CN107694346A - A kind of preparation method of water process brominated polyphenylether anisotropic membrane - Google Patents
A kind of preparation method of water process brominated polyphenylether anisotropic membrane Download PDFInfo
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- CN107694346A CN107694346A CN201710929381.5A CN201710929381A CN107694346A CN 107694346 A CN107694346 A CN 107694346A CN 201710929381 A CN201710929381 A CN 201710929381A CN 107694346 A CN107694346 A CN 107694346A
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- polyphenylene oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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Abstract
A kind of preparation method the invention discloses water process with brominated polyphenylether anisotropic membrane, belongs to water-treatment technology field, comprises the following steps：Polyphenylene oxide and catalyst are added in organic solvent and are warming up to whole dissolvings；0 DEG C is cooled to, adds bromating agent, realizes the phenyl ring bromination of polyphenylene oxide, reaction is completed, and washing removes catalyst, and stratification obtains the polyphenylene oxide of phenyl ring bromination；Bromating agent and catalyst are added in the organic layer that above-mentioned layering is obtained, through secondary bromination reaction, the methyl bromide of polyphenylene oxide is realized, reaction completion, washes and remove catalyst, stratification obtains the polyphenylene oxide of methyl bromide；Water is added in the organic layer that above-mentioned layering is obtained and emulsifying agent carries out distillation procedure, distills out organic solvent, then is soaked in the gel inversion of phases solvent that acetone and ammonia spirit are formed, polymer separates out, and obtains brominated polyphenylether anisotropic membrane.It is modified by polyphenylene ether, prepares a kind of selective penetrated property good water process brominated polyphenylether anisotropic membrane.
Description
Technical field
A kind of preparation method the present invention relates to water process with brominated polyphenylether anisotropic membrane, belong to water technology neck
Domain.
Background technology
The Organic Pollution solved in water is one of important topic of environmental protection, wherein to compel the most the problem of chlorohydrocarbon
Cut.In addition, ketone, ether, alcohol, amine and phenol are also important pollution sources, can using the infiltration evaporation process of organic permselective membrane
Effectively the aqueous solution containing a small amount of organic liquor is handled, and organic liquor is recycled, the key of the process water process
It is the selection of membrane material.
Polyphenylene oxide (chemical name be poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate, abbreviation PPO) is that a kind of physics, chemical property are steady
Fixed thermoplastic polymer, have it is excellent both mechanically and thermally, be not only it is a kind of with high glass transition temperature heat-resisting works modeling
Material, and have very high transmitance to various gases, homogeneous, asymmetric or modified PPO is used in many researchs both at home and abroad
In gas separation membrane, good transmission and separating property are shown.Polyphenylene oxide is due to higher glass transition temperature and preferable machine
Tool intensity, it is set to can be used as solvent separation, the membrane material of water process.
Ehter bond containing polarized in the main chain of PPO molecules, the liquid different to polarity is possible to by this structure and mixed
Thing realizes separation, but the polarity that ehter bond can be provided is limited, and in water process, itself selectivity is relatively low and can not
Dissolve in polar non-solute used in usual film forming procedure, thus be not widely used.
The content of the invention
The present invention provides a kind of preparation method of water process brominated polyphenylether anisotropic membrane, utilizes radical reaction and parent
The methyl and phenyl ring of electricity reaction polyphenylene ether have carried out bromination respectively and have been modified, and improve the polarity and selective penetrated property of polyphenylene oxide,
So as to prepare a kind of water process brominated polyphenylether anisotropic membrane.
To achieve the above object, the present invention uses following technical scheme：
A kind of water process preparation method of brominated polyphenylether anisotropic membrane, comprises the following steps：
(1) polyphenylene oxide (PPO) and catalyst are added in organic solvent and are warming up to whole dissolvings；
(2) 0 DEG C is cooled to, adds quantitative bromating agent, realizes the phenyl ring bromination of polyphenylene oxide, reaction is completed, and washing removes
Catalyst, stratification obtain the polyphenylene oxide of phenyl ring bromination；
(3) quantitative bromating agent and catalyst are added in the organic layer for obtaining above-mentioned layering, it is real through secondary bromination reaction
The methyl bromide of existing polyphenylene oxide, reaction are completed, and washing removes catalyst, and stratification obtains the polyphenylene oxide of methyl bromide；
(4) water is added in the organic layer for obtaining above-mentioned layering and emulsifying agent carries out distillation procedure, distills out organic solvent,
Soaked again in the gel inversion of phases solvent that acetone and ammonia spirit are formed, polymer separates out, and it is asymmetric to obtain brominated polyphenylether
Film.
