CN109777078A - A kind of polyphenylene oxide graphene proton membrane and preparation method thereof - Google Patents
A kind of polyphenylene oxide graphene proton membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polyphenylene oxide graphene proton membranes, it is composed of the following raw materials by weight: bromohexane 2-4, polyphenylene oxide 100-120, benzotriazole modified graphene 10-13, 2-mercaptobenzimidazole 0.6-1, Sucrose acetoisobutyrate 0.1-0.2, molybdenum boride 1-2, dibutyl tin dilaurate 0.5-1, dispersing agent 1-2, ricinoleic acid 3-4, the present invention realizes the dispersion compatibility between graphene and polyphenylene oxide, to improve the mechanical stability of finished product, and pass through the modified proton conductivity that proton membrane can be improved of benzotriazole, improve the quality of finished product.
Description
Technical field
The invention belongs to proton membrane fields, and in particular to a kind of polyphenylene oxide graphene proton membrane and preparation method thereof.
Background technique
Polyphenylene oxide (PPO) is a kind of widely applied thermoplastic material, has good mechanical performance and water resistance, is shunk
Rate is low, nontoxic, and density is small, without highly polar group especially in PPO structure, electric performance stablity, can extensive temperature, humidity and
Good electrical property is kept in frequency range, and PPO molecular structure is simple, can carry out various modifications for different requirements,
Sulfonated poly (phenylene oxide) (SPPO) has excellent chemical property, is used on amberplex and charged filters pressing film in the past, and
SPPO has good thermal stability, therefore SPPO is considered as a kind of preferable proton conducting material, can be applicable to fuel electricity
Chi Zhong.But the conductivity of sulfonated poly (phenylene oxide) has bigger gap compared to for perfluorinated sulfonic acid Nafion membrane.And by from
It is to solve the problems, such as this good method that subconductivity, which enhances modification,.
Summary of the invention
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of polyphenylene oxide graphene proton membrane and
Preparation method.
To achieve the above object, the invention adopts the following technical scheme:
A kind of polyphenylene oxide graphene proton membrane, it is composed of the following raw materials by weight:
Bromohexane 2-4, polyphenylene oxide 100-120, benzotriazole modified graphene 10-13,2-mercaptobenzimidazole 0.6-1, second
Sour isobutyric acid sucrose ester 0.1-0.2, molybdenum boride 1-2, dibutyl tin dilaurate 0.5-1, dispersing agent 1-2, ricinoleic acid 3-4.
The dispersing agent is polyoxyethylene sorbitan monoleate.
The preparation method of the benzotriazole modified graphene, comprising the following steps:
Graphene oxide is taken, is added in the isopropanol of 6-8 times of its weight, increasing temperature is 60-70 DEG C, and triethylamine is added, and is protected
Precipitating is washed in temperature stirring 10-13 hours, filtering, and air drying obtains amination graphene；
Amination graphene is taken, is added in the dimethylformamide of 16-20 times of its weight, ultrasonic disperse 1-2 hours, is sent to
In 55-60 DEG C of water bath with thermostatic control, benzotriazole is added, insulated and stirred 16-20 hours, discharges, precipitating is washed, sent by filtering
Enter in baking oven, dries at 85-90 DEG C completely to get the benzotriazole modified graphene.
The graphene oxide, triethylamine, benzotriazole weight ratio be 35-40:3-4:0.1-0.2.
A kind of preparation method of polyphenylene oxide graphene proton membrane, comprising the following steps:
(1) bromohexane is taken, is added in the dimethylformamide of 3-5 times of its weight, it is 10-14 minutes ultrasonic；
(2) 2-mercaptobenzimidazole is taken, is added in the isopropanol of 2-4 times of its weight, the insulated and stirred 10-20 at 60-65 DEG C
Minute, obtain alcoholic solution；
(3) polyphenylene oxide is taken, is added in the dimethylformamide of 4-7 times of its weight, it is 10-20 minutes ultrasonic, with above-mentioned bromohexane
Dimethyl formamide solution mixing, be sent in 70-75 DEG C of water bath with thermostatic control, above-mentioned alcoholic solution, polyoxyethylene sorbitan monoleate be added, protect
Temperature stirs 10-15 hours, discharges, and filters, filter cake is washed, and is sent into baking oven, dry complete at 80-85 DEG C, and it is modified to obtain bromination
Polyphenylene oxide；
(4) above-mentioned bromination Noryl is taken, is added in the dimethylformamide of 30-40 times of its weight, stirs evenly, is obtained poly-
Phenylate amide solution；
(5) molybdenum boride, ricinoleic acid mixing are taken, insulated and stirred 1-2 hours at 55-60 DEG C, is added to mixture weight 10-15
It is 10-20 minutes ultrasonic in dimethylformamide again, it is mixed with above-mentioned benzotriazole modified graphene, ultrasonic 20-30 points
Clock obtains modified graphene dispersion liquid；
(6) above-mentioned polyphenylene oxide amide solution, the mixing of modified graphene dispersion liquid are taken, Sucrose acetoisobutyrate, two laurels is added
Sour dibutyl tin, ultrasound 1-2 hours, are poured into culture dish at 40-50 DEG C, are put into vacuum oven vacuum at 70-85 DEG C
Dry 20-30 hour, after film molding, it is put into 95-105 DEG C of thermostatic drying chamber processing 1-2 hours, takes off film, forced air drying, i.e.,
Obtain the polyphenylene oxide graphene proton membrane.
