CN102786667B - Block sulfonated polyphenylene, and preparation method and application thereof - Google Patents

Block sulfonated polyphenylene, and preparation method and application thereof Download PDF

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CN102786667B
CN102786667B CN201210260824.3A CN201210260824A CN102786667B CN 102786667 B CN102786667 B CN 102786667B CN 201210260824 A CN201210260824 A CN 201210260824A CN 102786667 B CN102786667 B CN 102786667B
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CN102786667A (en
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陈康成
陆一川
施立群
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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

A kind of block sulfonated polyphenyl and its preparation method and application
Technical field
The invention belongs to polymeric material field, relate in particular to a kind of block sulfonated polyphenyl and its preparation method and application.
Background technology
Proton exchange membrane not only can split cell forms the two poles of the earth but also effective proton conducting, was widely used in the field such as fuel cell and flow battery.At present, the perfluorinated sulfonic acid type proton exchange polymer membrane of the marketization, not only expensive, and also it is low to exist use temperature, and fuel and the large problem of ionogen transmitance, limited the marketization of fuel cell and flow battery greatly.
Aromatic sulfonated polymer, as SPSF, sulfonated poly (phenylene oxide), sulfonated polyether-ether-ketone and sulfonated polyimide etc. are widely studied as proton exchange membrane material.But, because these materials have self shortcoming, as not high in SPSF, sulfonated poly (phenylene oxide), sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) bad mechanical property, film-forming properties water resistance bad and sulfonated polyimide, these drawbacks limit their use.
Summary of the invention
The above-mentioned defect existing for aromatic sulfonated polymer in prior art, the invention provides a kind of block sulfonated polyphenyl and its preparation method and application, the present invention forms polymkeric substance by sulfonation segment and non-sulfonation segment by copolymerization, formation has the hydrophilic microfacies of sulfonation of proton conduction property and keeps the block sulfonated polyphenyl of the micro phase separation structure of the hydrophobic microfacies of non-sulfonation of film mechanical property, and the present invention simultaneously also provides the preparation method of sulfonated polyphenyl and the application in proton exchange membrane thereof.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
Block sulfonated polyphenyl, it is formed by copolymerization by sulfonation segment (A) and the non-sulfonation segment (B) with proton conduction property, and its structural formula is as shown in general formula (I):
Ar in described segment (A) 1for any one in following chemical structure:
Described Ar 2for any one in following chemical structure:
Described Ar 3for any one in following chemical structure:
Described Ar 4for any one in following chemical structure:
Described 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 described block sulfonated polyphenyl, comprises following preparation process:
(1) preparation taking-Cl group as the non-sulfonation segment (B) of terminal group: at N 2under protection, first by monomer A r 2and Ar 3be dissolved in non-protonic solvent described Ar 3with Ar 2mol ratio be 101:100-2:1, taking Lewis base as catalyzer, the consumption of described catalyzer is Ar 3the 2.4-3 of mole number doubly, reacts 2-24 hour, then react 12-24 hour at 120-180 DEG C at 80-120 DEG C, is cooled to room temperature; Then adding mole number 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 DEG C and continues reaction 24-48 hour, generate the non-sulfonation segment (B) taking-Cl group as end group;
By this reaction system solution filter, wash with water to neutrality and collect solid, this solid is through vacuum-drying, with described non-protonic solvent dissolving, using methyl alcohol or ethanol as precipitation agent, heavily separates out purification; Or directly this monomer is put into methyl alcohol or ethanol and stirred and spend the night, by unnecessary Ar 4monomer washes away, and obtains the non-sulfonation segment taking-Cl group as terminal group;
(2) preparation of block sulfonated polyphenyl: the sulfonated monomers metal-salt Ar that will form segment (A) 1with the non-sulfonation segment (B) taking-Cl group as terminal group, described Ar 1with the mol ratio of segment B be 5:1-100:1, at transition metal Ni[0], triphenylphosphine be coordination agent and the zinc powder catalyst system that is reductive agent, with non-protonic solvent be under reaction medium, the consumption of described catalyzer is Ar 1with the 5-20% of segment B mole number summation, the sulfonated monomers metal-salt Ar of proton conduction property will be there is 1carry out copolymerization with non-sulfonation segment (B), temperature of reaction is 50-100 DEG C, and the reaction times is 2-24 hour;
Reaction soln is poured in the water that contains HCl and stirred and spend the night, filter, the solid of collecting is heavily analysed after being again dissolved in above-mentioned solvent in toluene, obtains block sulfonated polyphenylene copolymerized.
Further improvement to technique scheme: described synthetic segment (A) sulfonated monomers Ar used 1metal-salt is the two chlorine aromatic compound monomers of sulfonation with following structure, and its structural formula is any one in following structure:
Wherein M is metal ion: Na +, K +, Li +in any one, X is-O-or-S-group.