Preferably, the catalyst in the step (1) is composite catalyst, and the composite catalyst dosage is described poly-
The 0.5wt%-1.5wt% of phenylate, the composite catalyst are made up of the raw material of following mass ratio：Iodine：Alchlor：Four chlorinations
Tin：Antimony trichloride=0.5:1:4:2.
Preferably, the organic solvent in the step (1) is toluene, chlorobenzene, the one or more in ethyl acetate, and institute
State 5-10 times that consumption of organic solvent is the polyphenylene oxide quality.
Preferably, the temperature of rising temperature for dissolving is 50-80 DEG C in the step (1).
Preferably, the bromating agent in the step (2) is bromine chloride, and the bromine chloride and the mol ratio of the polyphenylene oxide
For 0.3-0.5:1.
Preferably, the catalyst in the step (3) is any one in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate
Or it is a variety of, and the mol ratio of the catalyst and the polyphenylene oxide is 0.2-0.5:1.
Preferably, the bromating agent in the step (3) is in tetraethylammonium bromide, TBAB, C5H6Br2N2O2
Any one or more, and the mol ratio of the bromating agent and the polyphenylene oxide is 0.15-0.2:1.
Preferably, the bromination reaction temperature in the step (3) is 60-140 DEG C.
Preferably, the emulsifying agent in the step (4) is any in OP-10, fatty alcohol ether phosphate, phenolic ether phosphate
One or more, and the emulsifier is the 1wt%-5wt% of the water, the water consumption is the polyphenylene oxide quality
3-5 times.
Preferably, the dosage of the gel inversion of phases solvent in the step (4) is 2-3 times of the polyphenylene oxide quality, and
The mass ratio of the acetone and ammoniacal liquor is 2-5:1.
The present invention advantageous effects be：Using polyphenylene oxide as initiation material, radical reaction and electrophilic reaction pair are utilized
The methyl and phenyl ring of polyphenylene oxide have carried out bromination respectively and have been modified, and prepare brominated polyphenylether through two step bromination reactions, have saved bromine
Plain resource, degree of bromination is easy to control, improves the polarity of polyphenylene oxide；It is non-right that brominated polyphenylether is prepared using gel phase inversion
Claim film, be modified by bromination, the selective penetrated property of brominated polyphenylether anisotropic membrane improves, by controlling polyphenylene oxide methyl and phenyl ring
Degree of bromination so that selectivity and transmitance improve, and applied to the water process containing organic pollution, selectivity is good, thoroughly
Cross rate height.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
A kind of water process preparation method of brominated polyphenylether anisotropic membrane, comprises the following steps：
(1) by 1mol polyphenylene oxide (PPO) and composite catalyst (iodine：Alchlor：Butter of tin：Antimony trichloride=0.5:
1:4:2) it is added in organic solvent ethyl acetate, is warming up to 60 DEG C to whole dissolvings, organic solvent ethyl acetate dosage is institute
State polyphenylene oxide quality 5 times；
(2) it is cooled to 0 DEG C, adds 0.3mol bromine chlorides, after low-temperature insulation 1h, is warming up to normal temperature, realizes the benzene of polyphenylene oxide
Ring bromination, reaction are completed, and washing removes catalyst, and stratification obtains the polyphenylene oxide of phenyl ring bromination, and phenyl ring bromination degree is 26%；
(3) 0.2mol tetraethylammonium bromides and 0.2mol persulfuric acid are added in the organic layer for obtaining above-mentioned layering
Potassium, 80 DEG C are warming up to, through secondary bromination reaction, realize the methyl bromide of polyphenylene oxide, reaction is completed, washes and remove catalyst, quiet
Put layering and obtain the polyphenylene oxide of methyl bromide, methyl bromide degree is 13%；
(4) water is added in the organic layer for obtaining above-mentioned layering and fatty alcohol ether phosphate carries out distillation procedure, is distilled out
Organic solvent obtains product, then is soaked in the gel inversion of phases solvent that acetone and ammonia spirit are formed, and polymer separates out, and obtains
Brominated polyphenylether anisotropic membrane, and the emulsifier is the 2wt% of the water, the water consumption is the polyphenylene oxide quality
3 times, the dosage of gel inversion of phases solvent is 2 times of the polyphenylene oxide quality, and the mass ratio of the acetone and ammoniacal liquor is 2:1.
