CN103183704B - A kind of preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester - Google Patents
A kind of preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester, comprise the following steps: tribromoneoamyl alcohol joins in organic solvent by (1), the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:1 ~ 10, under whipped state, dissolves at temperature is 0 ~ 100 DEG C; (2) under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:1 ~ 10, add the first catalyzer simultaneously, the second catalyst reaction is slowly dripped at 10 ~ 100 DEG C, after dropwising at 10 ~ 100 DEG C insulation reaction 1 ~ 24h, carry out aftertreatment and obtain product.Present invention process step is simple, and product yield is high, Heat stability is good, content is high, and production energy consumption reduces, and greatly reduces three waste discharge, reduce energy consumption and the cost for wastewater treatment of product crystallization extraction, reduce production cost, there is not the generation of the three wastes such as waste water, there is not the problem of environmental pollution, alleviate environmental protection pressure, and product purity is high, foreign matter content is low, and yield is high.
Description
Technical field
The present invention relates to bromine phosphorus flame retardant, particularly relate to a kind of preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester.
Background technology
Three (tribromoneoamyl alcohol base) phosphoric acid ester is a kind of novel high-efficiency environment friendly bromine phosphorus flame retardant, has the characteristic of bromine system and phosphorus system two-phase fire retardant, has and better coordinate flame retardant effect, mainly can be used as the fire-retardant of high impact polystyrene (HIPS).High impact polystyrene is the polystyrene plastic with polybutadiene rubber modification, owing to being easy to injection moulding and extrusion moulding, and the price of relative moderate and more satisfactory application performance, having a wide range of applications in household electrical appliances, information products, food product pack, toy and stationery etc., is one of plastic raw materials the most frequently used in thermoplastics market.The fire retardant mainly halogen sb system that current flame-retarding HIPS is used, the mechanism of action of halogen containing flame-retardant catches living radical in the gas phase, namely at high temperature halogen containing flame-retardant decomposes the halogen free radical produced, high reactivity hydroxyl radical free radical in the inflammable gas produced with polymer unwinds or hydroperoxyl radical react and generate stable compound, thus interrupt chain type oxidising process, burning is slowed down, so that certainly puts out.In order to improve flame retarding efficiency, the general and synergist Sb of halogen containing flame-retardant
2o
3and use.
Three (tribromoneoamyl alcohol base) phosphate flame retardant is a kind of efficient flame-retarding agent, and the UL94V-2 level that may be used for HIPS is fire-retardant, and this fire retardant fusing point is low, good product mobility, and its fire retardant material can make larger thin wall parts.In addition, goods anti-ultraviolet property is excellent, can meet the requirement that processing more complicated product UL94V-2 level is fire-retardant.Simultaneously, the good light stability of this BACN and anti-uv-ray make it have excellent colour stability, and particularly it has the advantage of extraordinary compatibility and unsuitable frosting, make it can recycling use, be conducive to environmental protection, this be other fire retardant incomparable.
Prior art does not all relate to the preparation method of three (tribromoneoamyl alcohol base) of the present invention phosphoric acid ester.
Summary of the invention
For the defect of prior art, the object of this invention is to provide the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester that a kind of processing step simplifies, production cost is low, product yield is high, good product quality, three-waste pollution are few.
To achieve these goals, technical scheme of the present invention is as follows:
The invention provides a kind of preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester, comprise the following steps:
(1) join in organic solvent by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:1 ~ 10, under whipped state, dissolves at temperature is 0 ~ 100 DEG C;
(2) under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:1 ~ 10, add the first catalyzer simultaneously, the second catalyst reaction is slowly dripped at 10 ~ 100 DEG C, after dropwising at 10 ~ 100 DEG C insulation reaction 1 ~ 24h, carry out aftertreatment and obtain product.
As preferred technical scheme, the organic solvent that step (1) uses is benzene, one or more in tetrahydrofuran (THF), hexane, acetonitrile, tetracol phenixin, ethylene dichloride, chloroform.
As preferred technical scheme, the mass ratio of described tribromoneoamyl alcohol and organic solvent is 1:2 ~ 5.
As preferred technical scheme, the temperature of dissolving in described step (1) is 30 ~ 40 DEG C; The time of dissolving in described step (1) is 0.5 ~ 1h.
As preferred technical scheme, the mol ratio of described phosphorus oxychloride and tribromoneoamyl alcohol is 1:2.5 ~ 4.5.
As preferred technical scheme, described first catalyzer is Fe, FeCl
3, Al, ALCl
3, SnCl
4in one or more; Described first catalyzer is 1 ~ 10% of tribromoneoamyl alcohol quality.
As preferred technical scheme, described second catalyzer is one or more in triethylamine, ammonia, pyridine, quadrol; Described second catalyzer is 10 ~ 30% of tribromoneoamyl alcohol quality.
