CN1253491C - Process for synthesis of sulfonated polyimide proton transmission film - Google Patents
Process for synthesis of sulfonated polyimide proton transmission film Download PDFInfo
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- CN1253491C CN1253491C CNB2004100112056A CN200410011205A CN1253491C CN 1253491 C CN1253491 C CN 1253491C CN B2004100112056 A CNB2004100112056 A CN B2004100112056A CN 200410011205 A CN200410011205 A CN 200410011205A CN 1253491 C CN1253491 C CN 1253491C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention belongs to a method for synthesizing sulfonated polyimide proton transmission membranes. Albocarbon tetracid dianhydride, sulfonated diamine, common diamine, dehydrating catalysts and tertiary amine which are connected in a bridge mode are added into phenol solvent protected by nitrogen, the mixture is heated to 60 to 80 DEG C to keep stirring reaction for 1 to 2 hours, and then, the mixture is heated to 160 to 200 DEG C to keep polymerization reaction for 4 to 24 hours. After cooled, the mixture is sunk into ethanol, thoroughly washed and then dried. Reaction products are dissolved to lay a membrane and then are dried, the membrane is soaked into ethanol to be washed thoroughly to remove the solvent, and then, the membrane is put into chlorhydric acid to be soaked for 8 to 10 hours to remove the tertiary amine through neutralization. The membrane is taken out and put into deionized water to be repeatedly soaked for a plurality of times, and a brown yellow polyimide proton transmission membrane can be obtained after excess chlorhydric acid in the thin membrane is removed.
Description
Technical field
The invention belongs to the synthetic method of sulfonated polyimide proton transmission film.
Background technology
It is communications and transportation and other application need cleaning that polymer electrolyte fuel cells (PEFCs) has been counted as potential power resource, the quiet and portable energy.The PEFCs most important component is a polymer dielectric film itself.Sulfonation (per) fluoropolymer film Nafion almost is a proton transmission film in the present unique PEFCs of the being used in system with its higher specific conductivity and stability.Yet price of its costliness and higher methanol permeability have seriously limited it in the directly application of methanol fuel cell.In recent years based on sulfonated polyimide proton transmission film with its excellent mechanical property, thermal characteristics and hinder methanol permeability and the (S.Faure that has received increasing attention preferably, US Pat 6245881, Y.Woo, J.MembraneSci., 2003,220,31 and W.Essafi, Macromolecules 2004,37,1431).The proton conduction performance of some of them sulfonated polyimide near commercial Nafion film, has shown its extraordinary application prospect in the methanol fuel cell field.But the present major part of studying is confined to based on commercially available 1,1 ', 8, on the sulfonated polyimide of 8 '-naphthalene tetracarboxylic dianhydride synthetic.And its relatively poor solubility limits the use of sulfonated polyimide film and the further raising of performance thereof, though its hydrolytic resistance is better than common polyimide, the water stability life-span of its film awaits further to improve to satisfy the basic service requirements of fuel cell.The sulfonated polyimide of relevant bridging type naphthalene acid anhydride is not then seen relevant report.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of sulfonated polyimide proton transmission film.
The proton hydrogen of contained sulfonate radical can dissociate under the condition that water exists in the polymeric system, become free-moving proton, thereby polymeric film can conduct electricity, because its two anhydride component is the bridging type, has higher electronegativity, therefore the water stability of polyimide has obtained certain raising, and polymkeric substance generally all dissolves in N-Methyl pyrrolidone or phenol solvent.
