Background technology
The polymkeric substance that contains the sulfonic group structure is as polymer dielectric, owing to it has unique proton conductivity and other high-performance is applied to fuel cell [L.Carrette, K.A.Friedrich, U.Stimming. fuel cell (Fuel Cells), calendar year 2001, the 1st phase, page 5] in.Present business-like proton transmission film has the nafion film of E.I.Du Pont Company and the Dow film of DOW company etc., but because the cost of these several films is expensive and high-temperature behavior instability [Q.F.Li, R.He, J.O.Jensen, N.J.Bjerrum.Chemical material (Chemistry Material),, the 15th phase, the 4896th page in 2003], promoted the broad research of other types proton transfer film materials.The sulfonated aromatic polymer is as SPSF [P.G.Dinitrova, B.Baradie, D.Foscallo, C.Poinsignon, J.Y.Sanchez.Membrane science magazine (Journal ofMembrane Science), 2001, the 185 phases, the 594th page], sulfonated poly (phenylene oxide) [K.Miyatake, Y.Chikashige, M.Watanabe.Macromole (Macromolecules), 2003, the 36th phase, the 9691st page], sulfonated polyether-ether-ketone [K.D.Kreuer, membrane science magazine (Journal of Membrane Science), calendar year 2001, the 185th phase, the 29th page] etc. be relatively more active several proton transmission films of research.But the sulfonation degree of the proton transmission film of this several types be difficult for to be determined, the bad mechanical strength of film, and protonated degree is low etc., and reason has limited their use.
Two kinds of methods of synthetic main employing of present proton transmission film: a kind of is directly polymkeric substance to be carried out sulfonation [K.Miyatake, Y.Chikashige, M.Watanabe with chlorsulfonic acid or oleum.Macromole (Macromolecules), 2003, the 36th phase, the 9691st page].The shortcoming of this method is that the position of sulfonation degree and sulfonation point is wayward, and the poor repeatability of film properties can cause the degraded of polymkeric substance in the sulfonation process, causes physical strength to reduce.Another kind method is by condensation reaction condense together [F.Wang, M.Hickner, Y.S.Kim, T.A.Zawodzinski, J.E.McGrath with the comonomer of sulfonation and unsulfonated.Membrane science magazine (Journal of Membrane Science), 2002, the 197th phase, the 2318th page].The proton transmission film of this method preparation, sulfonic group directly is connected on the main chain, and the close electric structure on the phenyl ring reduces sulfonic protonated degree, causes proton conductivity low.And when film absorbs water, can lose due physical strength because degree of swelling is too big.
The proton transfer film material of biphenyl type, because of it has scale resistance, hydrolytic resistance and high thermal resistance and cause investigator's attention [H.Ghassmi, J.E.Mcgrath.Polymkeric substance (Polymer),, the 45th phase, the 5847th page in 2004], but the preparation of the biphenyl type proton transfer film material in the document is to adopt oleum directly polymkeric substance to be carried out sulfonation, and sulfonation post polymerization thing can not film forming, can't be applied in the fuel cell.
Summary of the invention
One of purpose of the present invention provides a kind of sulfonated polyphenyl type proton transfer film material;
Its structural formula is:
(1) wherein R is a kind of group, and its structural formula can be any one in the following array structure:
(2) x can get arbitrary value, and y is not equal to 0 arbitrary value.
Another object of the present invention provides a kind of synthetic method of sulfonated polyphenyl type proton transfer film material.
The present invention adopts Ni (0) catalyzed coupling reaction with 4 '-sodium sulfonate-2 first, two chloro monomers of 5-dichloro benzophenone and other structures carry out copolymerization, by regulating the proton transfer film material that two kinds of monomeric feed ratio (two kinds of monomeric feed ratio can be any mol ratio) obtain any sulfonation degree.This method reaction conditions gentleness, the reaction times is short, and sulfonation degree is easily controlled, the good film-forming property of polymkeric substance, and sulfonic group is positioned at the side chain of polymkeric substance, strengthened the anti-hydrolysis ability of polymkeric substance, improved the physical strength of film, and the tensile strength of film reaches more than the 1MPa.
