CN107694346B - Preparation method of brominated polyphenylene oxide asymmetric membrane for water treatment - Google Patents
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- CN107694346B CN107694346B CN201710929381.5A CN201710929381A CN107694346B CN 107694346 B CN107694346 B CN 107694346B CN 201710929381 A CN201710929381 A CN 201710929381A CN 107694346 B CN107694346 B CN 107694346B
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
The invention discloses a preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment, belonging to the technical field of water treatment and comprising the following steps: adding polyphenyl ether and a catalyst into an organic solvent, and heating until the polyphenyl ether and the catalyst are completely dissolved; cooling to 0 ℃, adding a brominating agent to brominate benzene rings of the polyphenyl ether, washing with water to remove the catalyst after the reaction is finished, and standing for layering to obtain the polyphenyl ether with the brominated benzene rings; adding a brominating agent and a catalyst into the organic layer obtained by layering, carrying out secondary bromination reaction to realize methyl bromination of the polyphenyl ether, washing with water to remove the catalyst after the reaction is finished, and standing and layering to obtain methyl brominated polyphenyl ether; and adding water and an emulsifier into the organic layer obtained by layering to perform distillation operation, distilling out the organic solvent, soaking in a gel phase conversion solvent formed by acetone and an ammonia water solution, and separating out a polymer to obtain the brominated polyphenylene oxide asymmetric membrane. The brominated polyphenylene oxide asymmetric membrane for water treatment with good selective permeability is prepared by modifying polyphenylene oxide.
Description
Technical Field
The invention relates to a preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment, belonging to the technical field of water treatment.
Background
The solution of organic pollution in water is one of the important issues for environmental protection, and the problem of chlorinated hydrocarbons is the most urgent. In addition, ketones, ethers, alcohols, amines and phenols are also important pollution sources, and an aqueous solution containing a small amount of organic liquid can be effectively treated and recovered for use by a pervaporation process in which the organic liquid preferentially permeates through the membrane, and the water treatment in the process is critical to the selection of the membrane material.
Polyphenylene oxide (chemical name is poly 2, 6-dimethyl-1, 4-phenylene oxide, PPO for short) is a thermoplastic polymer with stable physical and chemical properties, has excellent mechanical and thermal properties, is not only a heat-resistant engineering plastic with high glass transition temperature, but also has very high transmittance for various gases, and various researches at home and abroad use homogeneous phase, asymmetric or modified PPO for gas separation membranes, and shows good transmittance and separation properties. Polyphenylene oxide can be used as a membrane material for solvent separation and water treatment due to the higher glass transition temperature and better mechanical strength.
The main chain of PPO molecule contains polar ether bond, and the separation of liquid mixture with different polarities is possible through the structure, however, the polarity provided by the ether bond is limited, the selectivity is low during water treatment, and the PPO molecule can not be dissolved in polar aprotic solvent used in the common film forming process, so the PPO molecule is not widely used.
Disclosure of Invention
The invention provides a preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment, which is characterized in that methyl and benzene rings of polyphenylene oxide are respectively brominated and modified by utilizing free radical reaction and electrophilic reaction, so that the polarity and selective permeability of the polyphenylene oxide are improved, and the brominated polyphenylene oxide asymmetric membrane for water treatment is prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment comprises the following steps:
(1) adding polyphenylene oxide (PPO) and a catalyst into an organic solvent, and heating until the PPO and the catalyst are completely dissolved;
(2) cooling to 0 ℃, adding a quantitative brominating agent to brominate benzene rings of the polyphenyl ether, completing the reaction, washing with water to remove the catalyst, and standing for layering to obtain polyphenyl ether with brominated benzene rings;
(3) adding a certain amount of brominating agent and catalyst into the organic layer obtained by layering, carrying out secondary bromination reaction to realize methyl bromination of the polyphenyl ether, washing with water to remove the catalyst after the reaction is finished, and standing for layering to obtain methyl brominated polyphenyl ether;
(4) and adding water and an emulsifier into the organic layer obtained by layering to perform distillation operation, distilling out the organic solvent, soaking in a gel phase conversion solvent formed by acetone and an ammonia water solution, and separating out a polymer to obtain the brominated polyphenylene oxide asymmetric membrane.
