CN106750191B - Sulfonated polyether ketone copolymers of the main chain containing pyridine groups, preparation method and application - Google Patents

Sulfonated polyether ketone copolymers of the main chain containing pyridine groups, preparation method and application Download PDF

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CN106750191B
CN106750191B CN201611072673.3A CN201611072673A CN106750191B CN 106750191 B CN106750191 B CN 106750191B CN 201611072673 A CN201611072673 A CN 201611072673A CN 106750191 B CN106750191 B CN 106750191B
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pyridine groups
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pyridines
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李野
芦艾
耿呈祯
余凤湄
张倩
孙素明
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Abstract

The invention discloses a kind of sulfonated poly aryl ether ketone containing pyridine groups and preparation method thereof and its as the application of polymer dielectric film.The sulfonated poly aryl ether ketone that main chain contains pyridine groups is wherein prepared using nucleophilic condensation polymerization for monomer with the pyridines bis-phenol such as 3,5- dihydroxy-pyridines.Since pyridine groups and sulfonic acid group can form ionic bond, poly(aryl ether ketone) film has good dimensional stability, chemical stability, alcohol-rejecting ability in the present invention, has potential application prospect in fuel cell polyelectrolyte film field.

Description

Sulfonated polyether ketone copolymers of the main chain containing pyridine groups, preparation method and application
Technical field
The present invention relates to a kind of high molecular materials and preparation method thereof, and in particular to a kind of sulfonation of the main chain containing pyridine groups Poly(aryl ether ketone) and preparation method thereof, the invention further relates to the applications of sulfonated poly aryl ether ketone of the main chain containing pyridine groups, belong to Technical field of polymer materials.
Background technology
Fuel cell is a kind of device for directly converting the chemical energy of fuel to electric energy, due to high efficiency, low noise, low Pollution elastic can be arranged, and be widely used in military, civilian every field.On electricity generating principle, the matter in fuel cell Proton exchange plays proton conducting, while external closed circuit is transmitted the electronics generated on electrode, to real Energy conversion between the chemical energy and electric energy of existing fuel.As the critical component of battery system, the performance of membrane materials for electrolyte Decide the working efficiency of fuel cell.How to improve the proton conductivity of film, reduce the fuel crossover of film, obtains comprehensive The excellent proton-conductive films of energy are always the research emphasis of scholars.
Sulfonated poly aryl ether ketone is a kind of basis material of potential proton-conductive films, in its structure phenyl ring and ehter bond, carbonyl Base is alternately arranged, and rigid structure and flexible structure reasonable layout, structure have certain regularity, therefore this Type of Collective object has There are good mechanical performance, thermal stability and chemical stability, meanwhile, there is higher conductivity, excellent alcohol-rejecting ability simultaneously And it is cheap, meet requirement in fuel cell.But sulfonated poly aryl ether ketone Type of Collective object is in the higher situation of sulfonation degree Under, the water absorption and swelling of film is larger, and mechanical performance declines, while hindering the reduction of alcohol ability.It is to solve this one kind to prepare soda acid composite membrane One of method of problem, typically based on acidic sulfonated polymer, by small molecule or polymer containing basic group Carry out blending preparation as reinforcing agent, soda acid interact the ionic bond to be formed or hydrogen bond the alcohol-rejecting ability for improving membrane material, Mechanical performance and dimensional stability etc. have good effect.However, when using small molecule as reinforcing agent, for a long time During use, there are small molecule leakages；For macromolecule as modifying agent in application, usually because two kinds of polymer Consistency problem causes to be difficult to prepare uniform membrane material.
Invention content
