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Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic

A technology of engineering plastics and high temperature resistance, which is used in the synthesis of phosphate ester flame retardants, can solve the problems of not being able to withstand the processing temperature of engineering plastics, unable to meet the application requirements of plastics, and reducing the thermal deformation temperature of plastics. Low-cost, easy-to-absorb effects

Inactive Publication Date: 2008-06-11
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In the process of researching and developing substitutes for brominated flame retardants, phosphorus and phosphorus-nitrogen flame retardants are the first to be favored and valued, and the most studied are halogen-free phosphates, but phosphoric acid esters that can be used for flame-retardant plastics Esters cannot meet the application requirements of plastics (especially high-grade downstream plastics) due to the following problems
(1) Most of them have low heat resistance, and the initial decomposition temperature is mostly below 250°C, which cannot withstand the processing temperature of engineering plastics; (2) The phosphorus content is low, generally not exceeding 10%, so the flame retardant efficiency is limited; (3) ) are water-soluble and have low hydrolytic stability; (4) most of them have a large plasticizing effect, which reduces the heat distortion temperature of plastics; (5) there are currently some phosphate esters with high thermal stability, such as aromatic Bisphosphonates, but they are liquid, difficult to process, and have a significant plasticizing effect

Method used

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  • Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic
  • Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic
  • Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] In a 500ml four-neck flask equipped with a thermometer, constant pressure dropping funnel, mechanical stirring, reflux condenser and drying tube, add 150ml of acetonitrile, 6g of catalyst anhydrous aluminum trichloride and 113g of PEPA in sequence, and heat the mixture to reflux under stirring. , Add dropwise 18.5ml of phosphorus oxychloride. After the dropwise addition, keep warm at 80-83°C and reflux for 12 hours until no hydrogen chloride gas is released. Cool to room temperature, filter, wash with water until the filtrate is neutral, dry and weigh. Yield 80.5%.

Embodiment 2

[0026] In a 500ml four-neck flask equipped with a thermometer, constant pressure dropping funnel, mechanical stirring, reflux condenser and drying tube, add 150ml of acetonitrile, 1.5g of ferric chloride and 110g of PEPA in sequence, and heat the mixture to reflux under stirring for 2.5h Add 18ml of phosphorus oxychloride dropwise. After the dropwise addition, keep warm at 80-83°C for reflux reaction for 11 hours (when almost no hydrogen chloride is absorbed, hydrogen chloride is distilled intermittently under a certain negative pressure). Cool to room temperature, filter, wash with boiling water until the filtrate is neutral, dry, and weigh. Yield 87.2%.

Embodiment 3

[0028] In a 500ml four-necked flask equipped with a thermometer, a constant pressure dropping funnel, mechanical stirring, a reflux condenser and a drying tube, add 150ml of acetonitrile, 3.5g of ferric chloride and 110g of PEPA in sequence, and heat the mixture to reflux under stirring. Add 18ml of phosphorus oxychloride dropwise, keep warm at 80-83°C for reflux reaction for 14h (when almost no hydrogen chloride is absorbed, hydrogen chloride is intermittently evaporated at a certain negative pressure). Cool to room temperature, filter, wash with boiling water until the filtrate is neutral, dry, and weigh. The yield is 90.7%.

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Abstract

The invention relates to a synthesis method of engineer plastic high temperature resistant cage-type cyclic phosphate-3(1-oxo-1-phosphacyclopentene-2, 6, 7-trioxabicyclo [2, 2, 2] octane-4-methano) phosphate (abbreviated as trimer), wherein the trimer has symmetry cage-type cyclic structure (as below). The trimer has high temperature resistance (320DEG C) and phosphor content of 21.2%, which is not dissolved in water and is stable for hydrolysis. The trimer not contains halogen, affects little on flame retardant substrate and thermal deformation temperature. The synthesis materials are easily accessible. The invention has mild reaction conditions, low energy consumption, stable and controllable operation, while the yields in two steps both reach 90% at least, the hydrochloride generated in synthesis is completed absorbed, the generated some waste water can be treated biochemically to be discharged at standard, and the solvent can be circulated, to reduce environment pollution.

Description

technical field [0001] The invention relates to the synthesis of a phosphate flame retardant, belonging to the field of chemical synthesis. Background technique [0002] Cage-type cyclic phosphate is a new type, high-efficiency, temperature-resistant flame retardant, which belongs to the additive type. It can be blended with high polymer base material through a twin-screw extruder to produce flame-retardant plastics, especially high-grade flame-retardant engineering plastics, which are widely used in the manufacture of high-tech electronics, precision machinery, aerospace, etc. Devices and components to ensure the safety of products, reduce and eliminate fire hazards. Scientific experiments and years of practical experience have proved that the use of flame-retardant materials (mainly flame-retardant plastics) is one of the most important strategic measures to improve the fire safety of products, protect people's lives and property, and protect the environment. It is extrem...

Claims

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Application Information

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IPC IPC(8): C07F9/6574C08K5/527
Inventor 欧育湘李昕房小敏赵毅
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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