Preferably, the catalyst in the step (1) is a composite catalyst, the amount of the composite catalyst is 0.5 wt% -1.5 wt% of the polyphenylene ether, and the composite catalyst is composed of the following raw materials in percentage by mass: iodine: aluminum trichloride: tin tetrachloride: antimony trichloride ═ 0.5:1:4: 2.
Preferably, the organic solvent in the step (1) is one or more of toluene, chlorobenzene and ethyl acetate, and the amount of the organic solvent is 5-10 times of the mass of the polyphenylene ether.
Preferably, the temperature for raising the temperature for dissolving in the step (1) is 50-80 ℃.
Preferably, the brominating agent in the step (2) is bromine chloride, and the molar ratio of the bromine chloride to the polyphenylene ether is 0.3-0.5: 1.
Preferably, the catalyst in the step (3) is one or more of potassium persulfate, sodium persulfate and ammonium persulfate, and the molar ratio of the catalyst to the polyphenylene ether is 0.2-0.5: 1.
Preferably, the brominating agent in the step (3) is any one or more of tetraethylammonium bromide, tetrabutylammonium bromide and dibromohydantoin, and the molar ratio of the brominating agent to the polyphenylene ether is 0.15-0.2: 1.
Preferably, the bromination reaction temperature in said step (3) is 60-140 ℃.
Preferably, the emulsifier in the step (4) is any one or more of OP-10, fatty alcohol ether phosphate and phenol ether phosphate, and the amount of the emulsifier is 1 wt% -5 wt% of the water, and the amount of the water is 3-5 times of the mass of the polyphenylene oxide.
Preferably, the gel phase inversion solvent in the step (4) is used in an amount of 2-3 times the mass of the polyphenylene ether, and the mass ratio of the acetone to the ammonia water is 2-5: 1.
The beneficial technical effects of the invention are as follows: the method has the advantages that the polyphenyl ether is used as a starting raw material, methyl and benzene rings of the polyphenyl ether are respectively brominated and modified by utilizing a free radical reaction and an electrophilic reaction, and the brominated polyphenyl ether is prepared by a two-step bromination reaction, so that bromine resources are saved, the bromination degree is easy to control, and the polarity of the polyphenyl ether is improved; the brominated polyphenylene oxide asymmetric membrane is prepared by adopting a gel phase inversion method, the selective permeability of the brominated polyphenylene oxide asymmetric membrane is improved by bromination modification, the selectivity and the permeability are improved by controlling the bromination degree of methyl and benzene rings of the polyphenylene oxide, and the brominated polyphenylene oxide asymmetric membrane is applied to water treatment containing organic pollutants, has good selectivity and high permeability.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment comprises the following steps:
(1) adding 1mol of polyphenylene oxide (PPO) and a composite catalyst (iodine: aluminum trichloride: stannic chloride: antimony trichloride: 0.5:1:4:2) into organic solvent ethyl acetate, heating to 60 ℃ until the materials are completely dissolved, wherein the dosage of the organic solvent ethyl acetate is 5 times of the mass of the polyphenylene oxide;
(2) cooling to 0 ℃, adding 0.3mol of bromine chloride, keeping the temperature at low temperature for 1h, heating to normal temperature to brominate benzene rings of the polyphenyl ether, completing the reaction, washing with water to remove the catalyst, standing and layering to obtain the polyphenyl ether with the brominated benzene rings, wherein the degree of bromination of the benzene rings is 26%;
(3) adding 0.2mol of tetraethylammonium bromide and 0.2mol of potassium persulfate into the organic layer obtained by layering, heating to 80 ℃, carrying out secondary bromination reaction to realize methyl bromination of the polyphenyl ether, washing with water to remove the catalyst, standing and layering to obtain methyl brominated polyphenyl ether, wherein the methyl bromination degree is 13%;
(4) adding water and fatty alcohol ether phosphate into the organic layer obtained by layering for distillation operation, distilling out an organic solvent to obtain a product, soaking the product in a gel phase conversion solvent consisting of acetone and an ammonia water solution, and precipitating a polymer to obtain the brominated polyphenylene ether asymmetric membrane, wherein the dosage of the emulsifier is 2 wt% of the water, the dosage of the water is 3 times of the mass of the polyphenylene ether, the dosage of the gel phase conversion solvent is 2 times of the mass of the polyphenylene ether, and the mass ratio of the acetone to the ammonia water is 2: 1.