Chemical reaction process is as follows:
In the formula, the scope of X is 0.1-0.9;
Diacid wherein
Acid anhydride can be any one of following structure dianhydride;
4,4 '-dinaphthalene-1,1 ', 8,8 '-tetracarboxylic dianhydride
4,4 '-(4 ", the 4 -different propane of dioxy base-phenylbenzene)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(4 ", 4 -dimercapto-sulfobenzide)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(4 ", 4 -thioresorcin)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(4 ", 4 -dioxy base benzene)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(3 ", 3 -dioxy base benzene)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
Sulfonated diamines H
2N-R
1-NH
2Be any one of following structure diamines;
4,4 '-diaminodiphenylmethane-2,2 '-disulfonic acid 4,4 '-diamino-3,3 '-dimethyl diphenyl methane
-2,2 '-disulfonic acid
4,4 '-diamino-2,2 ' 3,3 '-dimethyl 24,4 '-diamino-2,2 '-dimethyl diphenyl-2,2 '-
Phenylmethane-2,2 '-the disulfonic acid disulfonic acid
4,4 '-diamino-3,3 '-dimethyl diphenyl 4,4 ,-benzidine-3,3 ,-disulfonic acid
-2,2 '-disulfonic acid
2,6 '-diaminostilbene, 3,5-trimethylbenzene sulfonic acid 3,5-diamino benzene sulfonic acid
4,4 '-diaminodiphenyl oxide-2,2 '-disulfonic acid 3,4 '-diaminodiphenyl oxide-2,3 '-disulfonic acid
4,4 '-diaminostilbene ", 3 " and-two phenoxy groups 3,3 '-diaminostilbene ", 3 " and-two phenoxy group benzene
Benzene-5 "-sulfonic acid-5 "-sulfonic acid
9,9 '-two (4-aminophenyl) fluorenes-2,7 '-2 4,4 '-diamino-4 ", 4 -two phenoxy group connection
Sulfonic acid benzene-3 ", 3 -disulfonic acid
4,4 '-diaminostilbene ", 4 "-two phenoxy groups-benzene
4,4 '-diamino-4 ", 4 -hexichol-2 "-sulfonic acid
Oxygen base-phenylbenzene different propane-5 ", 5 -
Disulfonic acid
Common diamines H
2N-R
2-NH
2Be any one of following structure diamines;
4,4 '-diaminodiphenylmethane 4,4 '-diamino-3,3 '-dimethyl diphenyl methane
4,4 '-diamino-2,2 ' 3,3 '-dimethyl hexichol
Methane 4,4 '-diamino-2,2 '-dimethyl diphenyl
4,4 '-diamino-3,3 '-dimethyl diphenyl
4,4-diamino-2,2 '-bis trifluoromethyl biphenyl
2,6-diaminostilbene, 3,5-trimethylbenzene mphenylenediamine
4,4 '-diaminodiphenyl oxide
3,4 '-diaminodiphenyl oxide
4,4 '-diaminostilbene ", 3 " and-two phenoxy groups 3,3 '-diaminostilbene ", 3 " and-two phenoxy group benzene
Benzene
4,4 '-diamino-4 ", 4 -two phenoxy group
9,9 '-two (4-aminophenyl) fluorenes biphenyl
4,4 '-diamino-4 ", 4 -hexichol oxygen 4,4 '-diaminostilbene " and, 4 "-two phenoxy group benzene
The different propane of base-phenylbenzene
Preparation process is as follows: with the naphthalene tetracarboxylic dianhydride of bridging; the sulfonated diamine; common diamine; dehydration catalyst and uncle's ammonia join in the phenol solvent of nitrogen protection; be warmed up to 60-80 ℃ of stirring reaction 1-2h; be warmed up to 160 ℃ of-200 ℃ of polyreaction 4h-20h again; sink in the ethanol after the reaction cooling; the thorough washing after drying; film is spread in its dissolving then; dry; be immersed in thorough washing in the ethanol again; remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization; taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.Its room-temperature conductivity is generally at 0.1S.cm
-1-0.3S.cm
-1Between.
Solvent for use of the present invention is phenol, cresols, P-Chlorophenol or N-Methyl pyrrolidone; Described dehydration catalyst is phenylformic acid, quinoline or isoquinoline 99.9, and its consumption is 1-1.5 a times of dicarboxylic anhydride; Described tertiary amine is triethylamine, Tributylamine, pyridine or pyrroles, and its consumption is 2-2.2 a times of sulfonation diamine; Described initial reaction temperature is 60-80 ℃, and the time is 1-2h; The end reaction temperature is 160 ℃-200 ℃, and the reaction times is 4-24 hour.
