CN109796315A - A kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether - Google Patents
A kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether Download PDFInfo
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- CN109796315A CN109796315A CN201910133120.1A CN201910133120A CN109796315A CN 109796315 A CN109796315 A CN 109796315A CN 201910133120 A CN201910133120 A CN 201910133120A CN 109796315 A CN109796315 A CN 109796315A
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Abstract
The present invention relates to a kind of preparation methods of high heat stability sex flame retardant methyl eight bromo ether, belong to and utilizes the technical field for being chemically synthesized bromide fire retardant, the present invention passes through tetrabromobisphenol A first and 3- halogenated methyl propylene prepares four bromo-ether of intermediate methyl, the conversion ratio that second step improves bromination addition reaction by the way that efficient catalyst is added reduces the generation of by-product, the thermal stability of product is improved by the way that specific anhydride compound is added in the product again, prepare the methyl eight bromo ether fire retardant with high thermal stability, the methyl eight bromo ether product that the present invention obtains has better stability, polypropylene plastics and fiber can be preferably applied to, polystyrene foam plastics, unsaturated polyester (UP), polycarbonate, polypropylene, synthetic rubber etc. it is fire-retardant, it is particularly useful for addition production XPS flame-retardant master batch.
Description
Technical field
The present invention relates to a kind of preparation methods of high heat stability sex flame retardant methyl eight bromo ether, belong to and are closed using chemical method
At the technical field of bromide fire retardant.
Background technique
In recent years, as modern compound probability rapidly develops and the promotion of fire safety consciousness, national legislation are forced in master
Industry is wanted to carry out the use of fire proofing.It is fire-retardant with the development of Chinese synthetic material industry and the continuous expansion of application field
Agent is each in building, weaving, plastics, electronic apparatus, communications and transportation, space flight and aviation, household furniture, interior decoration, clothing, food, lodging and transportion -- basic necessities of life etc.
It has obtained preferably applying in a field, and has played huge effect.
China's plastics industry has great structural adjustment, and the following flame retardant plastics will will increase, and will propose to plastics
Tightened up flame-retardancy requirements, shared ratio will be increased flame retardant plastics in the plastic, 2,2- bis- [3,5- bis- bromo- 4- (2,
The bromo- 2- methyl propoxyl group of 3- bis-) phenyl] propane (abbreviation methyl eight bromo ether) is that the novel bromine system of one kind that researches and develops in recent years is fire-retardant
Agent is mainly used for the application in order to substitute hexabromocyclododecane in retardant expanded polystyrene, and the country discloses at present
Patent synthetic route be the first step by bisphenol-A and 3- halogenated methyl propylene be that raw material prepares bis- [4- (the 2- methallyls of 2,2-
Oxygroup) phenyl] propane, bromine is added in second step, by addition reaction and substitution reaction prepare 2,2- it is bis- [3,5- bis- bromo- 4- (2,
The bromo- 2- methyl propoxyl group of 3- bis-) phenyl] propane, and foreign patent technology has no the thermal stability for effectively improving this fire retardant
Measure, thermal stability (i.e. temperature of initial decomposition) generally can only achieve 220 DEG C, limits its use, therefore compel to be essential
Research and develop a kind of fire retardant 2 with high thermal stability, bis- [3,5- bis- bromo- 4- (2, the 3- bis- bromo- 2- methyl propoxyl group) benzene of 2-
Base] bromopropane product.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether, this method is
Four bromo-ether of intermediate methyl is prepared first with tetrabromobisphenol A and 3- halogenated methyl propylene, is added bromine, is passed through addition reaction
Bis- [3,5- bis- bromo- 4- (2, the 3- bis- bromo- 2- methyl propoxyl group) phenyl] propane of 2,2- are prepared, and acid anhydrides chemical combination is added in the product
Object improves the thermal stability of product.
A kind of high heat stability sex flame retardant methyl eight bromo ether of the invention the preparation method is as follows:
(1) stirring be added into solvent A in tetrabromobisphenol A and piece alkali be warming up to and be completely dissolved, within specified temperatures to
Methylallyl chloride is added dropwise in solution, etherification reaction occurs and generates four bromo-ether of methyl, intermediate methyl tetrabromo is obtained by filtration in cooling
Ether；
(2) four bromo-ether of intermediate methyl is added in solvent B and is dissolved, material carries out washing point after all dissolving
Water, then be added effective catalyst and within specified temperatures be added bromine progress addition reaction obtain the molten of the eight bromo ether containing methyl
Liquid, then washed, distillation crystallization, filtering drying obtains methyl eight bromo ether；
(3) anhydride compound is added and the product of step (2) is sufficiently mixed, obtain high thermal stability methyl eight bromo ether
Fire retardant.
