resin |
-
2012
- 2012-11-07 CN CN2012104418898A patent/CN102924392A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 吴俊浩等: "1,3,5-三(五溴苄基)异氰尿酸酯的合成", 《化学通报（网络版）》 * |
| 王志峰: "氰尿酸及其衍生物的现状分析", 《现代化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420932A (en) * | 2013-08-26 | 2013-12-04 | 天津利安隆新材料股份有限公司 | Method for preparing 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate |
| CN103420932B (en) * | 2013-08-26 | 2016-02-17 | 天津利安隆新材料股份有限公司 | The preparation method of 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates |
| CN113683576A (en) * | 2021-08-24 | 2021-11-23 | 珠海宏昌电子材料有限公司 | Isocyanurate, preparation method thereof and application thereof in high-frequency and high-speed resin |
| CN113683576B (en) * | 2021-08-24 | 2022-08-30 | 珠海宏昌电子材料有限公司 | Isocyanurate, preparation method thereof and application thereof in high-frequency and high-speed resin |
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Application publication date: 20130213 |