As preferred technical scheme, in described step (2), the dropping temperature of the second catalyzer is 20 ~ 30 DEG C; In described step (2), the temperature of insulation reaction is 70 ~ 100 DEG C; In described step (2), the time of insulation reaction is 20 ~ 24h.
As preferred technical scheme, in step (2), aftertreatment comprises the following steps: cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:1 ~ 10, crystallize out, suction filtration, obtains product after washing and drying.
As preferred technical scheme, the mass ratio of described organic layer (in organic solvent in step (1)) and ethanol is for 1:2 ~ 5.
Owing to have employed technique scheme, the invention has the beneficial effects as follows:
Present invention process step is simple, and product yield is high, Heat stability is good, content is high, and production energy consumption reduces, and greatly reduces three waste discharge, reduce energy consumption and the cost for wastewater treatment of product crystallization extraction, reduce production cost, there is not the generation of the three wastes such as waste water, there is not the problem of environmental pollution, alleviate 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 80%, and purity reaches more than 99%, effectively improves quality and the thermostability of product.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
(1) join in organic solvent-benzene by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:1, under whipped state, at temperature is 30 DEG C, dissolves 1h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:2.5, adds the first catalyst Fe simultaneously, and the first catalyzer is 1% of tribromoneoamyl alcohol quality; The second catalyst of triethylamine reaction is slowly dripped at 20 DEG C, second catalyzer is 10% of tribromoneoamyl alcohol quality, after dropwising at 70 DEG C insulation reaction 23h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:1, crystallize out, suction filtration, obtains product after washing and drying.
Present invention process step is simple, and product yield is high, Heat stability is good, content is high, and production energy consumption reduces, and greatly reduces three waste discharge, reduce energy consumption and the cost for wastewater treatment of product crystallization extraction, reduce production cost, there is not the generation of the three wastes such as waste water, there is not the problem of environmental pollution, alleviate 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 80%, and purity reaches more than 99%, effectively improves quality and the thermostability of product.
Embodiment 2
(1) join in organic solvent tetrahydrofuran by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:2, under whipped state, at temperature is 35 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:3.5, adds the first catalyst Fe Cl simultaneously
3, the first catalyzer is 2% of tribromoneoamyl alcohol quality; The second catalyst ammonia reaction is slowly dripped at 25 DEG C, second catalyzer is 20% of tribromoneoamyl alcohol quality, after dropwising at 80 DEG C insulation reaction 22h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:2, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 3
(1) joined by tribromoneoamyl alcohol in organic solvent hexane, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:3, under whipped state, at temperature is 40 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:4.5, adds the first catalyst A l simultaneously, and the first catalyzer is 3% of tribromoneoamyl alcohol quality; The second catalyst pyridine reaction is slowly dripped at 30 DEG C, second catalyzer is 30% of tribromoneoamyl alcohol quality, after dropwising at 90 DEG C insulation reaction 21h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:3, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 4
(1) join in organic solvent acetonitrile by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:4, under whipped state, at temperature is 35 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:3, adds the first catalyst A lCl simultaneously
3, the first catalyzer is 4% of tribromoneoamyl alcohol quality; The second catalyzer reacting ethylenediamine is slowly dripped at 25 DEG C, second catalyzer is 15% of tribromoneoamyl alcohol quality, after dropwising at 100 DEG C insulation reaction 20h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:4, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 5
(1) join in organic solvent carbon tetrachloride by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:5, under whipped state, at temperature is 40 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:2, adds the first catalyst S nCl simultaneously
4, the first catalyzer is 5% of tribromoneoamyl alcohol quality; The second catalyst of triethylamine reaction is slowly dripped at 25 DEG C, second catalyzer is 25% of tribromoneoamyl alcohol quality, after dropwising at 80 DEG C insulation reaction 22h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:5, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 6
(1) joined by tribromoneoamyl alcohol in organic solvent ethylene dichloride, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:6, under whipped state, at temperature is 50 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:1, adds the first catalyst Fe simultaneously, and the first catalyzer is 6% of tribromoneoamyl alcohol quality; The second catalyst ammonia reaction is slowly dripped at 25 DEG C, second catalyzer is 12% of tribromoneoamyl alcohol quality, after dropwising at 80 DEG C insulation reaction 22h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:6, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 7
(1) join in organic solvents, chloroform by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:7, under whipped state, at temperature is 70 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:4, adds the first catalyst Fe Cl simultaneously
3, the first catalyzer is 7% of tribromoneoamyl alcohol quality; The second catalyst pyridine reaction is slowly dripped at 25 DEG C, second catalyzer is 16% of tribromoneoamyl alcohol quality, after dropwising at 50 DEG C insulation reaction 24h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:7, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 8
(1) join in organic solvent tetrahydrofuran by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:8, under whipped state, at temperature is 80 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:10, adds the first catalyst A l simultaneously, and the first catalyzer is 8% of tribromoneoamyl alcohol quality; The second catalyzer reacting ethylenediamine is slowly dripped at 25 DEG C, second catalyzer is 18% of tribromoneoamyl alcohol quality, after dropwising at 60 DEG C insulation reaction 23h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:8, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 9
(1) join in organic solvents, chloroform by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:9, under whipped state, at temperature is 100 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:8, adds the first catalyst A lCl simultaneously
3, the first catalyzer is 9% of tribromoneoamyl alcohol quality; The second catalyst of triethylamine reaction is slowly dripped at 25 DEG C, second catalyzer is 22% of tribromoneoamyl alcohol quality, after dropwising at 80 DEG C insulation reaction 22h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:9, crystallize out, suction filtration, obtains product after washing and drying.