In above-mentioned technical proposal, it is preferred that solvent A described in step (1) is in methanol, ethyl alcohol, ethylene glycol, water etc.
It is one or more；Preferably, the mass ratio of tetrabromobisphenol A and solvent A is 1:1~2；Preferably, tetrabromobisphenol A: piece alkali: methyl
Chloropropene molar ratio is 1:2.01~2.1:2.01~2.11；Preferably, when being added dropwise in step (1) specific temperature be 30 DEG C~
70℃。
Preferably, solvent B described in step (2) is alkane solvents, such as methylene chloride, dichloroethanes, carbon tetrachloride
It is 1~2g/1g methyl, four bromo-ether Deng, dosage；Preferably, the dosage of bromine be bromine and four bromo-ether molar ratio of methyl be 2.01~
2.05:1；Preferably, specific temperature is -10 DEG C~30 DEG C in step (2).
Preferably, effective catalyst described in step (2) is one of titanium tetrachloride, tin tetrachloride, and dosage is
0.005~0.02g/1g methyl, four bromo-ether.
Preferably, anhydride compound described in step (3) is acetic anhydride, maleic anhydride, maleic anhydride, adjacent benzene two
One of formic anhydride, additional amount are 0.005~0.02g/1g methyl eight bromo ether.
The present invention improves the conversion ratio of bromination addition reaction by new and effective catalyst, reduces the production of by-product
It gives birth to, and improves the thermal stability of product by the way that specific anhydride compound is added, prepare the first with superior heat-stability
Base eight bromo ether fire retardant, thermal stability can be increased to 250 DEG C or more from 220 DEG C, and can be used for adding preparation has high resistant fuel efficiency
The XPS flame-retardant master batch of fruit has better application prospect.
Detailed description of the invention
The nuclear magnetic resonance spectroscopy of Fig. 1 methyl eight bromo ether；
The infrared spectrum of Fig. 2 methyl eight bromo ether；
Specific embodiment
Embodiment 1
Solvent 250mL, deionized water 50ml is added, opens stirring and tetrabromobisphenol A 175g is added, piece alkali 26.4g is added, stirs
Mixing dissolves material all, is to slowly warm up to 30 DEG C, controls 40 DEG C or so dropwise addition methylallyl chloride 59.72g, is added dropwise, and rises
Temperature keeps thermotonus 8h, is cooled to 30 DEG C of suction filtrations, obtains four bromo-ether of methyl to 50 DEG C；Methylene chloride 300g is added, is stirred
Make material dissolution, the washing of 100g water is added and divides water, it is organic to be added to tin tetrachloride 3.15g, in 10 DEG C or so dropwise addition bromine 104g,
Reaction half an hour is added dropwise, water 100g is added and stirs half an hour, stands half an hour, moisture is gone out, water 300g is added, heating will
Solvent steams, and material is precipitated in water, and filtering drying obtains product, and then plus maleic anhydride 2g is uniformly mixed with material,
The weightless thermal decomposition temperature of obtained high thermal stability methyl eight bromo ether 1% is 245 DEG C.
Embodiment 2
Solvent 275mL, deionized water 50ml is added, opens stirring and tetrabromobisphenol A 175g is added, piece alkali 26.6g is added, stirs
Mixing dissolves material all, is to slowly warm up to 30 DEG C, controls 40 DEG C or so dropwise addition methylallyl chloride 60g, is added dropwise, is warming up to
60 DEG C, thermotonus 8h is kept, 30 DEG C of suction filtrations is cooled to, obtains four bromo-ether of methyl；Methylene chloride 325g is added, stirring makes object
Material dissolution is added the washing of 100g water and divides water, organic to be added to titanium tetrachloride 3.15g, in 20 DEG C or so dropwise addition bromine 104.2g, drop
Bi Fanying half an hour is added, water 100g is added and stirs half an hour, stands half an hour, moisture is gone out, water 300g is added, heating will be molten
Agent steams, and material is precipitated in water, and filtering drying obtains product, and then plus phthalic anhydride 3g is uniformly mixed, and obtains height
The weightless thermal decomposition temperature of thermal stability methyl eight bromo ether 1% is 255 DEG C.
