CN106589189A - Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production - Google Patents
Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production Download PDFInfo
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Abstract
The invention relates to a polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production. The method comprises the following steps: step one, preparing polypentabromobenzyl acrylate: (1) synthesizing pentabromotoluene, collecting hydrogen bromide gas, and adsorbing and filtering the hydrogen bromide gas by active carbon; (2) purifying the crude product of pentabromotoluene; (3) preparing pentabromobenzyl bromide from pentabromotoluene; (4) purifying the crude product of pentabromobenzyl bromide; (5) preparing pentabromobenzyl acrylate from pentabromobenzyl bromide; and (6) carrying out polymerization of pentabromobenzyl bromide; and step two, preparing tribromoneopentyl alcohol: (1) adding pentaerythritol, red phosphorus, hydrobromic acid (48%), and acetic acid into a reactor, and introducing hydrogen bromide gas obtained in the polypentabromobenzyl acrylate preparation into the reactor; (2) carrying out suction filtration to remove excess red phosphorus; and (3) adding methanol and active carbon into the lower layer to carry out degreasing; and (4) crystallizing the liquid. Compared with the prior art, the product quality is good, the product purity is high, and the production cost and the recovery and processing cost are reduced.
Description
Technical field
The present invention relates to fire retardant production preparation field, specifically applies to the polyacrylic acid pentabromo- of industrialized production
The method that benzyl ester is prepared with tribromoneoamyl alcohol.
Background technology
Polyacrylic acid pentabromo- benzyl ester belongs to Polymerized Brominated Flame Retardant, its bromine content up to 71.7%, except with excellent resistance
Fuel efficiency can be outer, and also with excellent thermo-chemical stability, the synthesis of polyacrylic acid pentabromo- benzyl ester is mainly (or brominated with toluene, bromine
Compound), acrylic acid be raw material, react progressively prepared under certain condition.Toluene and bromine reaction first is obtained pentabromotoluene, and five
Toluene bromide obtains pentabromobenzyl bromide with bromine (or bromine-containing compound) reaction, and pentabromobenzyl bromide is further obtained with propylene acid reaction
Polyacrylic acid five generated and polyreaction under initiator effect in pentabromobenzyl acrylate monomer, last pentabromobenzyl acrylate there is
Bromobenzyl ester.A large amount of bromination hydrogen can be generated in pentabromotoluene preparation process wherein, in pentabromobenzyl bromide building-up process
Part hydrogen bromide gas can be produced, these hydrogen bromide sour gas need the recycling cost in recycling, later stage to increase, from
And improve the total preparation cost of polyacrylic acid pentabromobenzyl bromide.
Tribromoneoamyl alcohol is the brominated fire retardant of a class, and its bromine content is 73.79%, belongs to fatty bromine, contains with high bromine
Measure and special stability, hydrolytic resistance and light stability are especially prominent, because which contains reactable functional group hydroxyl, therefore can
Use using the reaction intermediate as high molecular fire retardant or as reactive flame retardant.At present tribromoneoamyl alcohol be usually with
Tetramethylolmethane and hydrobromic acid（Concentration is 48% or 62%）For raw material, production is prepared by solvent of acetic acid, wherein hydrobromic
Consumption is very big, high cost.If the bromination hydrogen produced in polyacrylic acid pentabromobenzyl bromide preparation process is applied to tribromo
In the preparation process of neopentyl alcohol, the recycling of hydrogen bromide in polyacrylic acid pentabromobenzyl bromide preparation process on the one hand can be reduced
Cost, on the other hand replaces hydrobromic acid solution reduce the hydrobromic acid in tribromoneoamyl alcohol preparation process with bromination hydrogen
Consumption, and due in bromination hydrogen moisture-free move right reaction, accelerate tribromoneoamyl alcohol generating rate and product
Rate, reduces hydrogen bromide consumption cost, therefore the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production is coordinated with tribromoneoamyl alcohol
The method of preparation is necessary.