Embodiment 10
(1) join in organic solvent tetrahydrofuran by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:10, under whipped state, at temperature is 40 DEG C, dissolves 0.5h;
(2), under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:6, adds the first catalyst S nCl simultaneously
4, the first catalyzer is 10% of tribromoneoamyl alcohol quality; The second catalyst of triethylamine reaction is slowly dripped at 25 DEG C, second catalyzer is 26% of tribromoneoamyl alcohol quality, after dropwising at 80 DEG C insulation reaction 22h, cooling, washing, stratification, will organic layer be separated after be added drop-wise in ethanol, the mass ratio of organic layer (in organic solvent in step (1)) and ethanol for 1:10, crystallize out, suction filtration, obtains product after washing and drying.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (7)
1. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester, is characterized in that, comprise the following steps:
(1) join in organic solvent by tribromoneoamyl alcohol, the mass ratio of tribromoneoamyl alcohol and organic solvent is 1:1 ~ 10, under whipped state, dissolves at temperature is 0 ~ 100 DEG C;
(2) under whipped state, adding in step (1) gained reaction solution with the mol ratio of tribromoneoamyl alcohol is the phosphorus oxychloride of 1:1 ~ 10, add the first catalyzer simultaneously, the second catalyst reaction is slowly dripped at 10 ~ 100 DEG C, after dropwising at 10 ~ 100 DEG C insulation reaction 1 ~ 24h, carry out aftertreatment and obtain product;
Described first catalyzer is one or more in Fe and Al;
Described first catalyzer is 1 ~ 10% of tribromoneoamyl alcohol quality;
Described second catalyzer is one or more in ammonia, quadrol;
Described second catalyzer is 10 ~ 30% of tribromoneoamyl alcohol quality;
Described organic solvent is one or more in tetracol phenixin, ethylene dichloride, chloroform.
2. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester according to claim 1, it is characterized in that, the mass ratio of described tribromoneoamyl alcohol and organic solvent is 1:2 ~ 5.
3. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester according to claim 1, is characterized in that, the temperature of dissolving in described step (1) is 30 ~ 40 DEG C;
The time of dissolving in described step (1) is 0.5 ~ 1h.
4. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester according to claim 1, it is characterized in that, the mol ratio of described phosphorus oxychloride and tribromoneoamyl alcohol is 1:2.5 ~ 4.5.
5. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester according to claim 1, it is characterized in that, in described step (2), the dropping temperature of the second catalyzer is 20 ~ 30 DEG C; In described step (2), the temperature of insulation reaction is 70 ~ 100 DEG C; In described step (2), the time of insulation reaction is 20 ~ 24h.
6. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester according to claim 1, it is characterized in that, described aftertreatment comprises the following steps: cooling, washing, stratification, is added drop-wise in ethanol after being separated by organic layer, the mass ratio of organic layer and ethanol is 1:1 ~ 10, crystallize out, suction filtration, obtains product after washing and drying.
7. the preparation method of three (tribromoneoamyl alcohol base) phosphoric acid ester according to claim 6, it is characterized in that, the mass ratio of described organic layer and ethanol is 1:2 ~ 5.
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| CN104672278A (en) * | 2015-03-24 | 2015-06-03 | 宜兴市中正化工有限公司 | Method for synthesizing tri(tribromoneopentyl alcohol) phosphate |
| CN105254666B (en) * | 2015-11-11 | 2018-04-13 | 朱正直 | A kind of preparation method of Triphenyl phosphate |
| CN105646571B (en) * | 2016-01-26 | 2018-11-06 | 寿光市泰源化工有限公司 | It is a kind of to be easy to the three of industrialized production（Tribromoneoamyl alcohol base）Phosphate synthesis method |
| CN112778356B (en) * | 2020-12-26 | 2022-07-01 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
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