Embodiment 3
Solvent 300mL, deionized water 50ml is added, opens stirring and tetrabromobisphenol A 175g is added, piece alkali 26.8g is added, stirs
Mixing dissolves material all, is to slowly warm up to 30 DEG C, controls 50 DEG C or so dropwise addition methylallyl chloride 60.4g, is added dropwise, and heats up
To 70 DEG C, thermotonus 8h is kept, 30 DEG C of suction filtrations is cooled to, obtains four bromo-ether of methyl；Methylene chloride 350g is added, stirring makes
Material dissolution is added the washing of 100g water and divides water, organic to be added to titanium tetrachloride 3g, in 20 DEG C or so dropwise addition bromine 104.4g, drop
Bi Fanying half an hour is added, water 100g is added and stirs half an hour, stands half an hour, moisture is gone out, water 300g is added, heating will be molten
Agent steams, and material is precipitated in water, and filtering drying obtains product, and then plus maleic anhydride 4g is uniformly mixed, and obtains height
The weightless thermal decomposition temperature of thermal stability methyl eight bromo ether 1% is 256 DEG C.
Embodiment 4
Solvent 320mL, deionized water 50ml is added, opens stirring and tetrabromobisphenol A 175g is added, piece alkali 26.8g is added, stirs
Mixing dissolves material all, is to slowly warm up to 30 DEG C, controls 50 DEG C or so dropwise addition methylallyl chloride 60.4g, is added dropwise, and heats up
To 70 DEG C, thermotonus 8h is kept, 30 DEG C of suction filtrations is cooled to, obtains four bromo-ether of methyl；Methylene chloride 300g is added, stirring makes
Material dissolution is added the washing of 100g water and divides water, organic to be added to titanium tetrachloride 2.5g, in 20 DEG C or so dropwise addition bromine 103.5g,
Reaction half an hour is added dropwise, water 100g is added and stirs half an hour, stands half an hour, moisture is gone out, water 300g is added, heating will
Solvent steams, and material is precipitated in water, and filtering drying obtains product, and phthalic anhydride 2.5g is then added and is uniformly mixed, institute
Obtaining the weightless thermal decomposition temperature of high thermal stability methyl eight bromo ether 1% is 252 DEG C.
Embodiment 5
Solvent 320mL, deionized water 50ml is added, opens stirring and tetrabromobisphenol A 175g is added, piece alkali 26.8g is added, stirs
Mixing dissolves material all, is to slowly warm up to 30 DEG C, controls 50 DEG C or so dropwise addition methylallyl chloride 60.4g, is added dropwise, and heats up
To 70 DEG C, thermotonus 8h is kept, 30 DEG C of suction filtrations is cooled to, obtains four bromo-ether of methyl；Methylene chloride 300g is added, stirring makes
Material dissolution is added the washing of 100g water and divides water, organic to be added to tin tetrachloride 2.5g, in 20 DEG C or so dropwise addition bromine 103.5g,
Reaction half an hour is added dropwise, water 100g is added and stirs half an hour, stands half an hour, moisture is gone out, water 300g is added, heating will
Solvent steams, and material is precipitated in water, and filtering drying obtains product, and maleic anhydride 2.2g is then added and is uniformly mixed, institute
Obtaining the weightless thermal decomposition temperature of high thermal stability methyl eight bromo ether 1% is 250 DEG C.
Embodiment 6
Solvent 300mL, deionized water 50ml is added, opens stirring and tetrabromobisphenol A 175g is added, piece alkali 26.6g is added, stirs
Mixing dissolves material all, is to slowly warm up to 30 DEG C, controls 50 DEG C or so dropwise addition methylallyl chloride 60.2g, is added dropwise, and heats up
To 70 DEG C, thermotonus 8h is kept, 30 DEG C of suction filtrations is cooled to, obtains four bromo-ether of methyl；Methylene chloride 300g is added, stirring makes
Material dissolution is added the washing of 100g water and divides water, organic to be added to tin tetrachloride 2.3g, in 20 DEG C or so dropwise addition bromine 103.8g,
Reaction half an hour is added dropwise, water 100g is added and stirs half an hour, stands half an hour, moisture is gone out, water 300g is added, heating will
Solvent steams, and material is precipitated in water, and filtering drying obtains product, and phthalic anhydride 2.5g is then added and is uniformly mixed, institute
Obtaining the weightless thermal decomposition temperature of high thermal stability methyl eight bromo ether 1% is 253 DEG C.