Embodiment
Embodiment 1
With 4; 4 '-dinaphthalene-1,1 ', 8; 8 '-tetracarboxylic dianhydride 0.1mol (39.4g), 4; 4 '-diaminodiphenylmethane-2,2 '-disulfonic acid 0.01mol (3.58g), 4,4 '-diaminodiphenylmethane 0.09mol (17.8g), phenylformic acid 0.12mol (12.2g) and triethylamine 0.2mol (20g) join among the cresols 900ml of nitrogen protection; be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, dry, be immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, and taking-up is put into deionized water and soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, the electric conductivity of 100% humidity is 0.062S.cm during its room temperature
-1
Embodiment 2
With 4,4 '-(4 "; the 4 -different propane of dioxy base-phenylbenzene)-1,1 ', 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (62.1g), 4; 4 '-diamino-3,3 '-dimethyl diphenyl methane-2,2 '-disulfonic acid 0.09mol (34.8g), 4; 4 '-diamino-3,3 '-dimethyl diphenyl methane 0.01mol (22.6g), phenylformic acid 0.13mol (15.9g) and Tributylamine 0.22mol (31.5g) join among the cresols 900ml of nitrogen protection; be warmed up to 80 ℃ of stirring reaction 1.5h; be warmed up to 160 ℃ of polyreaction 24h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, dry, be immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, and taking-up is put into deionized water and soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, the electric conductivity of 100% humidity is 0.12S.cm during its room temperature
-1
Embodiment 3
With 4; 4 '-(4 "; 4 -dimercapto-sulfobenzide)-1; 1 '; 8,8 '-naphthalene tetracarboxylic dianhydride 0.1mol (67.5g); 4,4 '-diamino-2; 2 ' 3; 3 '-dimethyl diphenyl methane-2,2 '-disulfonic acid 0.05mol (20.7g); 4,4 '-diamino-2; 2 ' 3; 3 '-dimethyl diphenyl methane 0.05mol (12.7g); phenylformic acid 0.15mol (18.3g) and pyridine 0.21mol (16.6g) join among the cresols 900ml of nitrogen protection, are warmed up to 60 ℃ of stirring reaction 1h, are warmed up to 180 ℃ of polyreaction 10h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, dry, be immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, and taking-up is put into deionized water and soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, the electric conductivity of 100% humidity is 0.09S.cm during its room temperature
-1
Embodiment 4
With 4; 4 '-(4 "; 4 -thioresorcin)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (53.5g), 4; 4 '-diamino-2,2 '-dimethyl diphenyl-2,2 '-disulfonic acid 0.03mol (11.2g), 4; 4 '-diamino-2; 2 '-dimethyl diphenyl 0.07mol (14.9g), quinoline 0.15mol (19.4g) and pyrroles 0.22mol (14.8g) join among the cresols 900ml of nitrogen protection, are warmed up to 70 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 12h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, dry, be immersed in thorough washing in the ethanol again, remove and desolvate, put it at last and soak 8h in the hydrochloric acid, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, the electric conductivity of 100% humidity is 0.2S.cm during its room temperature
-1
Embodiment 5
With 4; 4 '-(4 "; 4 -dioxy base benzene)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (50.2g), 4; 4 '-diamino-3,3 '-dimethyl diphenyl-2,2 '-disulfonic acid 0.05mol (18.6g), 4; 4 '-diamino-3; 3 '-dimethyl diphenyl 0.05mol (10.6g), quinoline 0.15mol (19.4g) and triethylamine 0.2mol (20g) join among the cresols 900ml of nitrogen protection, are warmed up to 70 ℃ of stirring reaction 1h, are warmed up to 200 ℃ of polyreaction 6h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, dry, be immersed in thorough washing in the ethanol again, remove and desolvate, put it at last and soak 9h in the hydrochloric acid, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, the electric conductivity of 100% humidity is 0.04S.cm during its room temperature
-1
Embodiment 6
