CN102924393A

CN102924393A - Production method of tris (2,4,6-tribromophenoxy) cyanurate

Info

Publication number: CN102924393A
Application number: CN2012104453779A
Authority: CN
Inventors: 孔庆池; 尹丽娟; 李懂懂; 李汝奕
Original assignee: China University of Petroleum East China
Current assignee: China University of Petroleum East China
Priority date: 2012-11-09
Filing date: 2012-11-09
Publication date: 2013-02-13
Anticipated expiration: 2032-11-09
Also published as: CN102924393B

Abstract

The invention relates to a production method of flame retardant tris (2,4,6-tribromophenoxy) cyanurate, belonging to the production field of the flame retardant. The production method comprises the following steps: dissolving phenol into a chlorobenzene solvent; then adding anhydrous aluminum trichloride as a catalyst; adding cyanuric chloride; reacting cyanuric chloride with phenol to synthesize the tris(2,4,6-tribromophenoxy)cyanurate; cooling and adding water; using bromine as a brominating agent; and brominating, washing, distilling, crystallizing, performing centrifugal separation and drying to obtain the finished product tris (2,4,6-tribromophenoxy) cyanurate. According to the production method provided by the invention, problems such as tribromophenol synthesis, purification and drying are avoided; the reaction is carried out in one reaction kettle; the treatment for purifying, separating and drying the intermediate product is omitted; the process is simplified and the energy consumption is reduced.

Description

A kind of three (tribromophenoxy)-cyanurate production methods

Technical field

The present invention relates to a kind of production method of fire retardant, be specifically related to the production method of a kind of fire retardant three (tribromophenoxy)-cyanurate, belong to the fire retardant production field.

Background technology

Three (tribromophenoxy)-cyanurates are a kind of outstanding fire retardants, have fabulous flame retardant properties, all its synthetic method have been done large quantity research both at home and abroad.

U.S. Albemarle Corporation is in the disclosed technology of US5965731, use acetone to make solvent, at first in anhydrous propanone, add tribromophenol, then add aqueous sodium hydroxide solution, make tribromophenol sodium acetone soln, under reflux temperature, drip the acetone soln of cyanuric chloride, made three (tribromophenoxy)-cyanurates.

Patent US4039538 discloses the use ethylene glycol monomethyl ether and has made the method that solvent synthesizes three (tribromophenoxy)-cyanurates, in the ethylene glycol monomethyl ether solvent, add tribromophenol and sodium hydroxide, make it generate tribromophenol sodium, then add cyanuric chloride and make its reaction, 214-216 ℃ of the product fusing point that obtains, yield are 86.5%, reuse solvent recrystallization, can obtain fusing point 229-231 ℃ product.

CN1888014, US5696302, US5907040 disclose use and the immiscible organic solvent of water is made the technology that solvent is produced three (tribromophenoxy)-cyanurates.Method is to allow first tribromophenol and sodium hydroxide reaction, make the tribromophenol sodium water solution, secondly, cyanuric chloride is added in the anhydrous organic solvent, after aqueous phase adds phase-transfer catalyst, cyanuric chloride solution is slowly added in the tribromophenol sodium solution, generate three (tribromophenoxy)-cyanurates with the reaction of tribromophenol sodium.

In the prior art, all be take tribromophenol, cyanuric chloride, sodium hydroxide as raw material, tribromophenol has suction, distillation character, and difficult dry, the drying process loss amount is large, produces tribromophenol and pollutes larger.

Summary of the invention

For the deficiencies in the prior art, the present invention proposes at first synthetic three (phenoxy group)-cyanurates, and then the technique of synthetic three (the tribromophenoxy)-cyanurates of bromination, specifically, phenol is dissolved in the chlorobenzene solvent, then add aluminum trichloride (anhydrous) and make catalyzer, add again cyanuric chloride, allow cyanuric chloride and phenol reactant synthesize three (phenoxy group)-cyanurates, cooling also adds entry, makees bromizating agent with bromine, through bromination, washing, distillation, crystallization, centrifugation, the techniques such as drying, obtain three (tribromophenoxy)-cyanurate finished products, the present invention has avoided tribromophenol synthetic, purify, the problems such as drying, reaction is carried out in a reactor, has saved the purification of intermediates, separate, drying waits processing, simplify technique, reduced energy consumption.

The principles of chemistry that the present invention adopts are: phenol generates three (phenoxy group)-cyanurate and HCl with the cyanuric chloride reaction under Catalyzed by Anhydrous Aluminium Chloride, hydrochloric acid is very easily water-soluble, and water absorbs; Three (phenoxy group)-cyanurates are dissolved in chlorobenzene, stay in the chlorobenzene, then add entry, bromine, allow bromine and three (phenoxy group)-cyanurate generation substitution reaction generate three (tribromophenoxy)-cyanurate and HBr, utilize HBr character soluble in water to change water over to.

The technical solution used in the present invention is:

(1) 300-350kg phenol is added in the 500kg chlorobenzene, then add aluminum trichloride (anhydrous) and make catalyzer, make solution A, the phenol amount of preferably using is 300kg, and the consumption of catalyzer is the 0.5-5% of phenol usage, preferred 1%;

(2) the 196kg cyanuric chloride is dissolved in the 500kg chlorobenzene, makes solution B;

(3) under normal pressure, temperature 10-132 ℃, B solution is splashed in the A solution, be warming up to 132 ℃, insulation reaction 1-5 hour, the HCl that reaction generates derives water with conduit and absorbs, the solution that obtains is three (phenoxy group) cyanurate chlorobenzene solution, and the preferred dropping temperature of the present invention is 132 ℃, preferred 3 hours of soaking time;

(4) solution that (3) is obtained is cooled to 0-60 ℃, and preferred 20-30 ℃, add 300-900kg water, preferred 828kg water drips the 1500-1558kg bromine under the frozen water cooling, preferred 1529kg bromine, then insulation reaction 1-3 hour, preferred 2 hours;

(5) standing demix, the upper strata is the HBr aqueous solution, separates, and lower floor is three (tribromophenoxy)-cyanurate chlorobenzene solutions, add sodium sulfite aqueous solution and make its pH=6-7, add water washing once, then add 1000kg water, distillation, chlorobenzene is steamed, three (tribromophenoxy)-cyanurate crystallizations, centrifugal, dry, obtain finished product.