Claims (7)
1. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether, which comprises the steps of:
(1) tetrabromobisphenol A is added into solvent A to stir to be warming up to piece alkali and is completely dissolved, within specified temperatures to solution
Middle dropwise addition methylallyl chloride occurs etherification reaction and generates four bromo-ether of methyl, and four bromo-ether of intermediate methyl is obtained by filtration in cooling；
(2) four bromo-ether of intermediate methyl being added in solvent B and is dissolved, material carries out washing and divides water after all dissolving,
Then effective catalyst is added and bromine progress addition reaction is added within specified temperatures and obtains the solution of eight bromo ether containing methyl, then
It is washed, distillation crystallization, filtering drying obtains methyl eight bromo ether,
(3) anhydride compound is added in the product obtained to step (2), is sufficiently mixed, obtains that there is high thermal stability
Methyl eight bromo ether fire retardant.
2. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether according to claim 1, which is characterized in that
Effective catalyst described in step (2) is one of titanium tetrachloride, tin tetrachloride, and dosage is 0.005~0.02g/1g first
Four bromo-ether of base.
3. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether according to claim 1, which is characterized in that
Anhydride compound described in step (3) be one of acetic anhydride, maleic anhydride, maleic anhydride, phthalic anhydride,
Dosage is 0.005~0.02g/1g methyl eight bromo ether.
4. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether according to claim 1, which is characterized in that
Solvent A described in step (1) is one of methanol, ethyl alcohol, ethylene glycol, water or a variety of.
5. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether according to claim 1, which is characterized in that
The solvent B is alkane solvents.
6. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether according to claim 1, which is characterized in that
Specific temperature described in step (1) is 30 DEG C~70 DEG C.
7. a kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether according to claim 1, which is characterized in that
Specific temperature described in step (2) is -10 DEG C~30 DEG C.
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Cited By (6)
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| CN112778100A (en) * | 2021-02-02 | 2021-05-11 | 山东迈特新材料科技有限公司 | Preparation method of high-purity flame retardant methyl tetrabromoether |
| CN112830868A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity methyl octabromoether |
| CN112830869A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity octabromoether |
| CN113548948A (en) * | 2021-08-17 | 2021-10-26 | 宿迁联盛科技股份有限公司 | Preparation method of methyl octabromoether |
| CN114195621A (en) * | 2021-12-14 | 2022-03-18 | 山东省海洋化工科学研究院 | Preparation method of methyl octabromoether |
| CN114805039A (en) * | 2022-04-13 | 2022-07-29 | 山东海王化工股份有限公司 | Production process of high-melting-point flame retardant methyl octabromoether |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778100A (en) * | 2021-02-02 | 2021-05-11 | 山东迈特新材料科技有限公司 | Preparation method of high-purity flame retardant methyl tetrabromoether |
| CN112830868A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity methyl octabromoether |
| CN112830869A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity octabromoether |
| CN112830868B (en) * | 2021-02-02 | 2023-02-17 | 山东迈特新材料科技有限公司 | Preparation method of methyl octabromoether |
| CN113548948A (en) * | 2021-08-17 | 2021-10-26 | 宿迁联盛科技股份有限公司 | Preparation method of methyl octabromoether |
| CN113548948B (en) * | 2021-08-17 | 2023-04-14 | 宿迁联盛科技股份有限公司 | Preparation method of methyl octabromoether |
| CN114195621A (en) * | 2021-12-14 | 2022-03-18 | 山东省海洋化工科学研究院 | Preparation method of methyl octabromoether |
| CN114195621B (en) * | 2021-12-14 | 2023-12-22 | 山东省海洋化工科学研究院 | Preparation method of methyl octabromoether |
| CN114805039A (en) * | 2022-04-13 | 2022-07-29 | 山东海王化工股份有限公司 | Production process of high-melting-point flame retardant methyl octabromoether |
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