The present invention adopts following component to synthesize sulfonated polyphenyl type proton transfer film material:
(1) monomer
(a) monomer 1 is to have in two chlorinated aromatic compounds of following structure any one:
(b) monomer 2 is the two chloro benzophenone sodium sulfonates with following structure:
(2) monomer 1 is an arbitrary value with the molar ratio of monomer 2, but the mole number of monomer 2 can not equal 0;
(3) reductive agent: zinc powder, reductive agent is 2: 1~10: 1 with the ratio of monomeric total mole number;
(4) catalyzer: nickelous bromide or nickelous chloride, catalyzer is 1: 2~1: 20 with the ratio of monomeric total mole number;
(5) coordination agent: triphenylphosphine, coordination agent is 1: 1~1: 8 with the ratio of monomeric total mole number;
(6) solvent: N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl sulfoxide (DMSO) (DMSO), its charging capacity are that 1mL/mmol~10mL/mmol is a benchmark with monomeric total mole number;
More than related monomeric total mole number be the mole number sum of monomer 1 and monomer 2;
(7) synthesis step
Make a gesture of measuring catalyzer according to set of dispense, coordination agent and reductive agent join in the reaction flask together, fill the nitrogen deoxygenation, add a small amount of solvent,, treat that solution becomes sorrel at 60~120 ℃ of stirring reactions, add remaining solvent and monomer 1 and monomer 2 again, continue reaction 2~8h, then reactant is poured in the HCl/ acetone soln of 25wt%, stir, filter collecting precipitation, with acetone backflow washing precipitation 4~8h, filter collecting precipitation, the dry product that gets.
Specific implementation method is as follows:
Embodiment 1:
With the 13mmol nickelous bromide, 25mmol triphenylphosphine and 100mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 20mL DMAc, at 120 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 30mL DMAc and 1mmol monomer 2 and 99mmol monomer 1a, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 96%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.37dL/g.
Embodiment 2:
With the 3mmol nickelous bromide, 6.25mmol triphenylphosphine and 500mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 30mL DMAc, at 90 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 120mL DMAc and 25mmol monomer 2 and 25mmol monomer 1b, reaction 5h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 20min, filter, throw out with 300mL acetone backflow 6h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 95%.NMP is a solvent, and 30 ℃ of logarithmic viscosity numbers of measuring product down are 0.76dL/g.
Embodiment 3:
With the 25mmol nickelous bromide, 50mmol triphenylphosphine and 300mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 20mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 450mL DMAc and 25mmol monomer 2 and 75mmol monomer 1c, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 86%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.67dL/g.
Embodiment 4:
With the 10mmol nickelous chloride, 28mmol triphenylphosphine and 350mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 130mL DMAc, at 120 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 650mL DMAc and 90mmol monomer 2 and 10mmol monomer 1d, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 600mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 92%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.91dL/g.
Embodiment 5:
With the 25mmol nickelous bromide, 80mmol triphenylphosphine and 400mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 80mL DMAc, at 90 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 260mL DMAc and 25mmol monomer 2 and 75mmol monomer 1e, reaction 4h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 40min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 90%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.53dL/g.
Embodiment 6:
With the 50mmol nickelous bromide, 70mmol triphenylphosphine and 300mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 100mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 350mL DMAc and 65mmol monomer 2 and 35mmol monomer 1f, reaction 2h pours reactant in the 800mL 25%HCl/ acetone soln then, stir 20min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 95%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.37dL/g.
Embodiment 7:
With the 5mmol nickelous chloride, 12.5mmol triphenylphosphine and 200mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 50mL DMAc, at 120 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 600mL DMAc and 24mmol monomer 2 and 76mmol monomer 1g, reaction 4h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 40min, filter, throw out with 800mL acetone backflow 8h, is filtered, 120 ℃ of oven dry obtain product.Productive rate 98%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 2.81dL/g.
Embodiment 8:
With the 46mmol nickelous bromide, 70mmol triphenylphosphine and 320mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 50mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 350mL DMAc and 15mmol monomer 2 and 85mmol monomer 1h, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 85%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.34dL/g.
