CN1406943A - Preparation of fire retardant of polyphosphate containing bromine - Google Patents
Preparation of fire retardant of polyphosphate containing bromine Download PDFInfo
- Publication number
- CN1406943A CN1406943A CN 01132768 CN01132768A CN1406943A CN 1406943 A CN1406943 A CN 1406943A CN 01132768 CN01132768 CN 01132768 CN 01132768 A CN01132768 A CN 01132768A CN 1406943 A CN1406943 A CN 1406943A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- oxygen
- containing bromine
- hosphospiro
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A process for preparing bromine-contained polyphosphate as fire-retarding agent features the progressive esterifying reactions between tetrabromobiphenol-A, bibromoneopentanediol, and 3,9-dichloro-2,4,8,10-tetraoxy-3,9-diphosphoryl spirocyclo [5,5]-3,9-dioxyhendecane.
Description
Fire retardant is to be added in the various materials, is a class chemosynthesis material of purpose to improve the material fire retardant performance.Scientific experiment has at present confirmed that most of organbromine compounds and organo phosphorous compounds all have flame-retarded efficiency in various degree, and mixes use two class materials according to certain proportion, and their flame-retarded efficiency also has synergy.Present commercial fire retardant is widely used in various materials.But these fire retardants exist the defective of many aspects such as migration to analyse white phenomenon, material mechanical performance and mechanical property decline, use properties variation etc. in application process.Scientific experiment proof aggretion type high molecular weight flame retardant has the following advantages: stablize good weatherability with good, the heat-resisting decomposition temperature height of material intermiscibility, use, with respect to some body materials, add the aggretion type high molecular weight flame retardant its mechanical property and processing characteristics are improved.
Based on above consideration, the present invention adopts now commercial reactive aryl bromide fire retardant tetrabromobisphenol-A, reactive alkyl bromide fire retardant 2,2-dibromo methyl isophthalic acid, ammediol, swelling property phosphate flame retardant 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane is as starting raw material of the present invention, provide a kind of novel fire retardant of polyphosphate containing bromine, it has following chemical structural formula:
Following formula n=6 wherein, 8......
The present invention proposes fire retardant of polyphosphate containing bromine, can prepare fire retardant of polyphosphate containing bromine of the present invention according to following technology.Synthetic method is preferably: at first in halogenated hydrocarbon solvent, adopt 2 of equimolar amount, 2-dibromo methyl isophthalic acid, ammediol, 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3, esterification takes place in 9-dioxy undecane and can being mixed together as the alkali of acid binding agent, makes 3-chloro-9-(dibromo neopentyl oxygen)-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane (A component).Representational halogenated hydrocarbon solvent is a chloroform, 1,2-ethylene dichloride, chlorobenzene and other aprotic polar solvent.The alkali that is suitable for is triethylamine, pyridine, N, accelerine.Above-mentioned esterification is under 10～120 ℃, and optimum temps is 30～60 ℃, finishes in 1～16 hour.
Above-mentioned esterification can be expressed with following reaction formula:
(A component)
Secondly in halogenated hydrocarbon solvent, adopt the tetrabromobisphenol-A of equimolar amount, 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3, esterification takes place in 9-dioxy undecane and can being mixed together as the alkali of acid binding agent.Make 3-chloro-9-(tetrabromobisphenol-A oxygen base)-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane (B component).Representational halogenated hydrocarbon solvent as hereinbefore.The alkali that is suitable for is identical with aforementioned regulation.Above-mentioned esterification is under 10～120 ℃, and optimum temps is 60～80 ℃, finishes in 1～16 hour.
Above-mentioned esterification can be expressed with following reaction formula:
(B component)
Moreover, the solution of the equimolar amount A component of aforementioned gained and the solution of B component and the acid binding agent alkali that can be used as of 2.5 times of molar weights are together mixed, the esterification polyreaction takes place, can make fire retardant of polyphosphate containing bromine of the present invention.Alkali as acid binding agent is identical with aforementioned regulation.The esterification polyreaction is under 30～180 ℃, and optimum temps is 80～90 ℃, finishes in 1～48 hour.