Embodiment 2
A kind of water process preparation method of brominated polyphenylether anisotropic membrane, comprises the following steps：
(1) by 1mol polyphenylene oxide (PPO) and composite catalyst (iodine：Alchlor：Butter of tin：Antimony trichloride=0.5:
1:4:2) it is added in organic solvent ethyl acetate, is warming up to 70 DEG C to whole dissolvings, organic solvent ethyl acetate dosage is institute
State polyphenylene oxide quality 7 times；
(2) it is cooled to 0 DEG C, adds 0.4mol bromine chlorides, after low-temperature insulation 1h, is warming up to normal temperature, realizes the benzene of polyphenylene oxide
Ring bromination, reaction are completed, and washing removes catalyst, and stratification obtains the polyphenylene oxide of phenyl ring bromination, and phenyl ring bromination degree is 28%；
(3) 0.15mol TBABs and 0.3mol persulfuric acid are added in the organic layer for obtaining above-mentioned layering
Sodium, 100 DEG C are warming up to, through secondary bromination reaction, realize the methyl bromide of polyphenylene oxide, reaction is completed, washes and remove catalyst, quiet
Put layering and obtain the polyphenylene oxide of methyl bromide, methyl bromide degree is 12%；
(4) water is added in the organic layer for obtaining above-mentioned layering and OP-10 carries out distillation procedure, organic solvent is distilled out and obtains
To product, then soaked in the gel inversion of phases solvent that acetone and ammonia spirit are formed, polymer separates out, and obtains brominated polyphenylether
Anisotropic membrane, and the emulsifier is the 3wt% of the water, the water consumption is 4 times of the polyphenylene oxide quality, gel
The dosage of inversion of phases solvent is 3 times of the polyphenylene oxide quality, and the mass ratio of the acetone and ammoniacal liquor is 3:1.
Embodiment 3
A kind of water process preparation method of brominated polyphenylether anisotropic membrane, comprises the following steps：
(1) by 1mol polyphenylene oxide (PPO) and composite catalyst (iodine：Alchlor：Butter of tin：Antimony trichloride=0.5:
1:4:2) it is added in organic solvent ethyl acetate, is warming up to 80 DEG C to whole dissolvings, organic solvent chlorobenzene dosage is described poly-
8 times of phenylate quality；
(2) it is cooled to 0 DEG C, adds 0.5mol bromine chlorides, after low-temperature insulation 1h, is warming up to normal temperature, realizes the benzene of polyphenylene oxide
Ring bromination, reaction are completed, and washing removes catalyst, and stratification obtains the polyphenylene oxide of phenyl ring bromination, and phenyl ring bromination degree is 29%；
(3) 0.2mol C5H6Br2N2O2s and 0.4mol sodium peroxydisulfates are added in the organic layer for obtaining above-mentioned layering, is risen
Temperature through secondary bromination reaction, realizes the methyl bromide of polyphenylene oxide, reacts and complete, washing removes catalyst, stands and divides to 120 DEG C
Layer obtains the polyphenylene oxide of methyl bromide, and methyl bromide degree is 13%；
(4) water is added in the organic layer for obtaining above-mentioned layering and phenolic ether phosphate carries out distillation procedure, is distilled out organic
Solvent obtains product, then is soaked in the gel inversion of phases solvent that acetone and ammonia spirit are formed, and polymer separates out, and obtains bromination
Polyphenylene oxide anisotropic membrane, and the emulsifier is the 4wt% of the water, the water consumption is the 5 of the polyphenylene oxide quality
Times, the dosage of gel inversion of phases solvent is 3 times of the polyphenylene oxide quality, and the mass ratio of the acetone and ammoniacal liquor is 4:1.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all skills in the present invention
On the basis of art scheme, those skilled in the art need not pay the various modifications that creative work can make or deformation still exists
In protection scope of the present invention.