The content of the invention
The present invention proposes the side prepared with tribromoneoamyl alcohol suitable for the polyacrylic acid pentabromo- benzyl ester of industrialized production
Method.
The technical scheme is that what is be achieved in that：Suitable for the polyacrylic acid pentabromo- benzyl ester and tribromo of industrialized production
The method that neopentyl alcohol is prepared, it is characterised in that comprise the following steps：
（One）It is prepared by polyacrylic acid pentabromo- benzyl ester：
1）Controlling reaction temperature is -5-10 DEG C of synthesis pentabromotoluene, collects bromination hydrogen and by bromination hydrogen Jing activated carbons
Adsorption filtration；
2）By step 1）Obtained pentabromotoluene crude product is 1 with solvent by weight:1-3 is mixed, and is stirred at 40-50 DEG C
2-5h is purified；
3）By step 2）Obtained pentabromotoluene is 1 with bromine, solvent by weight:0.5-1:2-3 is mixed, ultraviolet lighting
Penetrate 4-8h and prepare pentabromobenzyl bromide；
4）By step 3）Obtained pentabromobenzyl bromide crude product is 1 with solvent by weight：2-2.4 carries out mixing purification, at 30 DEG C
Under stir and wash 2h, be then centrifuged for drying；
5）By step 4）The pentabromobenzyl bromide acrylic acid synthesizing pentabromobenzyl ester for obtaining；
6）By step 5）The acrylic acid pentabromobenzyl ester for obtaining is polymerized, by substep addition initiator in polymerization process
Precise control molecular weight of product；
（Two）The preparation of tribromoneoamyl alcohol
1）Tetramethylolmethane, red phosphorus, 48% hydrobromic acid and acetic acid, stirring is added to be warming up to 45-55 DEG C, be passed through poly- in a kettle.
Pentabromobenzyl acrylate preparation process 1）The bromination hydrogen of middle gained, controls bromination hydrogen and is passed through speed for 50-200kg/
H, has been reacted completely by gas just and has been defined, and then heats to 120 DEG C, insulation reaction 10h；The effect for adding red phosphorus is by bromination
The bromine carried secretly in hydrogen is converted into hydrogen bromide and participates in reaction.
2）Temperature is cooled to into room temperature, sucking filtration removes excessive red phosphorus；
3）Reactant liquor stratification after filtration, lower floor's material are separated into defat reactor, add methanol, activated carbon to be taken off
Fat；
4）After de- ester terminates, activated carbon in feed liquid is filtered, clean feed liquid is crystallized, and obtains product.
As preferred technical scheme, in polyacrylic acid pentabromo- benzyl ester preparation process 1）Specially：Add in bromination kettle
Bromine, then Deca toluene again, the part by weight for controlling toluene with bromine is 1：19-25, the time for adding of toluene are controlled in 6-
In 10h, and insulation reaction 10-15h, after reaction terminates, unnecessary bromine is steamed, be centrifuged, and reacted material is washed to
It is neutral.
As preferred technical scheme, in polyacrylic acid pentabromo- benzyl ester preparation process 2）, step 3）, step 4）In solvent
It is any one in dichloroethanes, dichloromethane, chloroform and carbon tetrachloride.
As preferred technical scheme, in polyacrylic acid pentabromo- benzyl ester preparation process 5）Specially：By solvent, polymerization inhibitor,
In acrylic acid input reactor, then sodium carbonate is put in 1.5-2h, control temperature at 30-40 DEG C, after insulation 1h, will reaction
Temperature rises to 45-70 DEG C, puts into step 4）Obtained pentabromobenzyl bromide, wherein solvent, polymerization inhibitor, acrylic acid, sodium carbonate and five
The weight proportion of bromo benzyl bromo is (1-3.5)：(0.005-0.05):（1-2）：(0.12-3):1, then by reaction temperature in 1h
70-130 DEG C is inside risen to, 3h is incubated, by resulting material washing, recrystallization.More than 99.5%, color is pure to products obtained therefrom purity
White powder.
