A method for preparing tris(1,3-dichloropropyl) phosphate

Abstract

The invention discloses a method for preparing tris(1,3-dichloropropyl) phosphate. The method specifically comprises the following steps: adding phosphorus oxychloride and 1,3-dichloropropanol into areaction kettle at a time, stirring the phosphorus oxychloride and the 1,3-dichloropropanol, raising the temperature to 110 DEG, performing a reaction on the phosphorus oxychloride and the 1,3-dichloropropanol for 1-3h, raising the temperature to 180 DEG according to the 15-30-DEG C gradient, removing generated hydrogen chloride gas under a negative pressure condition and reducing the temperature,so as to obtain a crude product; washing the crude product with alkali and water in sequence and distilling, so as to obtain the tris(1,3-dichloropropyl) phosphate. Under a catalyst-free condition, the method has the advantages of being high in product purity, high in conversion rate, mild in process conditions, and simple in operation, avoiding a problem of aftertreatment of a catalyst and lowering the production cost.

Description

technical field

[0001] The invention belongs to the field of chemical synthesis, and in particular relates to a method for preparing tris(1,3-dichloropropyl) phosphate. Background technique

[0002] As a good flame retardant and flame retardant plasticizer, tris(1,3-dichloropropyl) phosphate is widely used in unsaturated polyester, rigid and flexible polyurethane foam, epoxy resin, phenolic resin , soft polyvinyl chloride, etc.

[0003] The synthesis of tris(1,3-dichloropropyl) phosphate at home and abroad is mainly based on the research on the reaction of epichlorohydrin and phosphorus oxychloride under the action of different catalysts. American Stauffer Chemical Company and Japan Daihachi Chemical Company have already produced it. In recent years, many scholars in my country have studied the synthesis of tris(1,3-dichloro-2-propyl) phosphate. The Chinese patents whose publication numbers are CN102863468A, CN107556338A, and CN102807581B respectively introduce epichlorohy...

Examples

Embodiment 1

[0021] At room temperature, add 153g of phosphorus oxychloride and 774g of 1,3-dichloropropanol (molar ratio: 1:6) into the reactor and stir to raise the temperature to 115°C. After reacting at this temperature for 1 hour, under negative pressure Under the condition of -0.002MPa, the hydrogen chloride gas generated by the reaction is removed to the hydrogen chloride absorption device, and at the same time, the temperature is gradually raised to 180°C at a rate of 15°C / h, and the reaction is continued for 1 hour. The crude product after cooling is washed with alkali, washed with water, and distilled to obtain triphosphate (1,3-dichloropropyl) ester, the purity is 98.87%, the yield is 85.79%, and the 1,3-dichloropropanol recovered by distillation is recycled as the reaction raw material.

Embodiment 2

[0023] At room temperature, add 153g of phosphorus oxychloride and 903g of 1,3-dichloropropanol (molar ratio: 1:7) into the reactor and stir to raise the temperature to 110°C. After reacting at this temperature for 1.5 hours, under negative pressure Under the condition of -0.003MPa, the hydrogen chloride gas generated by the reaction is removed to the hydrogen chloride absorption device, and at the same time, the temperature is gradually raised to 180 °C at a rate of 20 °C / h, and the reaction is continued for 2 hours. The crude product after cooling is washed with alkali, washed with water, and distilled to obtain triphosphate (1,3-dichloropropyl) ester, the purity is 99.01%, and the yield is 87.42%. The 1,3-dichloropropanol recovered by distillation is recycled as the reaction raw material.

Embodiment 3

[0025] At room temperature, add 153g of phosphorus oxychloride and 645g of 1,3-dichloropropanol (molar ratio: 1:5) into the reactor and stir to raise the temperature to 120°C. After reacting at this temperature for 1 hour, under negative pressure Under the condition of -0.003MPa, the hydrogen chloride gas generated by the reaction is removed to the hydrogen chloride absorption device, and at the same time, the temperature is gradually raised to 180°C at a rate of 30°C / h, and the reaction is continued for 2 hours. The crude product after cooling is washed with alkali, washed with water, and distilled to obtain triphosphate (1,3-dichloropropyl) ester, the purity is 98.77%, the yield is 86.83%, and the 1,3-dichloropropanol recovered by distillation is recycled as the reaction raw material.

technical field

[0001] The invention belongs to the field of chemical synthesis, and in particular relates to a method for preparing tris(1,3-dichloropropyl) phosphate. Background technique

[0002] As a good flame retardant and flame retardant plasticizer, tris(1,3-dichloropropyl) phosphate is widely used in unsaturated polyester, rigid and flexible polyurethane foam, epoxy resin, phenolic resin , soft polyvinyl chloride, etc.

[0003] The synthesis of tris(1,3-dichloropropyl) phosphate at home and abroad is mainly based on the research on the reaction of epichlorohydrin and phosphorus oxychloride under the action of different catalysts. American Stauffer Chemical Company and Japan Daihachi Chemical Company have already produced it. In recent years, many scholars in my country have studied the synthesis of tris(1,3-dichloro-2-propyl) phosphate. The Chinese patents whose publication numbers are CN102863468A, CN107556338A, and CN102807581B respectively introduce epichlorohy...

Examples

Embodiment 1

[0021] At room temperature, add 153g of phosphorus oxychloride and 774g of 1,3-dichloropropanol (molar ratio: 1:6) into the reactor and stir to raise the temperature to 115°C. After reacting at this temperature for 1 hour, under negative pressure Under the condition of -0.002MPa, the hydrogen chloride gas generated by the reaction is removed to the hydrogen chloride absorption device, and at the same time, the temperature is gradually raised to 180°C at a rate of 15°C / h, and the reaction is continued for 1 hour. The crude product after cooling is washed with alkali, washed with water, and distilled to obtain triphosphate (1,3-dichloropropyl) ester, the purity is 98.87%, the yield is 85.79%, and the 1,3-dichloropropanol recovered by distillation is recycled as the reaction raw material.

Embodiment 2

[0023] At room temperature, add 153g of phosphorus oxychloride and 903g of 1,3-dichloropropanol (molar ratio: 1:7) into the reactor and stir to raise the temperature to 110°C. After reacting at this temperature for 1.5 hours, under negative pressure Under the condition of -0.003MPa, the hydrogen chloride gas generated by the reaction is removed to the hydrogen chloride absorption device, and at the same time, the temperature is gradually raised to 180 °C at a rate of 20 °C / h, and the reaction is continued for 2 hours. The crude product after cooling is washed with alkali, washed with water, and distilled to obtain triphosphate (1,3-dichloropropyl) ester, the purity is 99.01%, and the yield is 87.42%. The 1,3-dichloropropanol recovered by distillation is recycled as the reaction raw material.

Embodiment 3

[0025] At room temperature, add 153g of phosphorus oxychloride and 645g of 1,3-dichloropropanol (molar ratio: 1:5) into the reactor and stir to raise the temperature to 120°C. After reacting at this temperature for 1 hour, under negative pressure Under the condition of -0.003MPa, the hydrogen chloride gas generated by the reaction is removed to the hydrogen chloride absorption device, and at the same time, the temperature is gradually raised to 180°C at a rate of 30°C / h, and the reaction is continued for 2 hours. The crude product after cooling is washed with alkali, washed with water, and distilled to obtain triphosphate (1,3-dichloropropyl) ester, the purity is 98.77%, the yield is 86.83%, and the 1,3-dichloropropanol recovered by distillation is recycled as the reaction raw material.

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