CN1312198C - Sulphonated poly(aryl ether ketone) block polybutadiene copolymer and process for preparing same - Google Patents
Sulphonated poly(aryl ether ketone) block polybutadiene copolymer and process for preparing same Download PDFInfo
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- CN1312198C CN1312198C CNB2005100263934A CN200510026393A CN1312198C CN 1312198 C CN1312198 C CN 1312198C CN B2005100263934 A CNB2005100263934 A CN B2005100263934A CN 200510026393 A CN200510026393 A CN 200510026393A CN 1312198 C CN1312198 C CN 1312198C
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Abstract
The present invention discloses a sulphonated poly (aryl ether ketone) block polybutadiene copolymer and a preparation method thereof, and the formula of the copolymer is disclosed in the specification. Dihydric phenol monomers and 4, 4'-diflubenzophenone are adopted as raw materials to synthesize a polyaryletheretherketone copolymer; then a sulfonated polyaryletheretherketone blocking butadiene rubber copolymer is synthesized from the polyaryletheretherketone copolymer and polybutadiene of terminal hydroxyl under an alkaline catalysis condition; finally, a polybutadiene chain segment is sulfonated with acetyl sulphonic acid ester, and an object product of a sulphonated poly (aryl ether ketone) block polybutadiene copolymer is obtained. The present invention integrates the favorable structure, the thermal stability and the mechanical properties of polyaryletherketone and the high structural segment movement capability of polybutadiene, and can be used for preparing high performance proton exchange film materials.
Description
Technical field: the invention belongs to a kind of functional high molecule material and preparation method thereof, particularly a kind of sulphonated poly (aryl ether ketone) block polybutadiene copolymer that is used for the fuel battery proton exchange film material and preparation method thereof.
Background technology: Proton Exchange Membrane Fuel Cells is with it starts fast, characteristics such as pollution-free, energy density height become the fuel cell development gradually main flow.Because proton exchange membrane is one of key part of such fuel cells, its property relationship is to the overall performance of whole fuel cell system, so great amount of manpower and material resources have all been dropped into to its research in countries in the world.Though the full fluorin proton exchange film performance of widespread use at present is fine, but its manufacturing cost height, service temperature is low, fuel infiltration is serious when being applied to direct methanol fuel cell, and floride-free or partially fluorinated proton exchange membrane therefore with low cost, excellent property has become the research focus.Finding that in research process sulfonated aromatic ring polymkeric substance has preferable performance, is the material that is hopeful to substitute the perfluorinated sulfonic acid proton exchange membrane most; The perfluorinated sulfonic acid proton exchange membrane has been because the microphase-separated of molecular structure has formed rich ionic channel, still has a very high proton conductivity even therefore its loading capacity is very low.In order to make sulfonation aromatic ring polymkeric substance also can develop good phase separation structure, generally can take two kinds of methods, a kind of is the flexible hydrophilic chain of grafting certain-length on aromatic ring; Another method is a preparation sulfonated segmented copolymer.Relatively these two kinds of method sulfonated segmented copolymers can be controlled the degree that is separated more accurately by the means of molecular designing, simultaneously can also introduce the motor capacity that some flexible segments improve molecular chain, promote the gathering of sulfonic acid group to form ionic channel, improve the specific conductivity of proton exchange membrane, be published in as Holdcroft S. " Macromolecules " 2004; 37 (5): the film of introducing in 1678 with the inclined to one side fluorine polyethylene and ethylene copolymers preparation of SPSF block, even under the condition of very low loading capacity, still have good specific conductivity.
Summary of the invention: the present invention is by the end group polycondensation of polyaryletherketone and polyhutadiene, preparation is used for the sulphonated poly (aryl ether ketone) block polybutadiene copolymer of the floride-free or low fluorine of proton exchange membrane material, not only combine the constructional feature of two kinds of block segments, and the gathering that the selectivity sulfonation of flexible polybutadiene segments more helps sulfonic acid group formed ionic channel, therefore can be used to prepare the proton exchange membrane material that high electricity is led.