As preferred technical scheme, in polyacrylic acid pentabromo- benzyl ester preparation process 5）In solvent be dichloroethanes, two
Any one in chloromethanes, chloroform, glycol monoethyl ether, polymerization inhibitor be hydroquinone, tert-butyl phenol, MEHQ,
Any one or a few in 1,4-benzoquinone.
As preferred technical scheme, in polyacrylic acid pentabromo- benzyl ester preparation process 6）Specially：Add in a kettle.
Solvent, adds step 5）The acrylic acid pentabromobenzyl ester of synthesis, then leads to nitrogen, and reaction temperature is warming up to 60 DEG C, is subsequently adding
First step initiator, adds second step initiator, insulation reaction 1-3h at 70 DEG C to be subsequently adding the initiation of the 3rd step after insulation 1-3h
Agent, insulation reaction 1-3h at 80 DEG C, after reaction terminates, are centrifuged sucking filtration, obtain polyacrylic acid pentabromo- benzyl ester, wherein five bromobenzyl of acrylic acid
Base ester, solvent, first step initiator, second step initiator, the weight proportion of the 3rd step initiator are 1:（1~5）:(0.001~
0.05): (0.001~0.05): (0.001~0.05)。
As preferred technical scheme, in polyacrylic acid pentabromo- benzyl ester preparation process 6）In solvent be ethanol, isooctanol,
Any one in glycol dimethyl ether, ethylene glycol monomethyl ether, chlorobenzene；First step initiator, second step initiator and the 3rd step are drawn
Agent is sent out using dibenzoyl peroxide, azodiisobutyronitrile, any one or a few in 2,2'-Azobis(2,4-dimethylvaleronitrile).
As preferred technical scheme, tribromoneoamyl alcohol preparation process 1）Middle tetramethylolmethane, red phosphorus, 48% hydrobromic acid and
The weight proportion of acetic acid is 1:(0.001~0.05)：(1~5):(0.50~3.00)；
As preferred technical scheme, tribromoneoamyl alcohol preparation process 3）Middle skimming temp is 80 DEG C, and degreasing time is 10h, first
1.2-3 times for lower floor's weight of material of alcohol consumption.
As preferred technical scheme, tribromoneoamyl alcohol preparation process 4）Crystallization operation be specially：Clean feed liquid is led to
Cross head tank to be slowly added dropwise toward water, 2-3 times for feed liquid weight of the water yield.
As a result of above-mentioned technical proposal, the present invention has beneficial effect following prominent：
1st, the bromination hydrogen produced in polyacrylic acid pentabromo- benzyl ester preparation process is passed into into tribromoneoamyl alcohol bromination reaction kettle
In, the utilization rate of bromination hydrogen and bromine is high, is conducive to industrialized production, two kinds of fire retardants to coordinate synthesis, both saved bromination
The cost of hydrogen recycling, and the usage amount of hydrogen bromide in tribromoneoamyl alcohol preparation process will be reduced, greatly reduce
Production cost.
2nd, during polyacrylic acid pentabromo- benzyl ester is prepared, for pentabromotoluene, pentabromobenzyl bromide are purified immediately, adopt
With specific purification step, colourity is not only ensure that, and improves purity, in the course of the polymerization process, drawn by using combination
Agent substep addition precise control molecular weight of product is sent out, molecular weight is obtained 30000 or so, high-purity, poly- the third of high stability
Olefin(e) acid pentabromobenzyl ester.
3rd, the present invention can realize the synthesis of tribromoneoamyl alcohol at ambient pressure, and by adding materials and controlling progressively
Reaction temperature, it is ensured that the mildness of reaction condition, especially realizes being reacted at ambient pressure, and final product quality
Higher, preferably, purity is more than 98% to crystal formation.