The pyridine groups that ionic bond can be formed with sulfonic acid group are introduced by the present invention from the angle of molecular structure In main polymer chain, sulfonated polyether ketone copolymers of the main chain containing pyridine groups are prepared for, and provide the type material and exist Application in terms of proton exchange membrane material.
Obtained sulfonated polyether ketone copolymers of the main chain containing pyridine groups of the present invention are by following four structures alone It is connected and composed with singly-bound, as follows：
Wherein AR1For any one in following structural formula：
Wherein AR2For any one in following structural formula：
A kind of system of it is another object of the present invention to provide main chains sulfonated polyether ketone copolymers containing pyridine groups Preparation Method, reaction equation principle are as follows：
It is as follows：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, it is bis- that a mol are added Phenol monomer, b mol dis (4-hydroxyphenyl)(2-pyridyl) methane monomers, 4,4 '-difluoro benzophenones of c mol, 3,3 '-sodium disulfonate -4 d mol, 4 '-difluoros Benzophenone, using 1.05~1.5 (a+b) mol potassium carbonate or sodium carbonate as salt forming agent, with dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or sulfolane are solvent, using toluene or dimethylbenzene as water entrainer, reaction system solid content It is 15%~30%；In 120 DEG C~140 DEG C band water 3~6 hours, then steam water entrainer, then be warming up to 140 DEG C~200 DEG C after Continuous reaction 6~30 hours；It is poured the mixture into after the reaction was complete in distilled water or acetone, obtains yellowish color strip-shaped solid, crushed It is washed 3~5 times, then is washed with distilled water 3~5 times with acetone at after fine powder；Finally dried to get to master at 60 DEG C~80 DEG C Chain sulfonated poly aryl ether ketone containing pyridine groups.
In above-mentioned steps, a+b=c+d；By controlling the ratio of a and b, containing for pyridine groups in polymer can be adjusted Amount, and a > 0, b > 0；By controlling the ratio of c and d, the sulfonation degree of polymer, and 0,2 > 2d/ (c of c > 0, d > can be adjusted + d) > 0, sulfonation degree is 2d/ (c+d).
Wherein, selected dis (4-hydroxyphenyl)(2-pyridyl) methane monomer is 2,3- dihydroxy-pyridines, 2,4- dihydroxy-pyridines, 2,5- dihydroxy pyrroles Pyridine, 2,6- dihydroxy-pyridines, 3,4- dihydroxy-pyridines, one kind in 3,5- dihydroxy-pyridines, structure are as follows：
Selected biphenol monomer is tetramethyl biphenyl diphenol, hydroquinone, '-biphenyl diphenol, hexafluoro bisphenol-a, bisphenol-A, benzene One in base hydroquinone, trifluoromethyl hydroquinone, 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxy benaophenonels Kind, structure is as follows：
The application of the invention further relates to main chains sulfonated polyether ketone copolymers containing pyridine groups, particular as poly- Polymer electrolyte membrane material is applied in fuel cell.
The main chain membrane material of sulfonated poly aryl ether ketone containing pyridine groups prepared by the present invention has preferable dimensional stability, relatively low Methanol permeability and higher antioxidative stabilizer and good proton conductivity, therefore with traditional aromatic series polyelectrolyte Film is compared, and is a kind of novel polymer dielectric film material haveing excellent performance, being capable of dielectric film field in a fuel cell It has a good application prospect.
Specific implementation mode
Embodiment 1：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.08mol Bisphenol-A, 0.02mol 2,3- dihydroxy-pyridines, 4,4 '-difluoro benzophenones of 0.05mol, 3,3 '-sodium disulfonate -4 0.05mol, 4 '-difluoro benzophenones, using 1.05mol potassium carbonate as salt forming agent, using dimethylformamide as solvent, using toluene as water entrainer； 120 DEG C of band water 3 hours, then steam water entrainer, then are warming up to 140 DEG C the reaction was continued 20 hours；By mixture after the reaction was complete It pours into distilled water, obtains yellowish color strip-shaped solid, washed 3 times with acetone after being ground into fine powder, then be washed with distilled water 3 times； Finally dried to get the ketone copolymers of sulfonated polyether containing pyridine groups for being 1.0 to sulfonation degree at 60 DEG C.
