CN102786667A - Block sulfonated polyphenylene, and preparation method and application thereof - Google Patents
Block sulfonated polyphenylene, and preparation method and application thereof Download PDFInfo
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- CN102786667A CN102786667A CN2012102608243A CN201210260824A CN102786667A CN 102786667 A CN102786667 A CN 102786667A CN 2012102608243 A CN2012102608243 A CN 2012102608243A CN 201210260824 A CN201210260824 A CN 201210260824A CN 102786667 A CN102786667 A CN 102786667A
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Abstract
The invention provides block sulfonated polyphenylene, and a preparation method and application thereof. According to the invention, the method employs a catalyst system consisting of transition metal Ni[0] used as a catalyst, triphenylphosphine used as a coordination agent and zinc powder used as a reducing agent, and an aprotic solvent is used as a reaction medium for copolymerization of sulfonated monomers having proton conduction performance and non-sulfonated monomers so as to obtain the target block sulfonated polyphenylene copolymer. The copolymer is dissolved in an organic solvent so as to obtain a uniform solution, and a membrane is prepared by using a casting or tape casting process. The sulfonated polyphenylene proton exchange membrane provided by the invention has excellent proton conduction performance under the condition of low humidity, high chemical stability and high mechanical properties, can be used in the fields of proton exchange membrane fuel cells and redox flow batteries, and has a wide application range and a good commercial application prospect.
Description
Technical field
The invention belongs to polymeric material field, relate in particular to a kind of block sulfonated polyphenyl.
Background technology
PEM not only can split cell forms the two poles of the earth but also effective proton conducting, was widely used in fields such as fuel cell and flow battery.At present, the perfluorinated sulfonic acid type proton exchange polymer membrane of the marketization not only cost an arm and a leg, and it is low to exist use temperature, and fuel and the big problem of ionogen transmitance have limited the marketization of fuel cell and flow battery greatly.
Aromatic sulfonated polymer, like SPSF, sulfonated poly (phenylene oxide), sulfonated polyether-ether-ketone and sulfonated polyimide etc. as proton exchange membrane material by broad research.But, because these materials have the shortcoming of self, like SPSF, sulfonated poly (phenylene oxide), sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) bad mechanical property, film-forming properties is bad and the water resistance of sulfonated polyimide is not high, these drawbacks limit their use.
Summary of the invention
Above-mentioned defective to aromatic sulfonated polymer existence in the prior art; The invention provides a kind of block sulfonated polyphenyl; The present invention forms polymkeric substance with sulfonation segment and non-sulfonation segment through copolymerization; Formation has the hydrophilic microfacies of sulfonation of proton conduction performance and the block sulfonated polyphenyl of the micro phase separation structure of the hydrophobic microfacies of non-sulfonation that keeps the film mechanical property, and the present invention simultaneously also provides the preparation method of sulfonated polyphenyl and the application on PEM thereof.
For realizing the foregoing invention purpose, the present invention adopts following technical proposals to be achieved:
Block sulfonated polyphenyl, it is formed through copolymerization by sulfonation segment (A) with proton conduction performance and non-sulfonation segment (B), and its structural formula is shown in general formula (I):
Ar in the said segment (A)
1Be in the following chemical structure any one:
Said Ar
2Be in the following chemical structure any one:
Said Ar
3Be in the following chemical structure any one:
Said Ar
4Be in the following chemical structure any one:
Said linking group X is-O-or-S-;
Wherein the scope of m and n is the arbitrary integer of [1,100].