Further improvement to technique scheme: synthetic described non-sulfonation segment (B) monomer A r used 2one in following compounds:
Further improvement to technique scheme: described monomer A r 3one in following compounds:
Further improvement to technique scheme: described monomer A r 4one in following compounds:
Further improvement to technique scheme: described non-protonic solvent is DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone.
Further improvement to technique scheme: described lewis-base catalyst is K 2cO 3or Na 2cO 3.
The application of block sulfonated polyphenyl described in the present invention also provides in preparation proton exchange membrane.
The making method of described proton exchange membrane is that described block sulfonated polyphenyl is dissolved in non-protonic solvent, and its mass body volume concentrations 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:
The present invention adopts transition metal Ni[0] catalyst system that is reductive agent as catalyzer, triphenylphosphine as coordination agent and zinc powder, sulfonated monomers and non-sulfonation segment (B) are carried out to polymerization, form the block sulfonated polyphenyl with the segment (A) of sulfonic acid group and the segment (B) of non-sulfonation.By regulating the mol ratio of sulfonated monomers and non-sulfonation segment (B), can accurately control the sulfonation degree of block polyphenyl proton exchange membrane.
Sulfonated polyphenyl of the present invention is by having the sulfonation segment (A) of proton conduction property and the block polymer that keeps the non-sulfonation segment (B) of film mechanical property to form by covalent attachment, after described sulfonated polyphenyl is dissolved in solution, smear shaping at substrate, the dry sulfonated polyphenyl proton exchange membrane of making.The proton exchange membrane making has excellent chemical stability, high mechanical strength and the high-proton-conductivity under low humidity.
Read by reference to the accompanying drawings after the specific embodiment of the present invention, it is clearer that the other features and advantages of the invention will become.
Brief description of the drawings
Fig. 1 is the transmission electron microscope figure of the proton exchange membrane that makes of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in further detail.
Embodiment 1
The present embodiment is to synthesize sulfonated polyphenyl block polyether ether ketone copolymers as example, and structural formula is as follows, and concrete preparation method comprises the following steps:
(1), the preparation taking-Cl group as non-sulfonation segment (B) polyether-ether-ketone of end group: at N 2under protection, first will serve as Ar 24 of monomer, 4-dichloro benzophenone (10mmol) and as Ar 32 of monomer, 2-(4-hydroxybenzene) HFC-236fa (11mmol) is dissolved in N,N-dimethylacetamide (DMAC) solvent, adds K 2cO 3(20mmol), at 100 DEG C, react 2 hours, then at 160-180 DEG C, react 20 hours, be cooled to room temperature.Now, monomer A r 2and Ar 3react the oligomeric segment of rear formation taking-OH group as end, the length n=M of described oligomeric segment ar2/ (M ar3-M ar2), the mole number that wherein M is monomer, the length n=10 of described oligomeric segment.According to calculate end-OH or-mole number of SH group determines end-blocking monomer A r 4amount, add the Ar as capping group herein 4monomer (4-fluorobenzoyl), to chlorobenzene 2.6mmol, is elevated to 150 DEG C by the temperature of this reaction system and continues reaction 24 hours.
This reaction system solution is poured into water, filters, solid washes with water to neutrality, collects.This solid is at 80 DEG C after vacuum-drying, and with DMF dissolving, concentration is 30%wt, using 500ml methyl alcohol as precipitation agent, heavily separates out purification.Obtaining taking-Cl group as the non-sulfonation segment (B) of end is dichloro end-blocking poly-(ether ether ketone), described 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 2under protection by 10mmol nickelous bromide; 100mmol triphenylphosphine and 600mmol zinc powder join in reaction flask; add 15mlDMAC; the system that is stirred at the 60 DEG C look that reddens; add (A) segment sulfonated monomers 2 of 50mmol; 2-(3-sodium sulfonate) benzoyl group-4,4-DCBP) and the DMAc solution of the 35wt% of 5mmol segment (B) dichloro end-blocking poly-(ether ether ketone).System is warming up to 80 DEG C, reaction 8h.The reaction soln of thickness is poured in the 10%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, dry, obtain block sulfonated polyphenyl of the present invention, length m=10 of described sulfonated polyphenyl segment, yield is 94%.Taking DMSO(dimethyl sulfoxide (DMSO)) be solvent, the logarithmic viscosity number of product 35 DEG C time (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
Embodiment 2
The present embodiment is taking the sulfonated polyphenyl block polyether ether ketone copolymers of embodiment 1 as example, and structural formula is with embodiment 1, and concrete preparation method comprises the following steps:
(1), the preparation taking-Cl group as non-sulfonation segment (B) polyether-ether-ketone of end group: at N 2under protection, first will serve as Ar 24 of monomer, 4-difluoro benzophenone (15mmol) and as Ar 32 of monomer, 2-(4-hydroxybenzene) in HFC-236fa (16mmol) DMF solvent, add K 2cO 3(20mmol), under 100 ° of C, react 2 hours, then at 120-140 DEG C, react 20 hours, be cooled to room temperature.Now, monomer A r 2and Ar 3react the oligomeric segment of rear formation taking-OH group as end, the length n=15 of described oligomeric segment.Add the Ar as capping group 4monomer (4-fluorobenzoyl), to chlorobenzene 3.6mmol, is elevated to 150 DEG C by the temperature of this reaction system and continues reaction 24 hours.