Embodiment 2：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.07mol Hexafluoro bisphenol-a, 0.03mol 2,4- dihydroxy-pyridines, 4,4 '-difluoro benzophenones of 0.06mol, 3,3 '-disulfonic acid of 0.04mol 4,4 '-difluoro benzophenone of sodium-, using dimethylacetylamide as solvent, is band water with dimethylbenzene using 1.1mol sodium carbonates as salt forming agent Agent；In 120 DEG C of band water 4 hours, water entrainer is then steamed, then is warming up to 150 DEG C the reaction was continued 16 hours；It will be mixed after the reaction was complete It closes object to pour into acetone, obtains yellowish color strip-shaped solid, washed 5 times with acetone after being ground into fine powder, then be washed with distilled water 5 It is secondary；Finally dried to get the ketone copolymers of sulfonated polyether containing pyridine groups for being 0.8 to sulfonation degree at 80 DEG C.
Embodiment 3：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.09mol Hydroquinone, 0.01mol 2,5- dihydroxy-pyridines, 4,4 '-difluoro benzophenones of 0.04mol, 3,3 '-disulfonic acid of 0.06mol 4,4 '-difluoro benzophenone of sodium-, using N-Methyl pyrrolidone as solvent, is band water with toluene using 1.2mol potassium carbonate as salt forming agent Agent；In 130 DEG C of band water 5 hours, water entrainer is then steamed, then is warming up to 170 DEG C the reaction was continued 14 hours；It will be mixed after the reaction was complete It closes object to pour into distilled water, obtains yellowish color strip-shaped solid, washed 4 times with acetone after being ground into fine powder, then be washed with distilled water 4 It is secondary；Finally dried to get the ketone copolymers of sulfonated polyether containing pyridine groups for being 1.2 to sulfonation degree at 70 DEG C.
Embodiment 4：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.06mol Trifluoromethyl hydroquinone, 0.04mol 2,6- dihydroxy-pyridines, 4,4 '-difluoro benzophenones of 0.03mol, 0.07mol 3,3 '-sodium disulfonate -4,4 '-difluoro benzophenones, using 1.3mol sodium carbonates as salt forming agent, using dimethyl sulfoxide (DMSO) as solvent, with two Toluene is water entrainer；In 120 DEG C of band water 3 hours, water entrainer is then steamed, then is warming up to 170 DEG C the reaction was continued 30 hours；Reaction Completely after pour the mixture into acetone, obtain yellowish color strip-shaped solid, wash 3 times with acetone after being ground into fine powder, then with steaming Distilled water is washed 3 times；Finally dried to get the ketone copolymers of sulfonated polyether containing pyridine groups for being 1.4 to sulfonation degree at 60 DEG C.
Embodiment 5：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.05mol '-biphenyl diphenol, 0.05mol 3,4- dihydroxy-pyridines, 4,4 '-difluoro benzophenones of 0.07mol, 3,3 '-disulfonic acid of 0.03mol 4,4 '-difluoro benzophenone of sodium-, using 1.4mol potassium carbonate as salt forming agent, using sulfolane as solvent, using toluene as water entrainer；140 DEG C band water 6 hours, then steams water entrainer, then is warming up to 200 DEG C the reaction was continued 6 hours；It is poured the mixture into after the reaction was complete In distilled water, yellowish color strip-shaped solid is obtained, is washed 5 times with acetone after being ground into fine powder, then be washed with distilled water 5 times；Finally It is dried to get the ketone copolymers of sulfonated polyether containing pyridine groups for being 0.6 to sulfonation degree at 80 DEG C.
Embodiment 6：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.04mol Phenyl hydroquinone, 0.06mol 3,5- dihydroxy-pyridines, 4,4 '-difluoro benzophenones of 0.08mol, 3,3 '-two sulphurs of 0.02mol 4,4 '-difluoro benzophenone of sour sodium-, using 1.5mol sodium carbonates as salt forming agent, using dimethylformamide as solvent, using dimethylbenzene as band Aqua；In 120 DEG C of band water 6 hours, water entrainer is then steamed, then is warming up to 150 DEG C the reaction was continued 10 hours；It will after the reaction was complete Mixture pours into acetone, obtains yellowish color strip-shaped solid, is washed 4 times with acetone after being ground into fine powder, then be washed with distilled water 4 It is secondary；Finally dried to get the ketone copolymers of sulfonated polyether containing pyridine groups for being 0.4 to sulfonation degree at 70 DEG C.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that people in the art Member can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen in principle disclosed in the present application Within scope and spirit.