Sulphonated poly (aryl ether ketone) block polybutadiene copolymer of the present invention, its repeated structural unit is as follows:
Wherein the polymerization degree is respectively, n=20-100, m
1=1-80, m
2=1-40, p=5-50.
The method of the preparation of sulphonated poly (aryl ether ketone) block polybutadiene copolymer of the present invention is as follows: followingly all represent with mass parts
(a) with 1 one 2 parts of diphenol monomers and 1 part 4,4 '-difluoro benzophenone at room temperature is dissolved in the mixed organic solvents of 5-30 part, under nitrogen environment, be warming up to 160 ℃, react after 1-4 hour, rise to 190 ℃ of reactions 14-20 hour again, after reaction finishes, reaction product is cooled to room temperature, behind the B suction filtration, filtrate is poured in 25-70 part methyl alcohol or the alcohol solvent, stir fast simultaneously, generate precipitation, behind the suction filtration filter cake is placed in 80 ℃ of deionized waters heating and stirred 2-5 hour, suction filtration obtains the polyaryletherketone of terminal hydroxy group again; Wherein mixed organic solvents is N-N-methyl-2-2-pyrrolidone N-and toluene or N, N_ N,N-DIMETHYLACETAMIDE and toluene, and N-N-methyl-2-2-pyrrolidone N-wherein, N, the mass ratio of N '-N,N-DIMETHYLACETAMIDE and toluene is 1.5: 1-4: 1;
(b) 5-10 part terminal hydroxy group polyaryletherketone is dissolved in 100-500 part 1,1,2, in the 2-tetrachloroethane, add 1-5 part terephthalyl chloride then, and in reaction soln, drip 1-5 part pyridine, be warming up to 100 ℃, reacted 1-5 hour, and elevated temperature to 150 ℃ backflow 10-30 hour again, obtained the polyaryletherketone of acid chloride end groups;
(c) 1-5 part hydroxy-terminated polybutadienes is added 15-50 part 1,1,2, in the 2-tetrachloroethane, at room temperature stir, contain 1 of 2-10 part acid chloride end groups polyaryletherketone to its adding then to dissolving fully, 1,2, the solution of 2-tetrachloroethane adds 0.2-1 part pyridine at last again as catalyzer, be warming up to 100 ℃, reacted 6-24 hour, and after reaction is finished, be cooled to room temperature, pour in 500-1500 part methyl alcohol or the ethanol and precipitate, the filter cake that suction filtration obtains is washed 2 times with 20-40 part methyl alcohol or ethanol, with 80 ℃ of deionization poach suction filtration after 2-5 hour, obtains poly (aryl ether ketone) block polybutadiene copolymer;
(d) 1 part of poly (aryl ether ketone) block polybutadiene copolymer is dissolved in the tetrahydrofuran (THF) or the N of 15-40 part; in the dinethylformamide and stir; drip the acetyl sulphonate of 0.5-10 part then; reacted 5-24 hour down at 40 ℃-100 ℃; after reaction finishes; 7-20 part tetrahydrofuran (THF) or N are removed in underpressure distillation; N '-dimethyl formamide; in then solution being poured in the methyl alcohol of 100-200 part or the alcohol solvent; solution with 5-20 part 20%NaOH is regulated PH to 7-8; the precipitation that obtains behind the suction filtration is used twice of 20-40 part methyl alcohol or washing with alcohol and vacuum-drying 12-24 hour again; product heats in 80 ℃ of deionized waters and stirred 2-5 hour the most at last, and it is sulphonated poly (aryl ether ketone) block polybutadiene copolymer that suction filtration obtains target product.
The structure of hydroxy-terminated polybutadienes used in the present invention is shown below:
Wherein, polymerization degree m=20-100.
Diphenol monomer used in the present invention is 4,4-dihydroxy-diphenyl propane, 4,4-dihydroxyl phenylbenzene HFC-236fa or 4,4-'-biphenyl diphenol.