This reaction system solution is poured into water, filters, solid washes with water to neutrality, collects.This solid is at 80 DEG C after vacuum-drying, and with DMF dissolving, concentration is 30%wt, using 500ml methyl alcohol as precipitation agent, heavily separates out purification.Obtain taking-Cl group as the non-sulfonation segment of end, described 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 2under protection by 10mmol nickelous bromide; 100mmol triphenylphosphine and 600mmol zinc powder join in reaction flask; add 15mlDMAC(N; N-N,N-DIMETHYLACETAMIDE); the system that is stirred at the 60 DEG C look that reddens; add (A) segment sulfonated monomers 2 of 50mmol, 2-(3-sodium sulfonate) benzoyl group-4,4-DCBP and 2.5mmol(B) the DMAc solution of 35wt% of segment dichloro end-blocking poly-(ether ether ketone).System is warming up to 80 DEG C, reaction 8h.The reaction soln of thickness is poured in the 10%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, dry, obtain block sulfonated polyphenyl of the present invention, described sulfonated polyphenyl chain length m=20, yield is 94%.Taking DMSO(dimethyl sulfoxide (DMSO)) be solvent, the logarithmic viscosity number of product 35 DEG C time (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
Embodiment 3
The present embodiment is to synthesize the poly-octafluoro biphenyl thioether copolymer of sulfonated polyphenyl block as example, and structural formula is as follows, and concrete preparation method comprises the following steps:
(1), the preparation of the poly-octafluoro biphenyl thioether of the non-sulfonation segment (B) taking-Cl group as end group: at N 2under protection, first will serve as Ar 2the perfluorinated biphenyl (20mmol) of monomer and as Ar 32 of monomer, 2-(4-sulfydryl benzene) propane (21mmol) is dissolved in DMF solvent, adds K 2cO 3(20mmol), at 80 DEG C, react 2 hours, then at 120-140 DEG C, react 12 hours, be cooled to room temperature.Now, monomer A r 2and Ar 3react the oligomeric segment of rear formation taking-SH group as end, the length n=20 of segment in the present embodiment.Add Ar4 monomer (4-fluorobenzoyl) as capping group to chlorobenzene 2.4mmol, the temperature of this reaction system is elevated to 120 DEG C and continues reaction 24 hours.
This reaction system solution is poured into water, filters, solid washes with water to neutrality, collects.This solid after vacuum-drying, is poured solid in 500ml methanol solution into and is stirred 12h at 80 DEG C, filters.Obtain taking-Cl group as the non-sulfonation segment of end, described non-sulfonation chain length n=20, it is 11800 that GPC records molecular weight Mn.
(2), the preparation of the poly-octafluoro biphenyl thioether copolymer of sulfonated polyphenyl block: at N 2under protection by 14mmol nickelous bromide; 100mmol triphenylphosphine and 800mmol zinc powder join in reaction flask; add 15mlDMAC(N; N-N,N-DIMETHYLACETAMIDE); the system that is stirred at the 60 DEG C look that reddens; add (A) segment sulfonated monomers 2 of 60mmol, 2-(4-sodium sulfonate phenoxy group) benzoyl group-4,4-DCBP and 2mmol(B) the DMAc solution of 30wt% of the poly-octafluoro biphenyl thioether of segment dichloro end-blocking.System is warming up to 80 DEG C, reaction 8h.The reaction soln of thickness is poured in the 15%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, dry, obtain block sulfonated polyphenyl of the present invention, described sulfonated polyphenyl chain length m=30, yield is 96%.Taking DMSO(dimethyl sulfoxide (DMSO)) be solvent, the logarithmic viscosity number of product 35 DEG C time (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
Embodiment 4
The present embodiment is to synthesize the poly-fluorenes phenylate sulfone copolymer of sulfonated polyphenyl block as example, and structural formula is as follows, and concrete preparation method comprises the following steps:
(1), the preparation of the poly-fluorenes phenylate sulfone of the non-sulfonation segment (B) taking-Cl group as end group: at N 2under protection, first will serve as Ar 24 of monomer, 4-difluorodiphenyl sulfone (20mmol) and as Ar 39 of monomer, 9-bis-(4-benzene sulfone) fluorenes (21mmol) is dissolved in DMF solvent, adds K 2cO 3(20mmol), at 80 DEG C, react 2 hours, then at 120-140 DEG C, react 12 hours, be cooled to room temperature.Now, monomer A r 2and Ar 3react the oligomeric segment of rear formation taking-SH group as end, the length n=20 of described oligomeric segment.Add the Ar as capping group 4monomer (4-fluorobenzoyl), to chlorobenzene 2.4mmol, is elevated to 120 DEG C by the temperature of this reaction system and continues reaction 24 hours.