With 4,4 '-dinaphthalene-1,1 '; 8; 8 '-tetracarboxylic dianhydride 0.1mol (39.4g), 4,4 '-benzidine-3,3 '-disulfonic acid 0.07mol (24.2g), 4; 4 '-diamino-2; 2 '-bis trifluoromethyl biphenyl 0.03mol (9.6g), quinoline 0.12mol (15.5g) and triethylamine 0.2mol (20g) join among the P-Chlorophenol 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 200 ℃ of polyreaction 4h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, dry, be immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, and taking-up is put into deionized water and soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, the electric conductivity of 100% humidity is 0.3S.cm during its room temperature
-1
Embodiment 7
With 4,4 '-dinaphthalene-1,1 '; 8,8 '-tetracarboxylic dianhydride 0.1mol (39.4g), 2,6-diaminostilbene; 3,5-trimethylbenzene sulfonic acid 0.07mol (6.9g), 2,6-diaminostilbene; 3; 5-trimethylbenzene 0.03mol (4.5g), phenylformic acid 0.1mol (12.2g) and triethylamine 0.2mol (20g) join among the P-Chlorophenol 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 200 ℃ of polyreaction 24h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 8
With 4; 4 '-(4 "; 4 -dimercapto-sulfobenzide)-1,1 ', 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (67.5g), 3; 5-diamino benzene sulfonic acid 0.09mol (16.9g), mphenylenediamine 0.01mol (1.1g), quinoline 0.12mol (15.5g) and triethylamine 0.21mol (21g) join among the P-Chlorophenol 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 9
With 4; 4 '-(4 "; 4 -thioresorcin)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (53.5g), 4; 4 '-diaminodiphenyl oxide-2; 2 '-disulfonic acid 0.03mol (10.8g), 4; 4 '-diaminodiphenyl oxide 0.07mol (14.0g), phenylformic acid 0.1mol (12.2g) and triethylamine 0.21mol (21g) join among the cresols 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 10
With 4; 4 '-(4 "; 4 -dioxy base benzene)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (50.2g), 3; 4 '-diaminodiphenyl oxide-2; 3 '-disulfonic acid 0.04mol (14.4g), 3; 4 '-diaminodiphenyl oxide 0.06mol (12.0g), phenylformic acid 0.1mol (12.2g) and pyridine 0.2mol (15.8g) join among the N-Methyl pyrrolidone 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 11
With 4; 4 '-(4 "; the 4 -different propane of dioxy base-phenylbenzene)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (62.1g), 4; 4 '-diaminostilbene "; 3 "-two phenoxy group benzene-5 "-sulfonic acid 0.04mol (14.8g), 4,4 '-diaminostilbene ", 3 " and-two phenoxy group benzene 0.06mol (17.5g), quinoline 0.1mol (12.9g) and pyridine 0.2mol (15.8g) join among the N-Methyl pyrrolidone 900ml of nitrogen protection; and be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 12
With 4; 4 '-(4 "; 4 -dimercapto-sulfobenzide)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (64.5g), 3; 3 '-diaminostilbene "; 3 "-two phenoxy group benzene-5 "-sulfonic acid 0.04mol (14.9g), 3,3 '-diaminostilbene ", 3 " and-two phenoxy group benzene 0.06mol (17.5g), quinoline 0.1mol (12.9g) and pyridine 0.2mol (15.8g) join among the N-Methyl pyrrolidone 900ml of nitrogen protection; and be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 13
With 4; 4 '-(4 "; the 4 -different propane of dioxy base-phenylbenzene)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (62.1g), 9; 9 '-two (4-aminophenyl) fluorenes-2; 7 '-disulfonic acid 0.04mol (20.3g), 4,4 '-diamino-4 ", 4 -two phenoxy group biphenyl 0.06mol (22.1g), isoquinoline 99.9 0.14mol (18.1g) and pyridine 0.2mol (15.8g) join among the cresols 900ml of nitrogen protection; be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 14
With 4; 4 '-dinaphthalene-1; 1 '; 8; 8 '-tetracarboxylic dianhydride 0.1mol (39.4g), 4; 4 '-diamino-4 "; 4 -two phenoxy group biphenyl-3 "; 3 -disulfonic acid 0.04mol (21.1g), 9; 9 '-two (4-aminophenyl) fluorenes 0.06mol (20.9g), isoquinoline 99.9 0.14mol (18.1g) and pyridine 0.2mol (15.8g) join among the cresols 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 15
With 4; 4 '-(4 "; 4 -thioresorcin)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (53.5g), 4; 4 '-diamino-4 "; 4 -two phenoxy groups-phenylbenzene different propane-5 ", 5 -disulfonic acid 0.04mol (22.8g), 9,9 '-two (4-aminophenyl) fluorenes 0.06mol (17.4g), isoquinoline 99.9 0.14mol (18.1g) and pyridine 0.2mol (15.8g) join among the cresols 900ml of nitrogen protection; be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 16