The present invention also provides the preparation method of said block sulfonated polyphenyl, comprises following preparation process:
(1) with-the Cl group is the preparation of the non-sulfonation segment (B) of terminal group: at N
2Under the protection, earlier with monomer A r
2And Ar
3Be dissolved in the non-protonic solvent said Ar
3With Ar
2Mol ratio be 101:100-2:1, be catalyzer with the Lewis base, said catalyst consumption is Ar
3The 2.4-3 of mole number doubly reacted 2-24 hour down at 80-120 ℃, reacted 12-24 hour down at 120-180 ℃ again, was cooled to room temperature; Adding mole number then is Ar
2And Ar
3React remaining-OH or-1.0-1.5 of SH group mole number Ar doubly
4, the temperature of this reaction system is elevated to 100-150 ℃ continues reaction 24-48 hour, generate with-the Cl group is the non-sulfonation segment (B) of end group;
This reaction system solution is filtered, and water is washed till the neutral solid of collecting, and this solid dissolves with said non-protonic solvent through vacuum-drying, as precipitation agent, heavily separates out purification with methyl alcohol or ethanol; Perhaps directly this monomer is put into methyl alcohol or ethanol stirred overnight, with unnecessary Ar
4The monomer flush away, promptly obtain with-the Cl group is the non-sulfonation segment of terminal group;
(2) preparation of block sulfonated polyphenyl: the sulfonated monomers metal-salt Ar that will constitute segment (A)
1With with-the Cl group is the non-sulfonation segment (B) of terminal group, said Ar
1With the mol ratio of segment B be 5:1-100:1, transition metal Ni [0], triphenylphosphine be coordination agent and zinc powder be reductive agent catalyst system, use non-protonic solvent as under the reaction medium, said catalyst consumption is Ar
1With the 5-20% of segment B mole number summation, will have the sulfonated monomers metal-salt Ar of proton conduction performance
1Carry out copolymerization with non-sulfonation segment (B), temperature of reaction is 50-100 ℃, and the reaction times is 2-24 hour;
Reaction soln is poured into stirred overnight in the water that contains HCl, filtered, the solid of collecting is heavily analysed in toluene after being dissolved in the above-mentioned solvent again, promptly obtains block sulfonated polyphenylene copolymerized.
Further improvement to technique scheme: the used sulfonated monomers Ar of said synthetic segment (A)
1Metal-salt is the two chlorine aromatic compound monomers of sulfonation with following structure, and its structural formula is any one in the following structure:
Wherein M is metals ion: Na
+, K
+, Li
+In any one, X is-O-or-the S-group.
Further improvement to technique scheme: the synthetic used monomer A r of said non-sulfonation segment (B)
2A kind of in the following compounds:
Further improvement to technique scheme: said monomer A r
3A kind of in the following compounds:
Further improvement to technique scheme: said monomer A r
4A kind of in the following compounds:
Further improvement to technique scheme: said non-protonic solvent is N, dinethylformamide, DMAC N,N or N-Methyl pyrrolidone.
Further improvement to technique scheme: said lewis-base catalyst is K
2CO
3Or Na
2CO
3
The present invention also provides the application of described block sulfonated polyphenyl in the preparation PEM.
The making method of said PEM is that said block sulfonated polyphenyl is dissolved in the non-protonic solvent, and its mass and size concentration in solvent is 1%-35%, smears shaping at substrate, and the dry thick film of 10-100 μ m that forms.
Compared with prior art, advantage of the present invention and positively effect are:
It is the catalyst system of reductive agent as coordination agent and zinc powder as catalyzer, triphenylphosphine that the present invention adopts transition metal Ni [0]; Sulfonated monomers and non-sulfonation segment (B) are carried out polymerization, and formation has the segment (A) of sulfonic acid group and the block sulfonated polyphenyl of non-sulfonated segment (B).Through regulating the mol ratio of sulfonated monomers and non-sulfonation segment (B), can accurately control the sulfonation degree of block polyphenyl PEM.
Sulfonated polyphenyl of the present invention is by the sulfonation segment (A) with proton conduction performance and keeps the non-sulfonation segment (B) of film mechanical property to pass through the block polymer that covalent attachment forms; After said sulfonated polyphenyl dissolved in solution; Smear shaping at substrate, drying is processed the sulfonated polyphenyl PEM.The PEM that makes has excellent chemicalstability, high mechanical strength and the high proton conductivity ability under low humidity.
After advantages embodiment of the present invention, other characteristics of the present invention and advantage will become clearer.
Description of drawings
Fig. 1 is the transmission electron microscope figure of the PEM that makes of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is done further detailed explanation.