Embodiment 9:
With the 35mmol nickelous chloride, 100mmol triphenylphosphine and 1000mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 300mL DMAc, at 110 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 470mL DMAc and 65mmol monomer 2 and 25mmol monomer 1i, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 96%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.64dL/g.
Embodiment 10:
With the 10mmol nickelous bromide, 12.5mmol triphenylphosphine and 340mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 50mL DMAc, at 90 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 230mL DMAc and 32mmol monomer 2 and 68mmol monomer 1j, reaction 8h pours reactant in the 1300mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 800mL acetone backflow 8h, is filtered, 110 ℃ of oven dry obtain product.Productive rate 97%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.52dL/g.
Embodiment 11:
With the 15mmol nickelous bromide, 82mmol triphenylphosphine and 150mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 35mL DMAc, at 120 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 150mL DMAc and 45mmol monomer 2 and 55mmol monomer 1d, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 98%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.89dL/g.
Embodiment 12:
With the 28mmol nickelous bromide, 65mmol triphenylphosphine and 510mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 50mL DMAc, at 90 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 320mL DMAc and 70mmol monomer 2 and 30mmol monomer 1g, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 110 ℃ of oven dry obtain product.Productive rate 96%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.48dL/g.
Embodiment 13:
With the 19mmol nickelous bromide, 80mmol triphenylphosphine and 320mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 150mL DMAc, at 90 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 320mL DMAc and 33mmol monomer 2 and 67mmol monomer 1g, reaction 8h pours reactant in the 1000mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 110 ℃ of oven dry obtain product.Productive rate 86%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.48dL/g.
Embodiment 14:
With the 34mmol nickelous bromide, 48mmol triphenylphosphine and 400mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 50mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 250mL DMAc and 99mmol monomer 2 and 1mmol monomer 1e, reaction 8h pours reactant in the 800mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 85%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.69dL/g.
Embodiment 15:
With the 35mmol nickelous bromide, 65mmol triphenylphosphine and 500mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 20mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 650mL DMAc and 64mmol monomer 2 and 36mmol monomer 1k, reaction 8h pours reactant in the 1500mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 500mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 90%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.32dL/g.
Embodiment 16:
With the 45mmol nickelous bromide, 75mmol triphenylphosphine and 300mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 20mL DMAc, at 80 ℃ of stirring reactions.After the system for the treatment of becomes sorrel, add 450mL DMAc and 12mmol monomer 2 and 88mmol monomer 11, reaction 8h pours reactant in the 750mL 25%HCl/ acetone soln then, stir 30min, filter, with throw out with 250mL acetone backflow 8h, filter, 100 ℃ of oven dry obtain product.Productive rate 99%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.89dL/g.
Embodiment 17:
With the 55mmol nickelous bromide, 85mmol triphenylphosphine and 500mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 50mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 350mL DMAc and 12mmol monomer 2 and 88mmol monomer 1m, reaction 8h pours reactant in the 600mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 100mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 88%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.76dL/g.
Embodiment 18:
With the 75mmol nickelous bromide, 90mmol triphenylphosphine and 360mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 40mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 630mL DMAc and 76mmol monomer 2 and 24mmol monomer 1n, reaction 8h pours reactant in the 900mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 450mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 92%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 0.69dL/g.
Embodiment 19:
With the 55mmol nickelous bromide, 65mmol triphenylphosphine and 400mmol zinc powder join in the reaction flask, fill the nitrogen deoxygenation, add 35mL DMAc, at 80 ℃ of stirring reactions, after the system for the treatment of becomes sorrel, add 850mL DMAc and 38mmol monomer 2 and 62mmol monomer 1l, reaction 8h pours reactant in the 1250mL 25%HCl/ acetone soln then, stir 30min, filter, throw out with 550mL acetone backflow 8h, is filtered, 100 ℃ of oven dry obtain product.Productive rate 100%.NMP is a solvent, and the logarithmic viscosity number of measuring product in the time of 30 ℃ is 1.34dL/g.