Example 2
A preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment comprises the following steps:
(1) adding 1mol of polyphenylene oxide (PPO) and a composite catalyst (iodine: aluminum trichloride: stannic chloride: antimony trichloride: 0.5:1:4:2) into organic solvent ethyl acetate, heating to 70 ℃ until the materials are completely dissolved, wherein the dosage of the organic solvent ethyl acetate is 7 times of the mass of the polyphenylene oxide;
(2) cooling to 0 ℃, adding 0.4mol of bromine chloride, keeping the temperature at low temperature for 1h, heating to normal temperature to brominate benzene rings of the polyphenyl ether, completing the reaction, washing with water to remove the catalyst, standing and layering to obtain polyphenyl ether with brominated benzene rings, wherein the degree of bromination of the benzene rings is 28%;
(3) adding 0.15mol of tetrabutylammonium bromide and 0.3mol of sodium persulfate into the organic layer obtained by layering, heating to 100 ℃, carrying out secondary bromination reaction to realize methyl bromination of the polyphenylene ether, washing with water to remove the catalyst after the reaction is finished, standing and layering to obtain the methyl-brominated polyphenylene ether, wherein the methyl bromination degree is 12%;
(4) adding water and OP-10 into the organic layer obtained by layering for distillation operation, distilling out an organic solvent to obtain a product, soaking in a gel phase inversion solvent composed of acetone and an ammonia water solution, and precipitating a polymer to obtain the brominated polyphenylene oxide asymmetric membrane, wherein the dosage of the emulsifier is 3 wt% of the water, the dosage of the water is 4 times of the mass of the polyphenylene oxide, the dosage of the gel phase inversion solvent is 3 times of the mass of the polyphenylene oxide, and the mass ratio of the acetone to the ammonia water is 3: 1.
Example 3
A preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment comprises the following steps:
(1) adding 1mol of polyphenylene oxide (PPO) and a composite catalyst (iodine: aluminum trichloride: stannic chloride: antimony trichloride: 0.5:1:4:2) into an organic solvent ethyl acetate, heating to 80 ℃ until the mixture is completely dissolved, wherein the dosage of the organic solvent chlorobenzene is 8 times of the mass of the polyphenylene oxide;
(2) cooling to 0 ℃, adding 0.5mol of bromine chloride, keeping the temperature at low temperature for 1h, heating to normal temperature to brominate benzene rings of the polyphenyl ether, completing the reaction, washing with water to remove the catalyst, standing and layering to obtain the polyphenyl ether with the brominated benzene rings, wherein the degree of bromination of the benzene rings is 29%;
(3) adding 0.2mol of dibromohydantoin and 0.4mol of sodium persulfate into the organic layer obtained by layering, heating to 120 ℃, carrying out secondary bromination reaction to realize methyl bromination of the polyphenylene ether, washing with water to remove the catalyst after the reaction is finished, and standing for layering to obtain the methyl-brominated polyphenylene ether, wherein the methyl bromination degree is 13%;
(4) adding water and phenol ether phosphate into the organic layer obtained by layering for distillation operation, distilling out an organic solvent to obtain a product, soaking the product in a gel phase inversion solvent composed of acetone and an ammonia water solution, and precipitating a polymer to obtain the brominated polyphenylene ether asymmetric membrane, wherein the dosage of the emulsifier is 4 wt% of the water, the dosage of the water is 5 times of the mass of the polyphenylene ether, the dosage of the gel phase inversion solvent is 3 times of the mass of the polyphenylene ether, and the mass ratio of the acetone to the ammonia water is 4: 1.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and variations which do not require inventive efforts and are made by those skilled in the art are still within the scope of the present invention.