This reaction system solution is poured into water, filters, solid washes with water to neutrality, collects.This solid after vacuum-drying, is poured solid in 500ml methanol solution into and is stirred 12h at 80 DEG C, filters.Obtain taking-Cl group as the non-sulfonation segment of end, the length n=20 of described non-sulfonation segment.
(2), the preparation of the poly-fluorenes phenylate sulfone copolymer of sulfonated polyphenyl block: at N 2under protection by 14mmol nickelous bromide; 100mmol triphenylphosphine and 800mmol zinc powder join in reaction flask; add 15mlDMAC(N; N-N,N-DIMETHYLACETAMIDE); the system that is stirred at the 60 DEG C look that reddens; add (A) segment sulfonated monomers 2 of 60mmol, 2-(4-sodium sulfonate phenoxy group) benzoyl group-4,4-DCBP and 3mmol(B) the DMAc solution of 30wt% of the poly-octafluoro biphenyl thioether of segment dichloro end-blocking.System is warming up to 80 DEG C, reaction 8h.The reaction soln of thickness is poured in the 15%HCl aqueous solution of 500ml, stirred 12h, filter, solid is dried, and wash 12h with refluxing toluene, dry, obtain block sulfonated polyphenyl of the present invention, described sulfonated polyphenyl chain length m=20, yield is 96%.Taking DMSO(dimethyl sulfoxide (DMSO)) be solvent, the logarithmic viscosity number of product 35 DEG C time (content of polymkeric substance in DMSO is 0.05g/ml) is 0.65dL/g.
The above-mentioned block sulfonated polyphenyl making is dissolved in the solution such as DMSO, DMAc, DMF or NMP, and concentration is 5-20wt%, by this solution in sheet glass upper film forming.Dry 4-12 hour at 60-80 DEG C, water or alcohol immersion demoulding, clean with clear water after 12-36 hour by the HCl aqueous solution soaking of 5-15wt%, dry 2-10 hour at 100-150 DEG C, obtain the proton exchange membrane that block sulfonated polyphenyl is made, the physico-chemical property of described block sulfonated polyphenyl and proton exchange membrane thereof is as shown in table 1.
The physico-chemical property of the block sulfonated polyphenyl of table 1 and proton exchange membrane thereof
A:IEC is the titration determination value of loading capacity, in its bracket, is calculated value; B:WU is water ratio; At c:60 DEG C, the proton conductivity of the proton exchange membrane under different humidity.In table 1, can find out that the very approaching and molecular weight of the titration determination value of IEC and calculated value is 50000 left and right, illustrate that block sulfonated polyphenyl is successfully synthesized.These block sulfonated polyphenyl have shown the excellent proton conduction property in water and under low humidity.
The transmission electron microscope figure of proton exchange membrane as shown in Figure 1, shows in Fig. 1 that block sulfonated polyphenyl proton exchange membrane has the micro phase separation structure of obvious hydrophilic microfacies and hydrophobic microfacies, and hydrophilic microfacies interconnects, and has greatly improved proton conduction property.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these amendments or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.

Claims (2)

1. block sulfonated polyphenyl, is characterized in that it is formed by copolymerization by sulfonation segment (A) and the non-sulfonation segment (B) with proton conduction property, and its structural formula is as shown in logical formula I:
（Ⅰ）
Ar in described segment (A) 1for any one in following chemical structure:
?；
Described Ar 2for any one in following chemical structure:
；
Described Ar 3for any one in following chemical structure:
；
Described Ar 4for any one in following chemical structure:
；
Described linking group X is-O-or-S-;
Wherein the scope of m and n is the arbitrary integer of [1,100].
2. the application of block sulfonated polyphenyl according to claim 1 in preparation proton exchange membrane.
CN201210260824.3A 2012-07-25 2012-07-25 Block sulfonated polyphenylene, and preparation method and application thereof Active CN102786667B (en)

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