Advantages of the present invention:
The present invention uses triethylamine to handle graphene oxide first, then modified by benzotriazole, obtains benzotriazole
Modified graphene, later using bromohexane as material modification polyphenylene oxide, then the dimethyl formyl with benzotriazole modified graphene
Amine aqueous solution is blended, and intercalation modifying is carried out, so that the dispersion compatibility between graphene and polyphenylene oxide is realized, to improve finished product
Mechanical stability improve the quality of finished product and by the modified proton conductivity that proton membrane can be improved of benzotriazole.
Specific embodiment
Embodiment 1
A kind of polyphenylene oxide graphene proton membrane, it is composed of the following raw materials by weight:
Bromohexane 4, polyphenylene oxide 120, benzotriazole modified graphene 13,2-mercaptobenzimidazole 1, Sucrose acetoisobutyrate
0.2, molybdenum boride 2, dibutyl tin dilaurate 1, dispersing agent 2, ricinoleic acid 4.
The dispersing agent is polyoxyethylene sorbitan monoleate.
The preparation method of the benzotriazole modified graphene, comprising the following steps:
Graphene oxide is taken, is added in the isopropanol of 8 times of its weight, increasing temperature is 670 DEG C, and triethylamine is added, and heat preservation is stirred
It mixes 13 hours, filters, precipitating is washed, air drying obtains amination graphene；
Amination graphene is taken, is added in the dimethylformamide of 20 times of its weight, ultrasonic disperse 2 hours, is sent to 60 DEG C
In water bath with thermostatic control, benzotriazole is added, insulated and stirred 20 hours, discharges, precipitating is washed in filtering, is sent into baking oven, 90
It dries at DEG C completely to get the benzotriazole modified graphene.
The graphene oxide, triethylamine, benzotriazole weight ratio be 40:4:0.2.
A kind of preparation method of polyphenylene oxide graphene proton membrane, comprising the following steps:
(1) bromohexane is taken, is added in the dimethylformamide of 5 times of its weight, ultrasound 14 minutes；
(2) 2-mercaptobenzimidazole is taken, is added in the isopropanol of 4 times of its weight, insulated and stirred 10-20 minutes at 65 DEG C,
Obtain alcoholic solution；
(3) polyphenylene oxide is taken, is added in the dimethylformamide of 7 times of its weight, ultrasound 20 minutes, the diformazan with above-mentioned bromohexane
The mixing of base formamide solution, is sent in 75 DEG C of water bath with thermostatic control, above-mentioned alcoholic solution, polyoxyethylene sorbitan monoleate, insulated and stirred 15 is added
Hour, it discharges, filters, filter cake is washed, be sent into baking oven, drying completely, obtains bromination Noryl at 85 DEG C；
(4) above-mentioned bromination Noryl is taken, is added in the dimethylformamide of 40 times of its weight, is stirred evenly, obtain polyphenyl
Ether amide solution；
(5) molybdenum boride, ricinoleic acid mixing are taken, insulated and stirred 2 hours at 60 DEG C are added to 15 times of mixture weight of diformazan
In base formamide, ultrasound 20 minutes is mixed with above-mentioned benzotriazole modified graphene, and ultrasound 30 minutes obtains modified graphene
Dispersion liquid；
(6) above-mentioned polyphenylene oxide amide solution, the mixing of modified graphene dispersion liquid are taken, Sucrose acetoisobutyrate, two laurels is added
Sour dibutyl tin, ultrasound 2 hours, are poured into culture dish at 50 DEG C, and being put into vacuum oven, that 30 are dried in vacuo at 85 DEG C is small
When, after film molding, it is put into 105 DEG C of thermostatic drying chamber and handles 2 hours, take off film, forced air drying is to get the polyphenylene oxide graphite
Olefinic proton film.