Final reacting product can separate with classic methods.Method was the crystal salt that filters out in the reaction product system preferably.Most of solvent is removed in the distillation under negative pressure of filtrate part, and residue adopts ethanol sedimentation mode or spraying drying mode, eliminates solvent, makes product.The product that makes like this can further adopt the washing with alcohol method to purify.
According to the technology of preparing that the invention provides polyphosphate containing bromine group combustion agent, the product that conclusive evidence makes has 2,2-dibromo methyl isophthalic acid, 3 propylene glycol～3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane～tetrabromobisphenol-A replaces the regularity of equal poly structure.We discover and meet above-mentioned alternately such poly phosphate of homopolymerization rule, have the following service performance of fire retardant preferably: molecular-weight average 6～80,000,183～190 ℃ of softening temperatures, 270 ℃ of heat decomposition temperatures, bromine content 38%, phosphorus content 9.9%.
Know compound and be the commercial goods for above-mentioned three kinds as the starting raw material of starting raw material of the present invention and other.
Following example further specifies the process of preparation fire retardant of polyphosphate containing bromine of the present invention, but these examples are not interpreted as limitation of the present invention in all senses.
Example 1,
The present invention proposes the preparation of A component especially
In the reaction flask that agitator, reflux exchanger, dropping funnel are housed, add 55 gram (0.21 moles) 2,2-dibromo methyl isophthalic acid, 3 propylene glycol, 58 gram (0.21 moles) 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane, 22 gram (0.21 mole) triethylamines, 180 milliliter 1, the 2-ethylene dichloride.It is standby to stir down 40～60 ℃ of reactions 2 hours.
Example 2,
The present invention proposes the preparation of B component especially
In the reaction flask that agitator, reflux exchanger, dropping funnel are housed, add 114 gram (0.21 mole) tetrabromobisphenol-As, 58 gram (0.21 moles) 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane, 22 gram (0.21 mole) triethylamines, 180 milliliter 1, the 2-ethylene dichloride.It is standby to stir down 60～80 ℃ of reactions 2.5 hours.
Example 3,
The present invention proposes the preparation of fire retardant of polyphosphate especially
In the reaction flask that agitator, reflux exchanger, dropping funnel are housed, add 120 milliliter 1,2-ethylene dichloride, 55 gram (0.25 mole) triethylamines.Stir down, 80～90 ℃ of temperature controls splash into the A component solution of example 1 gained and the B component solution of example 2 gained simultaneously, and insulation reaction finished in 12 hours.Final reacting product solution is cooled to room temperature, removes by filter the triethylamine hydrochloride that crystallization is separated out.Distillation concentrated filtrate, residue spraying drying make fire retardant of polyphosphate containing bromine 235 grams, yield 93.4%.More than thick product purify for 3～5 times through washing with alcohol.
Claims (5)
1, the method for a kind of novel fire retardant of polyphosphate containing bromine of preparation, it has following chemical structural formula:
Following formula n=6 wherein, 8......
2, according to the method for claim 1, the synthesis material of fire retardant of polyphosphate containing bromine is a tetrabromobisphenol-A.
3, according to the method for claim 1, the synthesis material of fire retardant of polyphosphate containing bromine is 2,2-dibromo methyl isophthalic acid, ammediol.
4, according to the method for claim 1, the synthesis material of fire retardant of polyphosphate containing bromine is 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane.
5, according to the method for claim 1, the method for the synthetic novel fire retardant of polyphosphate containing bromine of this kind comprises:
(1) tetrabromobisphenol-A of equimolar amount and 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane and alkali reagent in halogenated hydrocarbon solvent, cold condition generation esterification, make 3-chloro-9-(dibromo neopentyl oxygen)-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane (following this is defined as the A component).
(2) 2 of equimolar amount, 2-dibromo methyl isophthalic acid, ammediol, 3,9-two chloro-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane and alkali reagent are in halogenated hydrocarbon solvent, and cold condition generation esterification makes 3-chloro-9-(tetrabromobisphenol-A oxygen base)-2,4,8,10-four oxygen-3,9-hosphospiro [5,5]-3,9-dioxy undecane (following this is defined as the B component).