4th, in tribromoneoamyl alcohol building-up process, reaction raw materials are used as by bromination hydrogen and replace part hydrobromic acid, made
In course of reaction, the amount of water is reduced, and is overcome the slow defect of reaction rate, is substantially increased reaction rate；Add in course of reaction
The bromine carried secretly in bromination hydrogen is converted into hydrogen bromide and participates in reaction, improves product yield and product purity by red phosphorus.
Specific embodiment
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described enforcement
Example is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the embodiment in the present invention, this area is common
The every other embodiment obtained under the premise of creative work is not made by technical staff, belongs to the model of present invention protection
Enclose.
Embodiment 1
Suitable for the method that polyacrylic acid pentabromo- benzyl ester and the tribromoneoamyl alcohol of industrialized production are prepared, including following step
Suddenly：
（One）It is prepared by polyacrylic acid pentabromo- benzyl ester：
1）Bromine is added in bromination kettle, then Deca toluene, controlling reaction temperature is -5 DEG C, the part by weight of toluene and bromine
For 1：19, the control of the time for adding of toluene is in 6h, the bromination hydrogen produced in collecting course of reaction and by bromination hydrogen Jing
Activated carbon adsorption is filtered, insulation reaction 10h, after reaction terminates, steams unnecessary bromine, is centrifuged, and by reacted material water
Neutrality is washed till, pentabromotoluene is obtained；
2）By step 1）Obtained pentabromotoluene crude product is 1 with dichloroethanes by weight:1 is mixed, and is stirred at 40 DEG C
5h is purified；
3）By step 2）Obtained pentabromotoluene is 1 with bromine, dichloroethanes by weight:0.5:2 are mixed, ultraviolet lighting
Penetrate 4h and prepare pentabromobenzyl bromide；
4）By step 3）Obtained pentabromobenzyl bromide crude product is 1 with dichloroethanes by weight：2 carry out mixing purification, at 30 DEG C
Under stir and wash 2h, be then centrifuged for drying；
5）By in dichloroethanes, hydroquinone, acrylic acid input reactor, then sodium carbonate is put in 1.5h, control temperature
At 30 DEG C, after insulation 1h, reaction temperature is risen to into 45 DEG C, put into step 4）It is obtained pentabromobenzyl bromide, wherein dichloroethanes, right
The weight proportion of Benzodiazepiness, acrylic acid, sodium carbonate and pentabromobenzyl bromide is 1：0.005：1：0.12：1, then reaction temperature is existed
70 DEG C are risen in 1h, 3h is incubated, by resulting material washing, recrystallization, acrylic acid pentabromobenzyl ester is obtained, products obtained therefrom purity exists
99.7%, form is fine white powder；
6）Ethanol is added in a kettle., adds step 5）The acrylic acid pentabromobenzyl ester of synthesis, then leads to nitrogen, reaction temperature
60 DEG C are warming up to, dibenzoyl peroxide are subsequently adding, after insulation 1h, are added dibenzoyl peroxide, insulation reaction at 70 DEG C
1h, is subsequently adding dibenzoyl peroxide, and insulation reaction 1h at 80 DEG C, after reaction terminates, is centrifuged sucking filtration, obtains polyacrylic acid pentabromo-
Benzyl ester, wherein acrylic acid pentabromobenzyl ester, ethanol are 1 with the weight proportion for adding dibenzoyl peroxide every time:1：0.001：
0.001：0.001.
（Two）The preparation of tribromoneoamyl alcohol
1）1 is pressed in a kettle.:0.001：1：0.50 weight proportion adds tetramethylolmethane, red phosphorus, 48% hydrobromic acid and vinegar
Acid, stirring are warming up to 45 DEG C, are passed through polyacrylic acid pentabromo- benzyl ester preparation process 1）The bromination hydrogen of middle gained, controls hydrogen bromide
It is 50kg/h that gas is passed through speed, then heats to 120 DEG C, insulation reaction 10h；
2）Temperature is cooled to into room temperature, sucking filtration removes excessive red phosphorus；
3）Reactant liquor stratification after filtration, lower floor's material are separated into defat reactor, add methanol, activated carbon to be taken off
Fat, skimming temp are 80 DEG C, and degreasing time is 10h, wherein 1.2 times for lower floor's weight of material of methanol usage；
4）After de- ester terminates, activated carbon in feed liquid is filtered, clean feed liquid is crystallized, obtain product, products obtained therefrom purity is
98.2%, wherein clean feed liquid is slowly added dropwise toward water by head tank during crystallization, 2 times for feed liquid weight of the water yield.