Claims (10)
1. a kind of water process preparation method of brominated polyphenylether anisotropic membrane, it is characterised in that comprise the following steps：
(1) polyphenylene oxide (PPO) and catalyst are added in organic solvent and are warming up to whole dissolvings；
(2) 0 DEG C is cooled to, adds quantitative bromating agent, realizes the phenyl ring bromination of polyphenylene oxide, reaction is completed, and washing removes catalysis
Agent, stratification obtain the polyphenylene oxide of phenyl ring bromination；
(3) quantitative bromating agent and catalyst are added in the organic layer for obtaining above-mentioned layering, through secondary bromination reaction, is realized poly-
The methyl bromide of phenylate, reaction are completed, and washing removes catalyst, and stratification obtains the polyphenylene oxide of methyl bromide；
(4) water and emulsifying agent are added in the organic layer for obtaining above-mentioned layering and carries out distillation procedure, distill out organic solvent, then
Soaked in the gel inversion of phases solvent that acetone and ammonia spirit are formed, polymer separates out, and obtains brominated polyphenylether anisotropic membrane.
A kind of 2. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Catalyst in the step (1) is composite catalyst, and the composite catalyst dosage is the 0.5wt%- of the polyphenylene oxide
1.5wt%, the composite catalyst are made up of the raw material of following mass ratio：Iodine：Alchlor：Butter of tin：Antimony trichloride=
0.5:1:4:2。
A kind of 3. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Organic solvent in the step (1) is toluene, chlorobenzene, the one or more in ethyl acetate, and the consumption of organic solvent
For 5-10 times of the polyphenylene oxide quality.
A kind of 4. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
The temperature of rising temperature for dissolving is 50-80 DEG C in the step (1).
A kind of 5. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Bromating agent in the step (2) is bromine chloride, and the bromine chloride and the mol ratio of the polyphenylene oxide are 0.3-0.5:1.
A kind of 6. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Catalyst in the step (3) is potassium peroxydisulfate, any one or more in sodium peroxydisulfate, ammonium persulfate, and described is urged
Agent and the mol ratio of the polyphenylene oxide are 0.2-0.5:1.
A kind of 7. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Bromating agent in the step (3) is any one or more in tetraethylammonium bromide, TBAB, C5H6Br2N2O2,
And the mol ratio of the bromating agent and the polyphenylene oxide is 0.15-0.2:1.
A kind of 8. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Bromination reaction temperature in the step (3) is 60-140 DEG C.
A kind of 9. preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, it is characterised in that
Emulsifying agent in the step (4) is OP-10, any one or more in fatty alcohol ether phosphate, phenolic ether phosphate, and institute
The 1wt%-5wt% that emulsifier is the water is stated, the water consumption is 3-5 times of the polyphenylene oxide quality.
10. a kind of preparation method of water process brominated polyphenylether anisotropic membrane according to claim 1, its feature exist
In the dosage of the gel inversion of phases solvent in the step (4) is 2-3 times of the polyphenylene oxide quality, and the acetone and ammonia
The mass ratio of water is 2-5:1.
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Cited By (3)
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| CN108409959A (en) * | 2018-04-09 | 2018-08-17 | 南阳师范学院 | A kind of bromomethylation polyphenylene oxide and preparation method thereof |
| CN108456304A (en) * | 2018-02-22 | 2018-08-28 | 潍坊玉成化工有限公司 | A kind of preparation method and applications of Noryl |
| CN111763205A (en) * | 2020-01-15 | 2020-10-13 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent compound, preparation method thereof and organic electroluminescent device |
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