The invention has the beneficial effects as follows: the present invention adopts directly synthetic three (the tribromophenoxy)-cyanurates of phenol, synthetic, purification, the drying of tribromophenol have been avoided, whole building-up process is carried out in a reactor, saved the processing such as purification, separation, drying of intermediates, simplify technique, reduced energy consumption.

Embodiment

Below further set forth the present invention with example, those skilled in the art can make suitable adjustment to various raw material consumptions, temperature of reaction, reaction times and processing mode according to this patent principle of design.

Example 1

In No. 1 reactor, add chlorobenzene 500kg, then add tribromophenol 300kg and aluminum trichloride (anhydrous) 3kg; Add chlorobenzene 500kg at No. 2 reactors, then add cyanuric chloride 196kg, stir and make its dissolving; No. 1 reactor is warming up to 132 ℃, under normal pressure No. 2 material in reactor is added drop-wise to reactor No. 1, the HCl that reaction produces derives with conduit, and water absorbs, after being added dropwise to complete, insulation reaction 3 hours, then, be cooled to 20 ℃, add 828kg water, the lower 1529kg bromine that drips of frozen water cooling.Insulation reaction 2 hours, standing demix is told the HBr aqueous solution on upper strata, in chlorobenzene layer, add sodium sulfite aqueous solution and make its pH=6-7, add water washing once, then add 1000kg water, distillation, chlorobenzene is steamed, three (tribromophenoxy)-cyanurate crystallizations, centrifugation, drying, obtain 1130kg three (tribromophenoxy)-cyanurate, 229-230 ℃ of product fusing point.

Example 2

In No. 1 reactor, add chlorobenzene 500kg, then add tribromophenol 300kg and aluminum trichloride (anhydrous) 6kg; Add chlorobenzene 500kg at No. 2 reactors, then add cyanuric chloride 196kg, stir and make its dissolving; Normal pressure, 20 ℃ No. 2 material in reactor are added drop-wise to reactor No. 1, the HCl that reaction produces derives water with conduit and absorbs; After being added dropwise to complete, be warming up to 132 ℃, then insulation reaction 5 hours, is cooled to 20 ℃, adds 700kg water, the lower 1529kg bromine that drips of frozen water cooling.Insulation reaction 2 hours, standing demix is told the HBr aqueous solution on upper strata, in chlorobenzene layer, add sodium sulfite aqueous solution and make its pH=6-7, add water washing once, then add 1000kg water, distillation, chlorobenzene is steamed, three (tribromophenoxy)-cyanurate crystallizations, centrifugation, drying, obtain 1128kg three (tribromophenoxy)-cyanurate, 228-230 ℃ of product fusing point.

Claims

1. the production method of (tribromophenoxy)-cyanurate, its feature may further comprise the steps:

300-350kg phenol is added in the 500kg chlorobenzene, and the aluminum trichloride (anhydrous) that then adds phenol usage 0.5-5% is made catalyzer, makes solution A; The 196kg cyanuric chloride is dissolved in the 500kg chlorobenzene, makes solution B; Under normal pressure, temperature 10-132 ℃, B solution is splashed in the A solution, be warming up to 132 ℃, insulation reaction 1-5 hour, the HCl that reaction generates derived water with conduit and absorbs, the solution that obtains is three (phenoxy group) cyanurate chlorobenzene solution; Three (phenoxy group) cyanurate chlorobenzene solution that obtains is cooled to 0-60 ℃, add 300-900kg water, under the frozen water cooling, drip the 1500-1558kg bromine, then insulation reaction 1-3 hour, standing demix, the upper strata is the HBr aqueous solution, separates, and lower floor is three (tribromophenoxy)-cyanurate chlorobenzene solutions, add sodium sulfite aqueous solution and make its pH=6-7, add water washing once, then add 1000kg water, distillation, chlorobenzene is steamed, three (tribromophenoxy)-cyanurate crystallizations, centrifugal, dry, obtain finished product.

2. the production method of three (tribromophenoxy)-cyanurates according to claim 1, it is characterized in that: preferred production stage is for adding 300kg phenol in the 500kg chlorobenzene, then the aluminum trichloride (anhydrous) that adds phenol usage 1% is made catalyzer, makes solution A; The 196kg cyanuric chloride is dissolved in the 500kg chlorobenzene, makes solution B; Under normal pressure, 132 ℃ of temperature, B solution is splashed in the A solution, insulation reaction 3 hours, the HCl that reaction generates derives water with conduit and absorbs, the solution that obtains is three (phenoxy group) cyanurate chlorobenzene solution; Three (phenoxy group) cyanurate chlorobenzene solution that obtains is cooled to 20-30 ℃, adds 828kg water, drip the 1529kg bromine under the frozen water cooling, then insulation reaction is 2 hours; Standing demix, the upper strata is the HBr aqueous solution, separates, and lower floor is three (tribromophenoxy)-cyanurate chlorobenzene solutions, add sodium sulfite aqueous solution and make its pH=6-7, add water washing once, then add 1000kg water, distillation, chlorobenzene is steamed, three (tribromophenoxy)-cyanurate crystallizations, centrifugal, dry, obtain finished product.