Embodiment 2
Suitable for the method that polyacrylic acid pentabromo- benzyl ester and the tribromoneoamyl alcohol of industrialized production are prepared, including following step
Suddenly：
（One）It is prepared by polyacrylic acid pentabromo- benzyl ester：
1）Bromine is added in bromination kettle, then Deca toluene, controlling reaction temperature is 10 DEG C, the part by weight of toluene and bromine
For 1：25, the time for adding of toluene is controlled in 10h, the bromination hydrogen produced in collecting course of reaction by bromination hydrogen
Body Jing activated carbon adsorption is filtered, insulation reaction 15h, after reaction terminates, steams unnecessary bromine, is centrifuged, and by reacted thing
Material is washed to neutrality, obtains pentabromotoluene；
2）By step 1）Obtained pentabromotoluene crude product is 1 with dichloromethane by weight:3 are mixed, and are stirred at 50 DEG C
2h is purified；
3）By step 2）Obtained pentabromotoluene is 1 with bromine, dichloromethane by weight:1:3 are mixed, ultraviolet light
8h prepares pentabromobenzyl bromide；
4）By step 3）Obtained pentabromobenzyl bromide crude product is 1 with dichloromethane by weight：2.4 carry out mixing purification, 30
Stir at DEG C and wash 2h, be then centrifuged for drying；
5）By in dichloromethane, tert-butyl phenol, acrylic acid input reactor, then sodium carbonate is put in 2h, control temperature and exist
40 DEG C, after insulation 1h, reaction temperature is risen to into 70 DEG C, put into step 4）Obtained pentabromobenzyl bromide, wherein dichloromethane, tertiary fourth
The weight proportion of base phenol, acrylic acid, sodium carbonate and pentabromobenzyl bromide is 3.5：0.05：2：3：1, then by reaction temperature in 1h
130 DEG C are risen to, 3h is incubated, by resulting material washing, recrystallization, acrylic acid pentabromobenzyl ester is obtained, products obtained therefrom purity exists
99.5%, form is fine white powder；
6）Isooctanol is added in a kettle., adds step 5）The acrylic acid pentabromobenzyl ester of synthesis, then leads to nitrogen, reaction temperature
Degree is warming up to 60 DEG C, is subsequently adding azodiisobutyronitrile, adds azodiisobutyronitrile after insulation 3h, insulation reaction 3h at 70 DEG C,
Azodiisobutyronitrile is subsequently adding, insulation reaction 3h at 80 DEG C, after reaction terminates, is centrifuged sucking filtration, obtains polyacrylic acid pentabromo- benzyl ester,
Wherein acrylic acid pentabromobenzyl ester, isooctanol and the weight proportion for adding azodiisobutyronitrile every time are 1：5：0.05：0.05：
0.05。
（Two）The preparation of tribromoneoamyl alcohol
1）1 is pressed in a kettle.:0.05：5：3.00 weight proportion adds tetramethylolmethane, red phosphorus, 48% hydrobromic acid and acetic acid,
Stirring is warming up to 55 DEG C, is passed through polyacrylic acid pentabromo- benzyl ester preparation process 1）The bromination hydrogen of middle gained, controls bromination hydrogen
The speed that is passed through of body is 200kg/h, then heats to 120 DEG C, insulation reaction 10h；
2）Temperature is cooled to into room temperature, sucking filtration removes excessive red phosphorus；
3）Reactant liquor stratification after filtration, lower floor's material are separated into defat reactor, add methanol, activated carbon to be taken off
Fat, skimming temp are 80 DEG C, and degreasing time is 10h, and methanol usage is 3 times of lower floor's weight of material；
4）After de- ester terminates, activated carbon in feed liquid is filtered, clean feed liquid is crystallized, obtain product, products obtained therefrom purity is
98.6%, wherein clean feed liquid is slowly added dropwise toward water by head tank during crystallization, 3 times for feed liquid weight of the water yield.