Embodiment 1
Present embodiment is an example with synthetic sulfonated polyphenyl block polyether ether ketone copolymers, and structural formula is following, and concrete preparation method may further comprise the steps:
(1), with-the Cl group is the preparation of non-sulfonation segment (B) polyetheretherketone of end group: at N
2Protection down earlier will be as Ar
2Monomeric 4,4-dichloro benzophenone (10mmol) and as Ar
3Monomeric 2,2-(4-hydroxybenzene) HFC-236fa (11mmol) is dissolved in DMAC N,N (DMAC) solvent, adds K
2CO
3(20mmol), reacted 2 hours down, reacted 20 hours down at 160-180 ℃ again, be cooled to room temperature at 100 ℃.At this moment, monomer A r
2And Ar
3Reaction accomplish back formation with-the OH group is the oligomeric segment of end, the length n=M of said oligomeric segment
Ar2/ (M
Ar3-M
Ar2), wherein M is monomeric mole number, the length n=10 of said oligomeric segment.-OH terminal according to calculating or-mole number of SH group confirms end-blocking monomer A r
4Amount, add Ar here as capping group
4Monomer (4-fluorobenzoyl) is to chlorobenzene 2.6mmol, the temperature of this reaction system is elevated to 150 ℃ continues reaction 24 hours.
This reaction system solution is poured in the water, filtered, the solid water is washed till neutrality, collects.This solid is used N after 80 ℃ of following vacuum-drying, the dinethylformamide dissolving, and concentration is 30%wt, as precipitation agent, heavily separates out purification with 500ml methyl alcohol.Promptly obtaining with-Cl group is that the non-sulfonation segment (B) of end is that the dichloro end-blocking gathers (ether ether ketone), said non-sulfonation segment (B) length n=10, and GPC records molecular weight Mn=5700.
(2), the preparation of sulfonated polyphenyl block polyether ether ketone copolymers: at N
2Protection is down with the 10mmol nickelous bromide; 100mmol triphenylphosphine and 600mmol zinc powder join in the reaction flask; Add 15mlDMAC, the system that under 60 ℃, the is stirred to look that reddens adds (A) segment sulfonated monomers 2 of 50mmol; 2-(3-sodium sulfonate) benzoyl group-4,4-DCBP) and 5mmol segment (B) dichloro end-blocking gather the DMAc solution of the 35wt% of (ether ether ketone).System is warming up to 80 ℃, reaction 8h.The heavy-gravity reaction soln is poured in the 10%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, oven dry obtains block sulfonated polyphenyl of the present invention, said sulfonated polyphenyl segmental length m=10, and yield is 94%.With DMSO (DMSO 99.8MIN.) is solvent, and the logarithmic viscosity number of product in the time of 35 ℃ (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
Embodiment 2
Present embodiment is an example with the sulfonated polyphenyl block polyether ether ketone copolymers of embodiment 1, and structural formula is with embodiment 1, and concrete preparation method may further comprise the steps:
(1), with-the Cl group is the preparation of non-sulfonation segment (B) polyetheretherketone of end group: at N
2Protection down earlier will be as Ar
2Monomeric 4,4-difluoro benzophenone (15mmol) and as Ar
3Monomeric 2,2-(4-hydroxybenzene) HFC-236fa (16mmol) N in the dinethylformamide solvent, adds K
2CO
3(20mmol), reaction is 2 hours under 100 ° of C, reacts 20 hours down at 120-140 ℃ again, is cooled to room temperature.At this moment, monomer A r
2And Ar
3Reaction accomplish back formation with-the OH group is the oligomeric segment of end, the length n=15 of said oligomeric segment.Adding is as the Ar of capping group
4Monomer (4-fluorobenzoyl) is to chlorobenzene 3.6mmol, the temperature of this reaction system is elevated to 150 ℃ continues reaction 24 hours.
This reaction system solution is poured in the water, filtered, the solid water is washed till neutrality, collects.This solid is used N after 80 ℃ of following vacuum-drying, the dinethylformamide dissolving, and concentration is 30%wt, as precipitation agent, heavily separates out purification with 500ml methyl alcohol.Promptly obtain with-the Cl group is terminal non-sulfonation segment, said non-sulfonation chain length n=15, GPC records molecular weight Mn=8100.