With 4; 4 '-(4 "; 4 -thioresorcin)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (53.5g), 4; 4 '-diaminostilbene "; 4 "-two phenoxy group benzene-2 "-sulfonic acid 0.04mol (14.9g), 4,4 '-diamino-4 ", the different propane 0.06mol of 4 -two phenoxy groups-phenylbenzene (24.6g), isoquinoline 99.9 0.12mol (15.5g) and triethylamine 0.2mol (20g) join among the cresols 900ml of nitrogen protection; be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 17
With 4; 4 '-dinaphthalene-1; 1 '; 8; 8 '-tetracarboxylic dianhydride 0.1mol (39.4g), 4; 4 '-diamino-4 "; 4 -two phenoxy group biphenyl-3 "; 3 -disulfonic acid 0.04mol (21.1g), 4,4 '-diaminostilbene ", 4 "-two phenoxy group benzene 0.06mol (17.5g), isoquinoline 99.9 0.12mol (15.5g) and triethylamine 0.2mol (20g) join among the cresols 900ml of nitrogen protection; be warmed up to 80 ℃ of stirring reaction 2h; be warmed up to 180 ℃ of polyreaction 18h again, sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 18
With 4; 4 '-(3 "; 3 -dioxy base benzene)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (50.2g), 9; 9 '-two (4-aminophenyl) fluorenes-2; 7 '-disulfonic acid 0.02mol (10.2g), 4; 4 '-diaminodiphenyl oxide 0.08mol (16.0g), isoquinoline 99.9 0.15mol (19.4g) and triethylamine 0.22mol (22g) join among the phenol 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 19
With 4; 4 '-(4 "; the 4 -different propane of dioxy base-phenylbenzene)-1; 1 '; 8; 8 '-naphthalene tetracarboxylic dianhydride 0.1mol (62.1g), 9; 9 '-two (4-aminophenyl) fluorenes-2; 7 '-disulfonic acid 0.03mol (15.3g), 9; 9 '-two (4-aminophenyl) fluorenes 0.07mol (24.4g), isoquinoline 99.9 0.15mol (19.4g) and triethylamine 0.22mol (22g) join among the phenol 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Embodiment 20
With 4,4 '-dinaphthalene-1,1 '; 8; 8 '-tetracarboxylic dianhydride 0.1mol (39.4g), 4,4 '-diaminodiphenyl oxide-2,2 '-disulfonic acid 0.05mol (18.0g), 4; 4-diamino-2; 2 '-bis trifluoromethyl biphenyl 0.05mol (16.0g), phenylformic acid 0.1mol (12.2g) and triethylamine 0.22mol (22g) join among the phenol 900ml of nitrogen protection, are warmed up to 80 ℃ of stirring reaction 2h, are warmed up to 180 ℃ of polyreaction 18h again; sink in the ethanol thorough washing after drying after the cooling.Film is spread in its dissolving then, and drying is immersed in thorough washing in the ethanol again, remove and desolvate, put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, taking-up is put into deionized water and is soaked repeatedly for several times, remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film.
Claims (4)
1. the synthetic method of a sulfonated polyimide proton transmission film, its chemical reaction process is as follows:
In the formula, the scope of X is 0.1-0.9;
Dicarboxylic anhydride wherein
Can be any one of following structure dianhydride;
4,4 '-dinaphthalene-1,1 ', 8,8 '-tetracarboxylic dianhydride
4,4 '-(4 ", the 4 -different propane of dioxy base-phenylbenzene)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(4 ", 4 -dimercapto-sulfobenzide)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(4 ", 4 -thioresorcin)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(4 ", 4 -dioxy base benzene)-1,1, ' 8,8 '-naphthalene tetracarboxylic dianhydride
4,4 '-(3 ", 3 -dioxy base benzene)-1,1 ', 8,8 '-naphthalene tetracarboxylic dianhydride
Sulfonated diamines H
2N-R
1-NH
2Be any one of following structure diamines;
4,4 '-diaminodiphenylmethane-2,2 '-disulfonic acid 4,4 '-diamino-3,3 '-dimethyl diphenyl methane-2,2 '-
Disulfonic acid
4,4 '-diamino-2,2 ' 3,3 '-dimethyl hexichol first 4,4 '-diamino-2,2 '-dimethyl diphenyl-2,2 '-two sulphurs
Alkane-2, the acid of 2 '-disulfonic acid
4,4 '-diamino-3,3 '-dimethyl diphenyl-2,2 '-4,4 '-benzidine-3,3 '-disulfonic acid
Disulfonic acid
2,6 '-diaminostilbene, 3,5-trimethylbenzene sulfonic acid 3,5-diamino benzene sulfonic acid
4,4 '-diaminodiphenyl oxide-2,2 '-disulfonic acid 3,4 '-diaminodiphenyl oxide-2,3 '-disulfonic acid
4,4 '-diaminostilbene ", 3 " and-two phenoxy group benzene 3,3 '-diaminostilbene ", 3 " and-two phenoxy group benzene
-5 "-sulfonic acid-5 "-sulfonic acid
9,9 '-two (4-aminophenyl) fluorenes-2,7 '-disulfonic acid 4,4 '-diamino-4 ", 4 -two phenoxy group biphenyl