(3) the A component phosphoric acid ester of equimolar amount and B component phosphoric acid ester and alkali reagent are in halogenated hydrocarbon solvent, and cold condition generation esterification polyreaction makes fire retardant of polyphosphate containing bromine of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132768 CN1406943A (en) | 2001-09-07 | 2001-09-07 | Preparation of fire retardant of polyphosphate containing bromine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132768 CN1406943A (en) | 2001-09-07 | 2001-09-07 | Preparation of fire retardant of polyphosphate containing bromine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1406943A true CN1406943A (en) | 2003-04-02 |
Family
ID=4671569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01132768 Pending CN1406943A (en) | 2001-09-07 | 2001-09-07 | Preparation of fire retardant of polyphosphate containing bromine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1406943A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293134C (en) * | 2005-07-05 | 2007-01-03 | 四川大学 | Phosphor-contained fire-retardant with two spirane structure and preparation method |
| CN105566385A (en) * | 2016-01-19 | 2016-05-11 | 苏州科技学院 | Method for preparing tetrabromobisphenol-A organic-phosphonate compound |
-
2001
- 2001-09-07 CN CN 01132768 patent/CN1406943A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293134C (en) * | 2005-07-05 | 2007-01-03 | 四川大学 | Phosphor-contained fire-retardant with two spirane structure and preparation method |
| CN105566385A (en) * | 2016-01-19 | 2016-05-11 | 苏州科技学院 | Method for preparing tetrabromobisphenol-A organic-phosphonate compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243385B (en) | A kind of DOPO based flameproofings and preparation method thereof | |
| CN100412162C (en) | Dicyclic phosphonate fire retardant and its synthesis | |
| CN105295093A (en) | Ring phosphonitrile type additive flame retardant and preparation method thereof | |
| CN1406943A (en) | Preparation of fire retardant of polyphosphate containing bromine | |
| CN102477151A (en) | Catalyst for preparation of polyester, its preparation method, and production method of polyester | |
| CN102675371A (en) | Cyclic phenyl phosphonate compound and method for preparing same | |
| JP2000219745A (en) | Flame-retardant compound, its production, and flame- retarded organic polymer material | |
| CN109111570A (en) | Linear phosphorous schiff bases carbon forming agent and its synthetic method | |
| CN1061660C (en) | Process for preparing tribromoneopentyl chloroalkyl phosphates | |
| CN102321245B (en) | Benzoguanamine carboxethyl phenylphosphinic acid condensation product and preparation method | |
| CN101899064B (en) | Preparation method of dihydric phenol di(dialkyl phenyl organic phosphate) | |
| CN101220054A (en) | Method for preparing Combretastatin A-4 phosphoric acid ester disodium salt | |
| CN110922636B (en) | Bisphenol acid-based phosphorus-nitrogen flame retardant and preparation method and application thereof | |
| CN101941989B (en) | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof | |
| CN1880324A (en) | Method for the production of hydroxymethyl alkyl phosphinic acids and its ester thereof | |
| CN114524843A (en) | Hydroxyl-terminated reactive flame retardant and preparation method thereof | |
| US3258492A (en) | P-chloro or hydroxy benzyl tertiary phosphine oxides | |
| CN102558228A (en) | Process for preparing diphenyl diphenoxy phosphoryl aniline compound | |
| CN101501048B (en) | Diaryl alkylphosphonates and method for preparing same | |
| CN1315854C (en) | Methyl-phospho-acid pentaerythritol ester with hydroxy and its preparation | |
| CN1208042A (en) | Preparation of dichloro pentaerythritol phosphite | |
| CN102408443B (en) | Preparation method of zoledronic acid | |
| CN113185547B (en) | Preparation method of compound with flame retardant property | |
| CN103554186A (en) | Preparation method of phosphonitrilic chloride trimer | |
| CN112011088B (en) | Flame retardant diphenyl phosphinidene organosilicon cage-like ester amine compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |