CN102643426A - Preparation method of novel polybenzimidazole resin - Google Patents
Preparation method of novel polybenzimidazole resin Download PDFInfo
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Abstract
The invention discloses novel polybenzimidazole resin and a preparation method of the novel polybenzimidazole resin. The preparation method of the novel polybenzimidazole resin comprises utilizing tetramines aromatic and binary aromatic carboxylic acid containing imidazole rings as raw materials, utilizing 2,4,6-pyridine tricarboxylic acid as a cross-linking agent and a reactant simultaneously, utilizing polyphosphoric acid as a reaction medium, and performing reaction at the temperature of 150+/-5 DEG C for 8-10 hours and at the temperature of 200+/-5 DEG C for 9-13 hours under nitrogen protection conditions to obtain polybenzimidazole with a carboxyl group or an amino group as an end group. The polybenzimidazole has high molecular weight, good chemical stability and heat-resisting performance, good solubility property in sulfuric acid and phosphoric acid and certain solubility property in dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide. The polybenzimidazole can serve as proton exchange membrane materials, adhesive materials, fiber materials and the like, and has wide application prospects.
Description
Technical field
The present invention relates to a kind of new functional macromolecule material and preparing method's research, particularly a kind of novel polyphenyl and imidazoles polymkeric substance and preparation method.
Background technology
Along with making rapid progress of science and technology, people are to raising and the development of aviation and aerospace technology and the progress of environmental quality requirement, development of new environmental protection and to have a polymer materials of resistance toheat extremely urgent.
Polybenzimidazole (PBI) polymkeric substance is meant the single order trapezoidal-structure polymkeric substance that contains imidazole ring in the backbone structure; Advantageous property such as it is high temperature resistant because of having, fire-retardant, radiation hardness and insulativity, chemical, binding property and physical strength are good often is used as mould material, electro-conductive material and fire retardant material etc.As far back as late 1950s, BrinkerK.C. etc. with diprotic acid and tetramine prepared in reaction the polybenzimidazole of first kind of fatty chain (Brinker K.C., Robinson I.M.USP, 2895948,1959).The sixties in 20th century, Vogel H. etc. synthesize the aromatic series polybenzimidazole (Vogel H., Marvel C.S.Journal of Polymer Science, 1961,50:511), from then on started the research and development beginning of PBI base polymer.
PBI has excellent comprehensive performances, and it has very high second-order transition temperature, generally more than 450 ℃.Make it important application arranged aspect high temperature resistant in that high temperature resistant filtration fabrics, protection clothes, suit, aircraft interior trim and other are many.The anti-combustion characteristic of PBI is outstanding, can be used for making manufacturing working suit such as bunker clothing, protective clothing, flying suit, racing car clothes, life-saving suit and iron and steel, glass etc.The good hygroscopicity of PBI, comfortable and easy to wear with the protective clothing that it is processed.PBI does not burn under hot environment, and is nontoxic smokeless, can be used for the interior material of aircraft, submarine and train etc., like ornamental, curtain, carpet, seat step, drop cloth and various ribbons etc.In industry, utilize the characteristics such as heat-resisting anti-combustion, chemical-resistant reagent of PBI fiber, filter cloth of processing or fabric can be used for the transmission of Industrial products filtration, waste water and the filtration of mud class, silt capture, stack gas and air filtration, high temperature or corrodibility material etc.In addition; With PBI as body material; Use strongthener such as spun glass, thomel, aramid fiber Kevlar fiber that it is strengthened; Process high performance matrix material and can be used for ablation resistant material and heat shield structure material; As be used for the control awl bar of fire-resistant cone, the guided missile leading edge of the radome of aircraft and spacecraft, make a return voyage device front shroud, wing and PC board, manufacturing rocket assist agent nozzle, the thermal insulation material of rocket firing system etc., also be simultaneously guided missile, the space shuttle case frame material of substituting preferably.Late 1990s, people were to the raising of environmental requirement along with the rise of fuel cell studies, and the research and development of non-fluorine aromatics PEM have caused investigators' great interest.Though PBI film itself only has weak electroconductibility (10
-7-10
-8S/cm); Therefore can not directly apply to fuel cell; But because PBI particular chemical structure; The specific alkaline structure that it has can be under high temperature or anhydrous condition behind an amount of mineral acid that mixed proton conducting, be applicable to the PEM of high temperature proton exchange film fuel cell, remedy the sixties in 20th century to a great extent
Therefore the defective of series perfluoro sulfonic acid membrane has received widely and having paid close attention to.Usefulness aromatic series quaternary amine such as Yu Xinhai and aromatic binary carboxylic acid 1: 1 in molar ratio preparation under polyphosphoric acid/Vanadium Pentoxide in FLAKES system effect has the good PBI polymkeric substance of molecular weight height, Heat stability is good, solvability and film forming properties; This preparation technology is simple, cost is low, easy to operate, can in general-purpose equipment, accomplish preparation process (Yu Xinhai, Xu Jun; Xu Yongfen; Chinese patent, 200810207616.0,2008); Fang Liang etc. are with 3, and 3 ', 4; 4 '-tetramino biphenyl and m-phthalic acid are that monomer prepares the polybenzimidazole sticker that molecular weight is 5000-16000 through polycondensation, and this sticker is used for fuel cell membrane electrode, can be used for hydrogen-oxygen, hydrogen-air fuel cell (Fang Liang being higher than under 100 ℃ of no humidification conditions; Fang Jianhua, Ma Zifeng etc., Chinese patent; 201110041193.1,2011); Han Kefei etc. (Han Kefei, Liang Jiapeng, Wang Zhongming etc., Chinese patent, 201110121715.9,2011) have prepared a series of polybenzimidazole resins that contain flexible group (ehter bond), and have good solubility, and the potential using value is arranged aspect fuel cell.
Summary of the invention
The present invention is from the Molecular Structure Design angle, and adopt synthetic fragrance quaternary amine monomer and the di-carboxylic acid monomer that contains the benzoglyoxaline ring, contain the tribasic carboxylic acid monomer of pyridine ring, the novel polyphenyl and the imidazoles of synthetic excellent performance, their repeated structural unit is following:
The quaternary amine monomer structure that arrives involved in the present invention is following:
Wherein, R
1Be generically and collectively referred to as Ar
1, its concrete structure formula is following:
A1 is wherein arranged) 3,3 ', 4,4 '-tetramino thionyl benzene, b1) 2; 2-two [3, the 4-diamino-phenyl] HFC-236fa, c1) 4,4 '-two [3,4-diaminobenzene sulfenyl] ditane, d1) 4; 4 '-two [3, the 4-diamino phenoxy] ditane, e1) 4,4 '-two [3, the 4-diamino phenoxy] diphenyl sulfide, f1) 2; 2-two [4-(3, the 4-diamino phenoxy) phenyl] HFC-236fa, g1) 2, [4-(3 for 2-two; 4-diaminobenzene sulfenyl) phenyl] HFC-236fa, h1) 2,2-two [4-(3,4-diaminobenzene sulfenyl) phenyl] propane
The dicarboxylic acid monomer's that the present invention is used structure is following:
HOOC——R
2——COOH
Wherein, R
2Be generically and collectively referred to as Ar
2, its concrete structure formula is following:
A2 is wherein arranged) 1, two (5-carboxylic acid-2-benzoglyoxaline) benzene of 3-, b2) 2, two (5-carboxylic acid-2-benzoglyoxaline) pyridines of 6-, c2) 3; Two (5-carboxylic acid-2-benzimidazolyl-) pyridines of 5-, d2) 5-sodium sulfonate-1, two (5-carboxylic acid-2-benzimidazolyl-) benzene of 3-, e2) 4,4 '-two (5-carboxylic acid-2-benzimidazolyl-) ditane, f2) 4; 4 '-two (5-carboxylic acid-2-benzimidazolyl-) benzophenone, g2) 4; 4 '-two (5-carboxylic acid-2-benzimidazolyl-) thionyl benzene, h2) 4,4 '-two (5-carboxylic acid-2-benzimidazolyl-) sulfobenzide, i2) N-3,5-two (5-carboxylic acid-2-benzimidazolyl-) phenyl] phthalic imidine, j2) 2; 2-[4; 4 '-two (5-carboxylic acid-2-benzimidazolyl-) phenyl] propane, k2) 2,2-[4,4 '-two (5-carboxylic acid-2-benzimidazolyl-) phenyl] HFC-236fa
The structure of the tricarboxylic acid linking agent that the present invention is used is following:
Wherein, R
3Be generically and collectively referred to as Ar
3, its concrete structure formula is following:
A3 is wherein arranged) 2,4,6-pyridine tricarboxylic acid, b3) 4,4, ' 4, "-[1,3, the 5-benzoglyoxaline] three phenylformic acid, c3) 4,4, ' 4; "-[1,3, the 5-benzoglyoxaline] pyridine tricarboxylic acid, d3) 4,4, ' 4, "-[1,3,5-benzene three sulfuryls] three phenylformic acid, e3) 4,4, ' 4; "-[1,3,5-benzene three oxygen bases] pyridine tricarboxylic acid, f3) 4,4, ' 4, "-[1,3,5-benzene three sulfenyls] pyridine tricarboxylic acid, g3) 4,4, ' 4; "-[1,3, the 5-phenmethyl] pyridine tricarboxylic acid h3) 4,4, ' 4, "-[1,3, the 5-phenylcarbamoyl] pyridine tricarboxylic acid, i3) 4,4; ' 4, "-[1,3,5-benzene three sulfoxide groups] pyridine tricarboxylic acid, j3) 4,4, ' 4, "-[1,3,5-benzene three sulfuryls] pyridine tricarboxylic acid
Following typical compound method is adopted in the preparation of polybenzimidazole among the present invention:
(1) programmed temperature method
At first; With rare gas element such as nitrogen or argon gas at room temperature to taking a breath in the reactor drum; Then fragrant quaternary amine or its hydrochloride monomer are added in the polyphosphoric acid with the di-carboxylic acid that contains the benzene imidazole ring, the binary acyl chlorides and tribasic carboxylic acid, tribasic carboxylic acid ester or the ternary acyl chlorides that contain the dicarboxylic esters of pyridine ring or contain the benzene imidazole ring; In nitrogen protection; Stir under the room temperature condition, above-mentioned fragrant quaternary amine or the monomeric mole number of its hydrochloride and contain the di-carboxylic acid of benzene imidazole ring, the dicarboxylic esters that contains the benzene imidazole ring or binary acyl chlorides and the ratio of tribasic carboxylic acid, the tribasic carboxylic acid ester that contains pyridine ring or ternary acyl chlorides mole number sum between 1-1.5.
Secondly, adopt programmed temperature method, under 150 ± 5 ℃ of temperature, react 8h, under 200 ± 5 ℃ of temperature, react 12h.
At last, after polyreaction finishes, pour in the deionized water after reaction mass is cooled to room temperature, to be settled out solid, then with dipping by lye to remove the solvent of remnants, be washed till neutrality with deionized water, 100 ℃ of vacuum-drying get final product polybenzimidazole resin.
(2) microwave irradiation
Present method and programmed temperature method difference were for second step, because the synthetic of PBI mainly carries out cyclization in polyphosphoric acid (PPA), this type reaction typical temperature height and time are long.Adopt synthetic this compounds of microwave irradiation, the reaction times obviously shortens, and operates easier.Adopt microwave irradiation generally to react 6-8h down and can make polybenzimidazole resin at 120 ± 5 ℃.
The polyreaction equation of novel polyphenyl of the present invention and imidazoles is following:
Resulting novel polyphenyl of the present invention and imidazoles polymkeric substance not only have solvability preferably in strongly-acid solvent such as sulfuric acid, phosphoric acid, methylsulfonic acid etc.; And at strong polar aprotic solvent such as N; Dinethylformamide, N; Have good solubility property in the single or mixed solvent such as N-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN., overcome and be only soluble in the defective in the strongly-acid protonic solvent in the past.
The resulting polymkeric substance of the present invention can be used as filamentary material, ion exchange membrane material, adhesive material etc., has broad application prospects.
Concrete embodiment
Following embodiment further specifies of the present invention, rather than limits scope of the present invention.
The preparation of the netted polybenzimidazole that embodiment 1 is uncrosslinked
(1) programmed temperature method
Checking resistance to air loss after connecting device, open nitrogen valve, open simultaneously and stir, is the fully emptying of air quilt in the reaction flask; After ventilation finishes, with 4,4 '-two [3, the 4-diamino phenoxy] diphenyl sulfide, 2; 4, the 6-pyridine tricarboxylic acid joins in the four-hole boiling flask with 3: 2 ratio of mol ratio; Add polyphosphoric acid (PPA) as solvent and water-retaining agent, in mechanical stirring, N
2Open heating unit after stirring 30min under the condition of protection, system is warming up in 150 ± 5 ℃ of scopes gradually, reaction 8h rises to 200 ± 5 ℃ with temperature; 12h is in reaction process in reaction, and along with the rising of temperature, system viscosity increases gradually, and the system color is by the brick-red black that becomes; Reaction is poured system in the deionized water into after finishing, and separates out solid; Filter, with solid with the sodium hydrogen carbonate solution washing to neutral, dry, the red-purple solid.
(2) microwave irradiation
Present method and programmed temperature method difference are reaction system under microwave radiation, and 120 ± 5 ℃ of scope internal reaction 8h can make uncrosslinked netted polybenzimidazole polymer.
Embodiment 2m: n=9: 1 type contains the preparation of benzimidazole structure polybenzimidazole
(1) programmed temperature method
Checking resistance to air loss after connecting device, open nitrogen valve, open simultaneously and stir, is the fully emptying of air quilt in the reaction flask; After ventilation finishes, with 4,4 '-two [3, the 4-diamino phenoxy] diphenyl sulfide, 1; Two (5-carboxylic acid-2-benzoglyoxaline) benzene, 2,4 of 3-, the 6-pyridine tricarboxylic acid joins in the four-hole boiling flask with the ratio of amount of substance than 1.05: 0.9: 0.1; Add PPA as solvent and water-retaining agent, in mechanical stirring, N
2Open heating unit after stirring 30min under the condition of protection, system is warming up in 150 ± 5 ℃ of scopes gradually, reaction 8h is increased to system temperature in 200 ± 5 ℃ of scopes; Reaction 12h, in reaction process, along with the rising of temperature, system viscosity increases gradually; The system color is by the brick-red light brown that becomes, and reaction is poured system in the deionized water into after finishing; Separate out solid, filter, with solid in sodium hydrogen carbonate solution soaked overnight to remove unnecessary acid; Filter, washing is to neutral, dry, the red-brown solid.
(2) microwave irradiation
Present method and programmed temperature method difference are reaction system under microwave radiation, 110 ± 5 ℃ of scope internal reaction 6h, and can make m: n=9: 1 type contains the benzimidazole structure polybenzimidazole.
Embodiment 3m: n=1: 1 type contains the preparation of benzimidazole structure polybenzimidazole
(1) programmed temperature method
Check resistance to air loss after connecting device, open nitrogen valve, open simultaneously and stir, make the fully emptying of air quilt in the reaction flask; After ventilation finishes, with 4,4 '-two [3, the 4-diamino phenoxy] diphenyl sulfide, 1; Two (5-carboxylic acid-2-benzoglyoxaline) benzene, 2,4 of 3-, the 6-pyridine tricarboxylic acid joins in the four-hole boiling flask than 2.5: 1: 1 with amount of substance; Add PPA as solvent and water-retaining agent, in mechanical stirring, N
2Open heating unit after stirring 30min under the condition of protection, system is warming up in 150 ± 5 ℃ of scopes gradually, reaction 8h is increased to system temperature in 200 ± 5 ℃ of scopes; Reaction 12h, in reaction process, along with the rising of temperature, system viscosity increases gradually; The system color is by the orange red dark-brown that becomes, and reaction is poured system in the deionized water into after finishing; Separate out solid, filter, with solid in sodium hydrogen carbonate solution soaked overnight to remove unnecessary acid; Filter, washing is to neutral, dry, the dark brown red solid.
(2) microwave irradiation
Present method and programmed temperature method difference are reaction system under microwave radiation, 110 ± 5 ℃ of scope internal reaction 7h, and can make m: n=1: 1 type contains the benzimidazole structure polybenzimidazole.
The preparation of the line style polybenzimidazole that contains benzoglyoxaline that embodiment 4 is uncrosslinked
(1) programmed temperature method
Check resistance to air loss after connecting device, open nitrogen valve, open simultaneously and stir, make the fully emptying of air quilt in the reaction flask; After ventilation finishes, with 4,4 '-two [3, the 4-diamino phenoxy] diphenyl sulfide, 1; Two (5-carboxylic acid-2-benzoglyoxaline) benzene of 3-are that 1: 1 ratio joins in the four-hole boiling flask with the amount of substance ratio, add PPA as solvent and water-retaining agent, in mechanical stirring; Open heating unit after stirring 30min under the condition of N2 protection, system is heated up gradually, system is warming up in 150 ± 5 ℃ of scopes gradually; Reaction 8h is increased to system temperature in 200 ± 5 ℃ of scopes, reaction 12h; Along with the rising of temperature, system viscosity increases gradually, and the system color changes into blackish green gradually.After reaction finished, cooling added deionized water in system, and system presents grass green, separates out solid, filtered, and solid soaked overnight in sodium hydrogen carbonate solution is filtered to remove unnecessary acid, and washing is to neutral, dry, the deep green solid.
(2) microwave irradiation
Present method and programmed temperature method difference are reaction system under microwave radiation, and 100 ± 5 ℃ of scope internal reaction 8h can make the uncrosslinked line style polybenzimidazole that contains benzoglyoxaline.
Claims (7)
1. the preparation method of novel polyphenyl and imidazoles polymkeric substance is characterized in that adopting solution polycondensation, is solvent with the polyphosphoric acid, is tetramine monomers with the tetramines aromatic; To contain the heterocyclic dicarboxylicacid is diprotic acid, be linking agent and serve as reactant with equal tricarboxylic acid, and under the nitrogen atmosphere, mechanical stirring; Reacting by heating number hour obtains thick polymers soln, is cooled to room temperature, and it is poured in the deionized water; Separate out solid, filter, washing, alkali cleaning; Washing to filtrating is neutral, and vacuum-drying obtains the polymer solids powder.
2. according to the preparation method of the polybenzimidazole described in the claim 1, it is characterized in that the heating means that adopted are programmed temperature method, i.e. room temperature reaction 30min, 150 ± 5 ℃ of scope internal reaction 8h, 200 ± 5 ℃ of scope internal reaction 12h.
3. according to the preparation method of the polybenzimidazole described in the claim 1, it is characterized in that the heating means that adopted are microwave irradiation, i.e. 120 ± 5 ℃ of scope internal reaction 8h.This method not only can shorten polymerization reaction time, and can make polymers of excellent properties.
4. according to the preparation method of the polybenzimidazole described in the claim 1, it is characterized in that the tetramine that is adopted is the tetramines aromatic that contains flexible group, is designated as R
1, its particular chemical formula is following:
5. according to the preparation method of the polybenzimidazole described in the claim 1, it is characterized in that the diprotic acid that is adopted is the dicarboxylicacid that contains the benzoglyoxaline ring, is designated as R
2, its particular chemical formula is following:
6. according to the preparation method of the polybenzimidazole described in the claim 1, it is characterized in that the tricarboxylic acid linking agent that is adopted is the equal tricarboxylic acid that contains pyridine ring or contain the benzoglyoxaline ring, is designated as R
3, its particular chemical formula is following:
7. according to the preparation method of the polybenzimidazole described in the claim 1, it is characterized in that the polymkeric substance that makes has following repeated structural unit:
In the above-mentioned repeated structural unit, imino-is a cis or trans.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755650A (en) * | 2013-10-24 | 2014-04-30 | 上海大学 | Triazole functionalized 4,4'-difluorophenyl sulfone compound and synthetic method thereof |
| CN103965474A (en) * | 2014-05-22 | 2014-08-06 | 胡国良 | Preparation method of sulfonated polymer for fuel batteries |
| CN104852060A (en) * | 2015-04-08 | 2015-08-19 | 北京化工大学 | Preparation method of non-platinum fuel-cell catalyst taking polybenzimidazole as nitrogen source |
| CN109251316A (en) * | 2018-08-15 | 2019-01-22 | 江苏常源新材料科技有限公司 | A kind of synthesis preparation method of polybenzimidazole resin |
| CN110066389A (en) * | 2019-03-15 | 2019-07-30 | 四川大学 | The ion monomer of the sulfonate structures containing benzheterocycle, ionomer and their preparation method and application with its flame-retardant and anti-dripping |
| CN110330511A (en) * | 2018-12-31 | 2019-10-15 | 湖北大学 | A kind of synthetic method and biological detection application of glyoxaline ligand |
| CN112820892A (en) * | 2019-11-18 | 2021-05-18 | 坤艾新材料科技(上海)有限公司 | Gas diffusion electrode and battery comprising same |
| CN114437351A (en) * | 2022-01-11 | 2022-05-06 | 深圳大学 | Preparation method and application of high-temperature fuel cell binder |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755650A (en) * | 2013-10-24 | 2014-04-30 | 上海大学 | Triazole functionalized 4,4'-difluorophenyl sulfone compound and synthetic method thereof |
| CN103755650B (en) * | 2013-10-24 | 2016-03-30 | 上海大学 | Triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof |
| CN103965474A (en) * | 2014-05-22 | 2014-08-06 | 胡国良 | Preparation method of sulfonated polymer for fuel batteries |
| CN104852060A (en) * | 2015-04-08 | 2015-08-19 | 北京化工大学 | Preparation method of non-platinum fuel-cell catalyst taking polybenzimidazole as nitrogen source |
| CN109251316A (en) * | 2018-08-15 | 2019-01-22 | 江苏常源新材料科技有限公司 | A kind of synthesis preparation method of polybenzimidazole resin |
| CN109251316B (en) * | 2018-08-15 | 2021-06-01 | 江苏常源新材料科技有限公司 | Synthetic preparation method of polybenzimidazole resin |
| CN110330511A (en) * | 2018-12-31 | 2019-10-15 | 湖北大学 | A kind of synthetic method and biological detection application of glyoxaline ligand |
| CN110066389A (en) * | 2019-03-15 | 2019-07-30 | 四川大学 | The ion monomer of the sulfonate structures containing benzheterocycle, ionomer and their preparation method and application with its flame-retardant and anti-dripping |
| CN112820892A (en) * | 2019-11-18 | 2021-05-18 | 坤艾新材料科技(上海)有限公司 | Gas diffusion electrode and battery comprising same |
| CN114437351A (en) * | 2022-01-11 | 2022-05-06 | 深圳大学 | Preparation method and application of high-temperature fuel cell binder |
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Application publication date: 20120822 |