-3 ", 3 -disulfonic acid
4,4 '-diamino-4 ", 4 -hexichol oxygen 4,4 '-diaminostilbene " and, 4 "-two phenoxy groups-benzene
Base-phenylbenzene different propane-5 ", 5 -disulfonic acid-2 "-sulfonic acid
Common diamines H
2N-R
2-NH
2Be any one of following structure diamines;
4,4 '-diaminodiphenylmethane 4,4 '-diamino-3,3 '-dimethyl diphenyl methane
4,4 '-diamino-2,2 ' 3,3 '-dimethyl 24,4 '-diamino-2,2 '-dimethyl diphenyl
Phenylmethane
4,4 '-diamino-3,3 '-dimethyl diphenyl 4,4-diamino-2,2 '-bis trifluoromethyl biphenyl
2,6-diaminostilbene, 3,5-trimethylbenzene mphenylenediamine
4,4 '-diaminodiphenyl oxide 3,4 '-diaminodiphenyl oxide
4,4 '-diaminostilbene ", 3 " and-two phenoxy groups 3,3 '-diaminostilbene ", 3 " and-two phenoxy group benzene
Benzene
9,9 '-two (4-aminophenyl) fluorenes 4,4 '-diamino-4 ", 4 -two phenoxy group
Biphenyl
4,4 '-diamino-4 ", 4 -hexichol 4,4 '-diaminostilbene " and, 4 -two phenoxy group benzene
The different propane of oxygen base-phenylbenzene
Preparation process is as follows:
Naphthalene tetracarboxylic dianhydride with bridging; the sulfonated diamine; common diamine; dehydration catalyst and uncle's ammonia join in the phenol solvent of nitrogen protection; be warmed up to 60-80 ℃ of stirring reaction 1-2h earlier; be warmed up to 160-200 ℃ again and continue reaction 4-24h; sink in the ethanol after the cooling; the thorough washing after drying; film is spread in its dissolving then; dry; be immersed in thorough washing in the ethanol again; put it into and soak 8-10h in the hydrochloric acid, tertiary amine is got rid of in neutralization, takes out then to put into deionized water and soaks several repeatedly; remove hydrochloric acid excessive in the film get final product brown xanchromatic polyimide proton transmission film, room-temperature conductivity is at 0.1S.cm
-1-0.3S.cm
-1Between.
2. the synthetic method of a kind of sulfonated polyimide proton transmission film as claimed in claim 1 is characterized in that, described phenol solvent is phenol, cresols, P-Chlorophenol or N-Methyl pyrrolidone.
3. the synthetic method of a kind of sulfonated polyimide proton transmission film as claimed in claim 1 is characterized in that, described dehydration catalyst is phenylformic acid, quinoline or isoquinoline 99.9, and its consumption is 1-1.5 a times of dicarboxylic anhydride.
4. the synthetic method of a kind of sulfonated polyimide proton transmission film as claimed in claim 1 is characterized in that, described tertiary amine is triethylamine, Tributylamine, pyridine or pyrroles, and its consumption is 2-2.2 a times of sulfonated diamine.
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| CN100404588C (en) * | 2005-11-18 | 2008-07-23 | 上海氯碱化工股份有限公司 | Method for preparing cross-linked polyimide membrane |
| CN100389142C (en) * | 2006-04-14 | 2008-05-21 | 中国科学院广州化学研究所 | Polyimide containing side chain of phosphate and its prepn process and film |
| CN100441616C (en) * | 2006-12-08 | 2008-12-10 | 中山大学 | Alcohol-rejecting proton exchange film for alcohol fuel cell and its preparation method |
| CN101139501B (en) * | 2007-10-11 | 2011-05-25 | 同济大学 | Polyimide thermostable aqueous dispersion coating material and preparation method and use thereof |
| CN101225166B (en) * | 2007-12-14 | 2010-12-08 | 哈尔滨工业大学 | Sulfonated naphthalene polyimide containing oxazole ring and preparation of proton exchange membrane thereof |
| CN102195060B (en) * | 2010-03-11 | 2013-06-19 | 王立全 | Method for preparing novel proton exchange membrane fuel cell |
| JP5732292B2 (en) * | 2011-03-28 | 2015-06-10 | 日東電工株式会社 | Sulfonic acid group-containing diamine compound and process for producing the same |
| CN102746511A (en) * | 2011-04-18 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Sulfonated polyimide with hydrolysis resistance, and preparation method and application thereof |
| CN103951824A (en) * | 2014-03-31 | 2014-07-30 | 房倩荷 | Soluble six-membered ring polyimide and preparation method thereof |
| US11898011B2 (en) | 2020-02-19 | 2024-02-13 | Dupont Electronics, Inc. | Polymers for use in electronic devices |
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