Claims (9)
1. A preparation method of a brominated polyphenylene oxide asymmetric membrane for water treatment is characterized by comprising the following steps:
(1) adding polyphenylene oxide (PPO) and a catalyst into an organic solvent, and heating until the PPO and the catalyst are completely dissolved;
(2) cooling to 0 ℃, adding a quantitative brominating agent to realize benzene ring bromination of the polyphenyl ether, completing the reaction, washing with water to remove the catalyst, standing and layering to obtain polyphenyl ether with benzene ring bromination, wherein the brominating agent is bromine chloride, and the molar ratio of the bromine chloride to the polyphenyl ether is 0.3-0.5: 1;
(3) adding a certain amount of brominating agent and catalyst into the organic layer obtained by layering, carrying out secondary bromination reaction to realize methyl bromination of the polyphenyl ether, washing with water to remove the catalyst after the reaction is finished, and standing for layering to obtain methyl brominated polyphenyl ether;
(4) and adding water and an emulsifier into the organic layer obtained by layering to perform distillation operation, distilling out the organic solvent, soaking in a gel phase conversion solvent formed by acetone and an ammonia water solution, and separating out a polymer to obtain the brominated polyphenylene oxide asymmetric membrane.
2. The preparation method of the brominated polyphenylene ether asymmetric membrane for water treatment as claimed in claim 1, characterized in that the catalyst in step (1) is a composite catalyst, and the amount of the composite catalyst is 0.5 wt% -1.5 wt% of the polyphenylene ether, and the composite catalyst is composed of the following raw materials by mass ratio: iodine: aluminum trichloride: tin tetrachloride: antimony trichloride ═ 0.5:1:4: 2.
3. The method for preparing the brominated polyphenylene ether asymmetric membrane for water treatment as claimed in claim 1, wherein the organic solvent in step (1) is one or more of toluene, chlorobenzene and ethyl acetate, and the amount of the organic solvent is 5-10 times of the mass of the polyphenylene ether.
4. The method for preparing a brominated polyphenylene ether asymmetric membrane for water treatment as claimed in claim 1, wherein the temperature for heating and dissolving in step (1) is 50-80 ℃.
5. The method for preparing the brominated polyphenylene ether asymmetric membrane for water treatment according to claim 1, wherein the catalyst in the step (3) is one or more of potassium persulfate, sodium persulfate and ammonium persulfate, and the molar ratio of the catalyst to the polyphenylene ether is 0.2-0.5: 1.
6. The method for preparing the brominated polyphenylene ether asymmetric membrane for water treatment according to claim 1, wherein the brominating agent in the step (3) is any one or more of tetraethylammonium bromide, tetrabutylammonium bromide and dibromohydantoin, and the molar ratio of the brominating agent to the polyphenylene ether is 0.15-0.2: 1.
7. The method for preparing a brominated polyphenylene ether asymmetric membrane for water treatment as claimed in claim 1, wherein the bromination reaction temperature in the step (3) is 60-140 ℃.
8. The method for preparing the brominated polyphenylene ether asymmetric membrane for water treatment as claimed in claim 1, wherein the emulsifier in step (4) is any one or more of OP-10, fatty alcohol ether phosphate and phenol ether phosphate, and the amount of the emulsifier is 1 wt% -5 wt% of the water, and the amount of the water is 3-5 times of the mass of the polyphenylene ether.
9. The method for preparing a brominated polyphenylene ether asymmetric membrane for water treatment as claimed in claim 1, wherein the amount of the gel phase inversion solvent used in step (4) is 2 to 3 times the mass of the polyphenylene ether, and the mass ratio of acetone to ammonia water is 2 to 5: 1.
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| 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 |
| CN108409959B (en) * | 2018-04-09 | 2020-08-21 | 南阳师范学院 | Bromomethylated polyphenyl ether and preparation method thereof |
| CN111153902A (en) * | 2020-01-15 | 2020-05-15 | 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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| US9593215B2 (en) * | 2014-12-23 | 2017-03-14 | The Regents Of The University Of California | Polymer useful for an ion exchange membrane |
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