(2), the preparation of sulfonated polyphenyl block polyether ether ketone copolymers: at N
2Protection is down with the 10mmol nickelous bromide; 100mmol triphenylphosphine and 600mmol zinc powder join in the reaction flask, add 15mlDMAC (DMAC N,N); The system that under 60 ℃, the is stirred to look that reddens; (A) segment sulfonated monomers 2 that adds 50mmol, 2-(3-sodium sulfonate) benzoyl group-4,4-DCBP and 2.5mmol (B) segment dichloro end-blocking gathers the DMAc solution of the 35wt% of (ether ether ketone).System is warming up to 80 ℃, reaction 8h.The heavy-gravity reaction soln is poured in the 10%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, oven dry obtains block sulfonated polyphenyl of the present invention, said sulfonated polyphenyl chain length m=20, and yield is 94%.With DMSO (DMSO 99.8MIN.) is solvent, and the logarithmic viscosity number of product in the time of 35 ℃ (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
Embodiment 3
It is example that present embodiment gathers octafluoro biphenyl thioether copolymer with synthetic sulfonated polyphenyl block, and structural formula is following, and concrete preparation method may further comprise the steps:
(1), be the preparation that the non-sulfonation segment (B) of end group gathers octafluoro biphenyl thioether with-Cl group: at N
2Protection down earlier will be as Ar
2Monomeric perfluorinated biphenyl (20mmol) and as Ar
3Monomeric 2,2-(4-sulfydryl benzene) propane (21mmol) is dissolved in N, in the dinethylformamide solvent, adds K
2CO
3(20mmol), reacted 2 hours down, reacted 12 hours down at 120-140 ℃ again, be cooled to room temperature at 80 ℃.At this moment, monomer A r
2And Ar
3Reaction accomplish back formation with-the SH group is the oligomeric segment of end, segmental length n=20 in the present embodiment.Adding, is elevated to 120 ℃ with the temperature of this reaction system and continues reaction 24 hours chlorobenzene 2.4mmol as the Ar4 monomer (4-fluorobenzoyl) of capping group.
This reaction system solution is poured in the water, filtered, the solid water is washed till neutrality, collects.This solid is poured solid in the 500ml methanol solution into and to be stirred 12h after 80 ℃ of following vacuum-drying, filters.Promptly obtain with-the Cl group is terminal non-sulfonation segment, said non-sulfonation chain length n=20, it is 11800 that GPC records molecular weight Mn.
(2), the sulfonated polyphenyl block gathers the preparation of octafluoro biphenyl thioether copolymer: at N
2Protection is down with the 14mmol nickelous bromide; 100mmol triphenylphosphine and 800mmol zinc powder join in the reaction flask, add 15mlDMAC (DMAC N,N); The system that under 60 ℃, the is stirred to look that reddens; (A) segment sulfonated monomers 2 that adds 60mmol, 2-(4-sodium sulfonate phenoxy) benzoyl group-4,4-DCBP and 2mmol (B) segment dichloro end-blocking gathers the DMAc solution of the 30wt% of octafluoro biphenyl thioether.System is warming up to 80 ℃, reaction 8h.The heavy-gravity reaction soln is poured in the 15%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, oven dry obtains block sulfonated polyphenyl according to the invention, said sulfonated polyphenyl chain length m=30, and yield is 96%.With DMSO (DMSO 99.8MIN.) is solvent, and the logarithmic viscosity number of product in the time of 35 ℃ (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
Embodiment 4
It is example that present embodiment gathers fluorenes phenylate sulfone copolymer with synthetic sulfonated polyphenyl block, and structural formula is following, and concrete preparation method may further comprise the steps:
(1), be the preparation that the non-sulfonation segment (B) of end group gathers fluorenes phenylate sulfone with-Cl group: at N
2Protection down earlier will be as Ar
2Monomeric 4,4-difluorodiphenyl sulfone (20mmol) and as Ar
3Monomeric 9,9-two (4-benzene sulfone) fluorenes (21mmol) is dissolved in N, in the dinethylformamide solvent, adds K
2CO
3(20mmol), reacted 2 hours down, reacted 12 hours down at 120-140 ℃ again, be cooled to room temperature at 80 ℃.At this moment, monomer A r
2And Ar
3Reaction accomplish back formation with-the SH group is the oligomeric segment of end, the length n=20 of said oligomeric segment.Adding is as the Ar of capping group
4Monomer (4-fluorobenzoyl) is to chlorobenzene 2.4mmol, the temperature of this reaction system is elevated to 120 ℃ continues reaction 24 hours.
This reaction system solution is poured in the water, filtered, the solid water is washed till neutrality, collects.This solid is poured solid in the 500ml methanol solution into and to be stirred 12h after 80 ℃ of following vacuum-drying, filters.Promptly obtain with-the Cl group is terminal non-sulfonation segment, said non-sulfonation segmental length n=20.
(2), the sulfonated polyphenyl block gathers the preparation of fluorenes phenylate sulfone copolymer: at N
2Protection is down with the 14mmol nickelous bromide; 100mmol triphenylphosphine and 800mmol zinc powder join in the reaction flask, add 15mlDMAC (DMAC N,N); The system that under 60 ℃, the is stirred to look that reddens; (A) segment sulfonated monomers 2 that adds 60mmol, 2-(4-sodium sulfonate phenoxy) benzoyl group-4,4-DCBP and 3mmol (B) segment dichloro end-blocking gathers the DMAc solution of the 30wt% of octafluoro biphenyl thioether.System is warming up to 80 ℃, reaction 8h.The heavy-gravity reaction soln is poured in the 15%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, oven dry obtains block sulfonated polyphenyl according to the invention, said sulfonated polyphenyl chain length m=20, and yield is 96%.With DMSO (DMSO 99.8MIN.) is solvent, and the logarithmic viscosity number of product in the time of 35 ℃ (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
The above-mentioned block sulfonated polyphenyl that makes is dissolved in the solution such as DMSO, DMAc, DMF or NMP, and concentration is 5-20wt%, and this solution is poured into film on sheet glass.60-80 ℃ was descended dry 4-12 hour; Water or alcohol immersion demoulding; HCl aqueous solution soaking with 5-15wt% was cleaned with clear water after 12-36 hour; 100-150 ℃ was descended dry 2-10 hour, obtained the PEM that block sulfonated polyphenyl is processed, and the physico-chemical property of said block sulfonated polyphenyl and PEM thereof is as shown in table 1.
The physico-chemical property of block sulfonated polyphenyl of table 1 and PEM thereof
A:IEC is the titration determination value of loading capacity, is calculated value in its bracket; B:WU is a water ratio; Under c:60 ℃, the proton conductivity of the PEM under the different humidity.Titration determination value and the calculated value that can find out IEC in the table 1 very near with molecular weight be about 50000, block sulfonated polyphenyl synthetic by success is described.These block sulfonated polyphenyl shown excellent in water with low humidity under the proton conduction performance.
The transmission electron microscope figure of PEM is as shown in Figure 1, shows among Fig. 1 that block sulfonated polyphenyl PEM has the micro phase separation structure of obvious hydrophilic microfacies and hydrophobic microfacies, and hydrophilic microfacies interconnects, and has improved the proton conduction performance greatly.
Above embodiment is only in order to explaining technical scheme of the present invention, but not limits it; Although the present invention has been carried out detailed explanation with reference to previous embodiment, for the person of ordinary skill of the art, still can make amendment to the technical scheme that previous embodiment is put down in writing, perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of relevant art scheme break away from the spirit and the scope of the present invention's technical scheme required for protection.
Claims (10)
1. block sulfonated polyphenyl is characterized in that it is formed through copolymerization by sulfonation segment (A) with proton conduction performance and non-sulfonation segment (B), and its structural formula is shown in general formula (I):
Ar in the said segment (A)
1Be in the following chemical structure any one:
Said Ar
2Be in the following chemical structure any one:
Said Ar
3Be in the following chemical structure any one:
Said Ar
4Be in the following chemical structure any one:
Said linking group X is-O-or-S-;
Wherein the scope of m and n is the arbitrary integer of [1,100].
2. the preparation method of block sulfonated polyphenyl according to claim 1 is characterized in that it comprises following concrete preparation process:
(1) with-the Cl group is the preparation of the non-sulfonation segment (B) of terminal group: at N
2Under the protection, earlier with monomer A r
2And Ar
3Be dissolved in the non-protonic solvent said Ar
3With Ar
2Mol ratio be 101:100-2:1, be catalyzer with the Lewis base, said catalyst consumption is Ar
3The 2.4-3 of mole number doubly reacted 2-24 hour down at 80-120 ℃, reacted 12-24 hour down at 120-180 ℃ again, was cooled to room temperature; Adding mole number then is Ar
2And Ar
3React remaining-OH or-1.0-1.5 of SH group mole number Ar doubly
4, the temperature of this reaction system is elevated to 100-150 ℃ continues reaction 24-48 hour, generate with-the Cl group is the non-sulfonation segment (B) of end group;
This reaction system solution is filtered, and water is washed till the neutral solid of collecting, and this solid dissolves with said non-protonic solvent through vacuum-drying, as precipitation agent, heavily separates out purification with methyl alcohol or ethanol; Perhaps directly this monomer is put into methyl alcohol or ethanol stirred overnight, with unnecessary Ar
4The monomer flush away, promptly obtain with-the Cl group is the non-sulfonation segment of terminal group;
(2) preparation of block sulfonated polyphenyl: the sulfonated monomers metal-salt Ar that will constitute segment (A)
1With with-the Cl group is the non-sulfonation segment (B) of terminal group, said Ar
1With the mol ratio of segment B be 5:1-100:1, transition metal Ni [0], triphenylphosphine be coordination agent and zinc powder be reductive agent catalyst system, use non-protonic solvent as under the reaction medium, said catalyst consumption is Ar
1With the 5-20% of segment B mole number summation, will have the sulfonated monomers metal-salt Ar of proton conduction performance
1Carry out copolymerization with non-sulfonation segment (B), temperature of reaction is 50-100 ℃, and the reaction times is 2-24 hour;
Reaction soln is poured into stirred overnight in the water that contains HCl, filtered, the solid of collecting is heavily analysed in toluene after being dissolved in the above-mentioned solvent again, promptly obtains block sulfonated polyphenylene copolymerized.
3. the preparation method of block sulfonated polyphenyl according to claim 2 is characterized in that the used sulfonated monomers Ar of said synthetic segment (A)
1Metal-salt is the two chlorine aromatic compound monomers of sulfonation with following structure, and its structural formula is any one in the following structure:
Wherein M is metals ion: Na
+, K
+, Li
+In any one, X is-O-or-the S-group.
4. the preparation method of block sulfonated polyphenyl according to claim 2 is characterized in that the synthetic used monomer A r of said non-sulfonation segment (B)
2A kind of in the following compounds:
5. the preparation method of block sulfonated polyphenyl according to claim 2 is characterized in that said monomer A r
3A kind of in the following compounds:
6. the preparation method of block sulfonated polyphenyl according to claim 2 is characterized in that said monomer A r
4A kind of in the following compounds:
7. the preparation method of block sulfonated polyphenyl according to claim 2 is characterized in that said non-protonic solvent is N, dinethylformamide, DMAC N,N or N-Methyl pyrrolidone.
8. the preparation method of block sulfonated polyphenyl according to claim 2 is characterized in that said lewis-base catalyst is K
2CO
3Or Na
2CO
3
9. according to the application of each described block sulfonated polyphenyl of claim 1-8 in the preparation PEM.
10. according to the application of each described block sulfonated polyphenyl of claim 1-8 in the preparation PEM; The making method that it is characterized in that said PEM is that said block sulfonated polyphenyl is dissolved in the non-protonic solvent; Its mass and size concentration in solvent is 1%-35%; Smear shaping at substrate, and the dry thick film of 10-100 μ m that forms.
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