Embodiment 3
Suitable for the method that polyacrylic acid pentabromo- benzyl ester and the tribromoneoamyl alcohol of industrialized production are prepared, including following step
Suddenly：
（One）It is prepared by polyacrylic acid pentabromo- benzyl ester：
1）Bromine is added in bromination kettle, then Deca toluene, controlling reaction temperature is 2 DEG C, the part by weight of toluene and bromine
For 1：22, the time for adding of toluene is controlled in 8h, the bromination hydrogen produced in collecting course of reaction by bromination hydrogen
Jing activated carbon adsorption is filtered, insulation reaction 13h, after reaction terminates, steams unnecessary bromine, is centrifuged, and by reacted material
Neutrality is washed to, pentabromotoluene is obtained；
2）By step 1）Obtained pentabromotoluene crude product is 1 with chloroform by weight:2 are mixed, and stir 3h and carry at 45 DEG C
It is pure；
3）By step 2）Obtained pentabromotoluene is 1 with bromine, chloroform by weight:0.7:2.5 are mixed, ultraviolet light
6h prepares pentabromobenzyl bromide；
4）By step 3）Obtained pentabromobenzyl bromide crude product is 1 with chloroform by weight：2.2 carry out mixing purification, at 30 DEG C
Stir and wash 2h, be then centrifuged for drying；
5）By in chloroform, MEHQ, acrylic acid input reactor, then sodium carbonate is put in 1.7h, control temperature
At 35 DEG C, after insulation 1h, reaction temperature is risen to into 60 DEG C, put into step 4）Obtained pentabromobenzyl bromide, wherein chloroform, to hydroxyl
The weight proportion of methyl phenyl ethers anisole, acrylic acid, sodium carbonate and pentabromobenzyl bromide is 2.5:0.02:1.5:2:1, then reaction temperature is existed
100 DEG C are risen in 1h, 3h is incubated, by resulting material washing, recrystallization, acrylic acid pentabromobenzyl ester is obtained, products obtained therefrom purity exists
99.6%, form is fine white powder；
6）Glycol dimethyl ether is added in a kettle., adds step 5）The acrylic acid pentabromobenzyl ester of synthesis, then leads to nitrogen,
Reaction temperature is warming up to 60 DEG C, is subsequently adding 2,2'-Azobis(2,4-dimethylvaleronitrile), adds 2,2'-Azobis(2,4-dimethylvaleronitrile) after insulation 2h, is incubated anti-at 70 DEG C
2h is answered, 2,2'-Azobis(2,4-dimethylvaleronitrile) is subsequently adding, insulation reaction 2h at 80 DEG C, after reaction terminates, is centrifuged sucking filtration, obtains polyacrylic acid pentabromo-
Benzyl ester.Wherein acrylic acid pentabromobenzyl ester, glycol dimethyl ether and the weight proportion for adding 2,2'-Azobis(2,4-dimethylvaleronitrile) every time are 1:3:
0.03:0.03:0.03。
（Two）The preparation of tribromoneoamyl alcohol
1）1 is pressed in a kettle.:0.02:3:2.00 weight proportion adds tetramethylolmethane, red phosphorus, 48% hydrobromic acid and acetic acid,
Stirring is warming up to 50 DEG C, is passed through polyacrylic acid pentabromo- benzyl ester preparation process 1）The bromination hydrogen of middle gained, controls bromination hydrogen
The speed that is passed through of body is 120kg/h, then heats to 120 DEG C, insulation reaction 10h；
2）Temperature is cooled to into room temperature, sucking filtration removes excessive red phosphorus；
3）Reactant liquor stratification after filtration, lower floor's material are separated into defat reactor, add methanol, activated carbon to be taken off
Fat, skimming temp are 80 DEG C, and degreasing time is 10h, and methanol usage is 2 times of lower floor's weight of material；
4）After de- ester terminates, activated carbon in feed liquid is filtered, clean feed liquid is crystallized, obtain product, products obtained therefrom purity is
98.5%, wherein clean feed liquid is slowly added dropwise toward water by head tank during crystallization, 2.5 times for feed liquid weight of the water yield.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. the method for being prepared with tribromoneoamyl alcohol suitable for the polyacrylic acid pentabromo- benzyl ester of industrialized production, its feature are existed