Embodiment 2
A kind of polyphenylene oxide graphene proton membrane, it is composed of the following raw materials by weight:
Bromohexane 2, polyphenylene oxide 100, benzotriazole modified graphene 10,2-mercaptobenzimidazole 0.6, Sucrose Acetate acid sucrose
Ester 0.1, molybdenum boride 1, dibutyl tin dilaurate 0.5, dispersing agent 1-2, ricinoleic acid 3.
The dispersing agent is polyoxyethylene sorbitan monoleate.
The preparation method of the benzotriazole modified graphene, comprising the following steps:
Graphene oxide is taken, is added in the isopropanol of 6 times of its weight, increasing temperature is 60 DEG C, and triethylamine, insulated and stirred is added
10 hours, precipitating was washed in filtering, and air drying obtains amination graphene；
Amination graphene is taken, is added in the dimethylformamide of 16-20 times of its weight, ultrasonic disperse 1 hour, is sent to 55 DEG C
Water bath with thermostatic control in, be added benzotriazole, insulated and stirred 16 hours, discharge, filtering, will precipitating washing, be sent into baking oven in,
It dries at 85 DEG C completely to get the benzotriazole modified graphene.
The graphene oxide, triethylamine, benzotriazole weight ratio be 35:3:0.1.
A kind of preparation method of polyphenylene oxide graphene proton membrane, comprising the following steps:
(1) bromohexane is taken, is added in the dimethylformamide of 3 times of its weight, ultrasound 10 minutes；
(2) 2-mercaptobenzimidazole is taken, is added in the isopropanol of 2 times of its weight, insulated and stirred 10-20 minutes at 60 DEG C,
Obtain alcoholic solution；
(3) polyphenylene oxide is taken, is added in the dimethylformamide of 4-7 times of its weight, ultrasound 10 minutes, two with above-mentioned bromohexane
The mixing of methylformamide solution, is sent in 70 DEG C of water bath with thermostatic control, above-mentioned alcoholic solution, polyoxyethylene sorbitan monoleate, insulated and stirred is added
It 10 hours, discharges, filters, filter cake is washed, be sent into baking oven, it is dry complete at 80 DEG C, obtain bromination Noryl；
(4) above-mentioned bromination Noryl is taken, is added in the dimethylformamide of 30 times of its weight, is stirred evenly, obtain polyphenyl
Ether amide solution；
(5) molybdenum boride, ricinoleic acid mixing are taken, insulated and stirred 1 hour at 55 DEG C is added to 10 times of mixture weight of diformazan
In base formamide, ultrasound 10 minutes is mixed with above-mentioned benzotriazole modified graphene, and ultrasound 20 minutes obtains modified graphene
Dispersion liquid；
(6) above-mentioned polyphenylene oxide amide solution, the mixing of modified graphene dispersion liquid are taken, Sucrose acetoisobutyrate, two laurels is added
Sour dibutyl tin, ultrasound 1 hour, is poured into culture dish at 40 DEG C, and being put into vacuum oven, that 20 are dried in vacuo at 70 DEG C is small
When, after film molding, it is put into 95 DEG C of thermostatic drying chamber and handles 1 hour, take off film, forced air drying is to get the polyphenylene oxide graphite
Olefinic proton film.
Performance test:
The proton conductivity of the polyphenylene oxide graphene proton membrane of embodiment 1 is 3.07 × 10-2Scm-1；
Mechanical mechanics property 37.5Mpa；
The proton conductivity of the polyphenylene oxide graphene proton membrane of embodiment 2 is 3.05 × 10-2Scm-1；
Mechanical mechanics property 37.7Mpa.
Claims (5)
1. a kind of polyphenylene oxide graphene proton membrane, which is characterized in that it is composed of the following raw materials by weight:
Bromohexane 2-4, polyphenylene oxide 100-120, benzotriazole modified graphene 10-13,2-mercaptobenzimidazole 0.6-1, second
Sour isobutyric acid sucrose ester 0.1-0.2, molybdenum boride 1-2, dibutyl tin dilaurate 0.5-1, dispersing agent 1-2, ricinoleic acid 3-4.
2. a kind of polyphenylene oxide graphene proton membrane according to claim 1, which is characterized in that the dispersing agent is poly- mountain
Pear ester 80.
3. a kind of polyphenylene oxide graphene proton membrane according to claim 1, which is characterized in that the benzotriazole changes
The preparation method of property graphene, comprising the following steps:
Graphene oxide is taken, is added in the isopropanol of 6-8 times of its weight, increasing temperature is 60-70 DEG C, and triethylamine is added, and is protected
Precipitating is washed in temperature stirring 10-13 hours, filtering, and air drying obtains amination graphene；
Above-mentioned amination graphene is taken, is added in the dimethylformamide of 16-20 times of its weight, ultrasonic disperse 1-2 hours, is sent into
Into 55-60 DEG C of water bath with thermostatic control, benzotriazole being added, insulated and stirred 16-20 hours, discharges, precipitating is washed in filtering,
It is sent into baking oven, dries at 85-90 DEG C completely to get the benzotriazole modified graphene.