Claims (5)

1. a kind of sulfonated polyether ketone copolymers of main chain containing pyridine groups, it is characterised in that：It is by following four structures alone It is connected and composed with singly-bound,
Wherein AR1For any one in following structural formula：
Wherein AR2For any one in following structural formula：
2. the preparation method of sulfonated polyether ketone copolymers of the main chain described in claim 1 containing pyridine groups, it is characterised in that packet Include following steps：
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added a mol bis-phenol lists Body, b mol dis (4-hydroxyphenyl)(2-pyridyl) methane monomers, 4,4 '-difluoro benzophenones of c mol, 3,3 '-sodium disulfonate -4 d mol, 4 '-difluorodiphenyls Ketone, using (1.05~1.5) (a+b) mol potassium carbonate or sodium carbonate as salt forming agent, with dimethylformamide, dimethylacetylamide, N- Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or sulfolane are solvent, and using toluene or dimethylbenzene as water entrainer, reaction system solid content is 15%~30%；In 120 DEG C~140 DEG C band water 3~6 hours, water entrainer is then steamed, then be warming up to 140 DEG C~200 DEG C continuation Reaction 6~30 hours；It is poured the mixture into after the reaction was complete in distilled water or acetone, obtains yellowish color strip-shaped solid, be ground into It is washed 3~5 times, then is washed with distilled water 3~5 times with acetone after fine powder；Finally dried to get to main chain at 60 DEG C~80 DEG C Sulfonated poly aryl ether ketone containing pyridine groups；
Wherein, a+b=c+d；By controlling the ratio of a and b, the content of pyridine groups in polymer, and a > 0, b > 0 are adjusted； By controlling the ratio of c and d, the sulfonation degree of polymer, and c > 0, d > 0,2 > 2d/ (c+d) > 0, sulfonation degree 2d/ are adjusted (c+d)。
3. the preparation method of sulfonated polyether ketone copolymers of the main chain as claimed in claim 2 containing pyridine groups, feature exist In：Selected dis (4-hydroxyphenyl)(2-pyridyl) methane monomer be 2,3- dihydroxy-pyridines, 2,4- dihydroxy-pyridines, 2,5- dihydroxy-pyridines, 2,6- bis- Pyridone, 3,4- dihydroxy-pyridines, one kind in 3,5- dihydroxy-pyridines, structure are as follows：
4. the preparation method of sulfonated polyether ketone copolymers of the main chain as claimed in claim 2 containing pyridine groups, feature exist In：Selected biphenol monomer is tetramethyl biphenyl diphenol, hydroquinone, '-biphenyl diphenol, hexafluoro bisphenol-a, bisphenol-A, phenyl pair One kind in benzenediol, trifluoromethyl hydroquinone, 4,4 '-dihydroxydiphenylsulisomers, 4,4'-Dihydroxybenzophenone, knot Structure is as follows：
5. main chain sulfonated polyether containing pyridine groups ketone copolymers described in claim 1 are answered as polymer dielectric film material For in fuel cell.
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CN101735591A (en) * 2009-11-20 2010-06-16 清华大学 Organic-inorganic hybrid cross-linked sulfonated polyaryletherketone polymer electrolyte material and preparation method thereof
CN101875722A (en) * 2009-11-27 2010-11-03 清华大学 Method for preparing polybenzimidazole/sulfonated polymer composite proton exchange membrane material
CN104098750A (en) * 2013-04-10 2014-10-15 中国科学院宁波材料技术与工程研究所 Aromatic polymer anion exchange resin with side chain containing sulfonamide quaternary ammonium salt, and preparation method and application thereof

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CN101735591A (en) * 2009-11-20 2010-06-16 清华大学 Organic-inorganic hybrid cross-linked sulfonated polyaryletherketone polymer electrolyte material and preparation method thereof
CN101875722A (en) * 2009-11-27 2010-11-03 清华大学 Method for preparing polybenzimidazole/sulfonated polymer composite proton exchange membrane material
CN104098750A (en) * 2013-04-10 2014-10-15 中国科学院宁波材料技术与工程研究所 Aromatic polymer anion exchange resin with side chain containing sulfonamide quaternary ammonium salt, and preparation method and application thereof

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