In comprising the following steps：
(1) prepared by polyacrylic acid pentabromo- benzyl ester：
1) controlling reaction temperature is -5-10 DEG C of synthesis pentabromotoluene, collects bromination hydrogen and by bromination hydrogen Jing activated carbons
Adsorption filtration；
2) by step 1) obtained in pentabromotoluene crude product and solvent by weight being 1:1-3 is mixed, and is stirred at 40-50 DEG C
2-5h is purified；
3) by step 2) obtained in pentabromotoluene and bromine, solvent by weight being 1:0.5-1:2-3 is mixed, ultraviolet lighting
Penetrate 4-8h and prepare pentabromobenzyl bromide；
4) by step 3) obtained in pentabromobenzyl bromide crude product and solvent by weight being 1：2-2.4 carries out mixing purification, at 30 DEG C
Under stir and wash 2h, be then centrifuged for drying；
5) by step 4) the pentabromobenzyl bromide acrylic acid synthesizing pentabromobenzyl ester that obtains；
6) by step 5) the acrylic acid pentabromobenzyl ester that obtains is polymerized, by substep addition initiator in polymerization process
Precise control molecular weight of product；
(2) preparation of tribromoneoamyl alcohol
1) tetramethylolmethane, red phosphorus, 48% hydrobromic acid and acetic acid, stirring is added to be warming up to 45-55 DEG C, be passed through poly- in a kettle.
Pentabromobenzyl acrylate preparation process 1) in gained bromination hydrogen, control bromination hydrogen be passed through speed be 50-200kg/
H, has been reacted completely by gas just and has been defined, and then heats to 120 DEG C, insulation reaction 10h；
2) temperature is cooled to into room temperature, sucking filtration removes excessive red phosphorus；
3) reactant liquor stratification after filtering, lower floor's material are separated into defat reactor, add methanol, activated carbon to be taken off
Fat；
4) after de- ester terminates, activated carbon in feed liquid is filtered, clean feed liquid is crystallized, and obtains product.
2. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
Standby method, it is characterised in that：1) it is specially in polyacrylic acid pentabromo- benzyl ester preparation process：Bromine is added in bromination kettle, so
Deca toluene again afterwards, the part by weight for controlling toluene with bromine is 1：19-25, the time for adding of toluene are controlled in 6-10h, and
Insulation reaction 10-15h, after reaction terminates, steams unnecessary bromine, is centrifuged, and reacted material is washed to neutrality.
3. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
Standby method, it is characterised in that：Polyacrylic acid pentabromo- benzyl ester preparation process 2), step 3), step 4) in solvent be two
Any one in ethyl chloride, dichloromethane, chloroform and carbon tetrachloride.
4. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
Standby method, it is characterised in that：5) it is specially in polyacrylic acid pentabromo- benzyl ester preparation process：Solvent, polymerization inhibitor, acrylic acid are thrown
Enter in reactor, then sodium carbonate is put in 1.5-2h, control temperature at 30-40 DEG C, after insulation 1h, reaction temperature is risen to
45-70 DEG C, put into step 4) obtained in pentabromobenzyl bromide, wherein solvent, polymerization inhibitor, acrylic acid, sodium carbonate and pentabromobenzyl bromide
Weight proportion be (1-3.5)：(0.005-0.05):(1-2)：(0.12-3):1, reaction temperature is risen to into 70- in 1h then
130 DEG C, 3h is incubated, by resulting material washing, recrystallization.
5. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 4
Standby method, it is characterised in that：Polyacrylic acid pentabromo- benzyl ester preparation process 5) in solvent be dichloroethanes, dichloromethane,
Any one in chloroform, glycol monoethyl ether, polymerization inhibitor be hydroquinone, tert-butyl phenol, MEHQ, in 1,4-benzoquinone
Any one or a few.
6. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
Standby method, it is characterised in that：6) it is specially in polyacrylic acid pentabromo- benzyl ester preparation process：Solvent is added in a kettle., plus
Enter step 5) the acrylic acid pentabromobenzyl ester that synthesizes, then lead to nitrogen, reaction temperature is warming up to 60 DEG C, is subsequently adding the first step and draws
Agent is sent out, after insulation 1-3h, adds second step initiator, insulation reaction 1-3h at 70 DEG C to be subsequently adding the 3rd step initiator, 80 DEG C
Lower insulation reaction 1-3h, after reaction terminates, is centrifuged sucking filtration, obtains polyacrylic acid pentabromo- benzyl ester, wherein acrylic acid pentabromobenzyl ester, molten
Agent, first step initiator, second step initiator, the weight proportion of the 3rd step initiator are 1:(1～5):(0.001～0.05):
(0.001～0.05):(0.001～0.05).
7. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 6
Standby method, it is characterised in that：Polyacrylic acid pentabromo- benzyl ester preparation process 6) in solvent be ethanol, isooctanol, ethylene glycol
Any one in dimethyl ether, ethylene glycol monomethyl ether, chlorobenzene；First step initiator, second step initiator and the 3rd step initiator are equal
Using any one or a few in dibenzoyl peroxide, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
8. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
Standby method, it is characterised in that：Tribromoneoamyl alcohol preparation process 1) in tetramethylolmethane, red phosphorus, 48% hydrobromic acid and acetic acid
Weight proportion is 1:(0.001～0.05)：(1～5):(0.50～3.00).
9. system is coordinated with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
Standby method, it is characterised in that：Tribromoneoamyl alcohol preparation process 3) in skimming temp be 80 DEG C, degreasing time is 10h, and methanol is used
Measure 1.2-3 times for lower floor's weight of material.
10. coordinate with tribromoneoamyl alcohol according to the polyacrylic acid pentabromo- benzyl ester suitable for industrialized production described in claim 1
The method of preparation, it is characterised in that：Tribromoneoamyl alcohol preparation process crystallization operation 4) is specially：By clean feed liquid by a high position
Groove is slowly added dropwise toward water, 2-3 times for feed liquid weight of the water yield.
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| CN201611024170.9A CN106589189A (en) | 2016-11-18 | 2016-11-18 | Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production |
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| CN107129431A (en) * | 2017-05-31 | 2017-09-05 | 山东日兴新材料股份有限公司 | A kind of synthetic method of tribromoneoamyl alcohol |
| CN107446073A (en) * | 2017-08-03 | 2017-12-08 | 山东日兴新材料股份有限公司 | A kind of synthetic method of polypentabrombenzamide acrylate |
| CN117024635A (en) * | 2023-07-28 | 2023-11-10 | 潍坊裕凯化工有限公司 | Method for preparing pentabromobenzyl polyacrylate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107129431A (en) * | 2017-05-31 | 2017-09-05 | 山东日兴新材料股份有限公司 | A kind of synthetic method of tribromoneoamyl alcohol |
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| CN117024635A (en) * | 2023-07-28 | 2023-11-10 | 潍坊裕凯化工有限公司 | Method for preparing pentabromobenzyl polyacrylate |
| CN117024635B (en) * | 2023-07-28 | 2024-04-02 | 潍坊裕凯化工有限公司 | Method for preparing pentabromobenzyl polyacrylate |
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Application publication date: 20170426 |