4. a kind of polyphenylene oxide graphene proton membrane according to claim 3, which is characterized in that the graphene oxide,
Triethylamine, benzotriazole weight ratio be 35-40:3-4:0.1-0.2.
5. a kind of preparation method of the polyphenylene oxide graphene proton membrane as described in any in claim 1-4, which is characterized in that packet
Include following steps:
(1) bromohexane is taken, is added in the dimethylformamide of 3-5 times of its weight, it is 10-14 minutes ultrasonic；
(2) 2-mercaptobenzimidazole is taken, is added in the isopropanol of 2-4 times of its weight, the insulated and stirred 10-20 at 60-65 DEG C
Minute, obtain alcoholic solution；
(3) polyphenylene oxide is taken, is added in the dimethylformamide of 4-7 times of its weight, it is 10-20 minutes ultrasonic, with above-mentioned bromohexane
Dimethyl formamide solution mixing, be sent in 70-75 DEG C of water bath with thermostatic control, above-mentioned alcoholic solution, polyoxyethylene sorbitan monoleate be added, protect
Temperature stirs 10-15 hours, discharges, and filters, filter cake is washed, and is sent into baking oven, dry complete at 80-85 DEG C, and it is modified to obtain bromination
Polyphenylene oxide；
(4) above-mentioned bromination Noryl is taken, is added in the dimethylformamide of 30-40 times of its weight, stirs evenly, is obtained poly-
Phenylate amide solution；
(5) molybdenum boride, ricinoleic acid mixing are taken, insulated and stirred 1-2 hours at 55-60 DEG C, is added to mixture weight 10-15
It is 10-20 minutes ultrasonic in dimethylformamide again, it is mixed with above-mentioned benzotriazole modified graphene, ultrasonic 20-30 points
Clock obtains modified graphene dispersion liquid；
(6) above-mentioned polyphenylene oxide amide solution, the mixing of modified graphene dispersion liquid are taken, Sucrose acetoisobutyrate, two laurels is added
Sour dibutyl tin, ultrasound 1-2 hours, are poured into culture dish at 40-50 DEG C, are put into vacuum oven vacuum at 70-85 DEG C
Dry 20-30 hour, after film molding, it is put into 95-105 DEG C of thermostatic drying chamber processing 1-2 hours, takes off film, forced air drying, i.e.,
Obtain the polyphenylene oxide graphene proton membrane.
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| CN115386214A (en) * | 2022-10-09 | 2022-11-25 | 万华化学（宁波）有限公司 | Weather-proof halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
| CN115746365A (en) * | 2022-11-17 | 2023-03-07 | 深圳市睿华涂布科技有限公司 | Direct-pressing latticed release film and preparation method thereof |
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| CN108134118A (en) * | 2017-12-25 | 2018-06-08 | 宁波卡尔新材料科技有限公司 | A kind of preparation method of triazole graphene modification sulphonation polyphenylene oxide proton membrane and mating film-forming process |
| CN108485231A (en) * | 2018-05-04 | 2018-09-04 | 芜湖天科生物科技有限公司 | A kind of epoxidation polyphenylene oxide conductive film and preparation method thereof |
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| CN107221691A (en) * | 2017-05-26 | 2017-09-29 | 厦门大学 | The preparation method of graphene oxide/imidazoles polyphenylene oxide composite anion exchange membrane |
| CN108134118A (en) * | 2017-12-25 | 2018-06-08 | 宁波卡尔新材料科技有限公司 | A kind of preparation method of triazole graphene modification sulphonation polyphenylene oxide proton membrane and mating film-forming process |
| CN108485231A (en) * | 2018-05-04 | 2018-09-04 | 芜湖天科生物科技有限公司 | A kind of epoxidation polyphenylene oxide conductive film and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115386214A (en) * | 2022-10-09 | 2022-11-25 | 万华化学（宁波）有限公司 | Weather-proof halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
| CN115386214B (en) * | 2022-10-09 | 2023-10-17 | 万华化学（宁波）有限公司 | Weather-resistant halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
| CN115746365A (en) * | 2022-11-17 | 2023-03-07 | 深圳市睿华涂布科技有限公司 | Direct-pressing latticed release film and preparation method thereof |
| CN115746365B (en) * | 2022-11-17 | 2023-08-01 | 深圳市睿华涂布科技有限公司 | Direct-pressure grid-shaped release film and preparation method thereof |
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