The entire reaction equation of the sulphonated poly (aryl ether ketone) block polybutadiene copolymer of the present invention's preparation can be expressed as:
The sulphonated poly (aryl ether ketone) block polybutadiene copolymer of the present invention preparation not only contains high thermal stability, the good polyaryletherketone structure of mechanical property; And the sulfonic acid group that is grafted on polybutadiene segments is convenient to the conduction of proton, so can be used for preparing the proton exchange membrane material that high electricity is led because the segmental flexibility can be easy to assemble the formation ionic channel.
Description of drawings
Fig. 1 is the infrared spectra of embodiment 1 sulphonated poly (aryl ether ketone) block polybutadiene copolymer.
Fig. 2 is the nucleus magnetic hydrogen spectrum of embodiment 1 sulphonated poly (aryl ether ketone) block polybutadiene copolymer.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
(a) take by weighing 4,4 '-difluoro benzophenone 4.360g (0.020mol), 4,4-dihydroxy-diphenyl propane 4.788g (0.021mol), salt of wormwood 3.174g (0.023mol), add in the three-necked bottle, be dissolved in it in 40g N-N-methyl-2-2-pyrrolidone N-(NMP) and the 17g toluene and stir, under nitrogen environment, be warming up to 160 ℃ then, react after 4 hours, rise to 190 ℃ of reactions 16 hours again.Reaction is finished postcooling to room temperature, behind the B suction filtration, the liquid that obtains is poured in the 150g dehydrated alcohol, stir fast simultaneously, precipitated in a large number, filter cake is washed 2 times with dehydrated alcohol, be placed in 80 ℃ of deionized waters heating then and stirred three hours, suction filtration obtains the polyaryletherketone 7.254g of terminal hydroxy group, productive rate 87.1% again;
(b) take by weighing 1.000g terminal hydroxy group polyaryletherketone, it is dissolved in 32g 1,1,2, in the 2-tetrachloroethane, at room temperature stir to dissolving fully, add the 0.203g p-phthaloyl chloride then, and in reaction soln, drip the 0.15g pyridine, be warming up to 100 ℃, reacted 1 hour, elevated temperature to 150 ℃ reaction is 19 hours again, obtains the polyphenylene oxide ketone of acid chloride end groups;
(c) take by weighing hydroxy-terminated polybutadienes 0.840g and be dissolved in 16g 1,1,2, in the 2-tetrachloroethane, at room temperature stir to dissolving fully, contain 1,1,2 of 1.000g acid chloride end groups polyaryletherketone to its adding then, the solution of 2-tetrachloroethane, drip the 0.15g pyridine at last, be warming up to 100 ℃, reacted 12 hours.After reaction is finished, be cooled to room temperature, pour in the 150g dehydrated alcohol and precipitate, the filter cake that suction filtration obtains is washed 2 times with dehydrated alcohol, with 80 ℃ of deionization poach suction filtration after 3 hours, obtains poly (aryl ether ketone) block polybutadiene copolymer;
(d) with 2g by 4; the poly (aryl ether ketone) block polybutadiene copolymer of 4-dihydroxy-diphenyl propane preparation is dissolved in the tetrahydrofuran (THF) of 44.3g and stirs; drip 10g acetyl sulphonate then; reacted 12 hours down at 75 ℃; after reaction finishes; product evaporates the 20g tetrahydrofuran (THF) with underpressure distillation; then solution is poured in the ethanol of 230g; NaOH solution 10g with 20% regulates PH to 7-8; the precipitation that obtains behind the suction filtration was used twice of 50g washing with alcohol and vacuum-drying 24 hours again; at last product is heated in 80 ℃ of deionized waters and stirred 3 hours; it is sulfonated polyether sulphone block polybutadiene copolymer 1.620g that suction filtration obtains target product; (wherein the polymerization degree is n=49, m
1=34, m
2=17, p=18), productive rate is 80.6%, and accompanying drawing 1 is the infrared spectra of this embodiment sulphonated poly (aryl ether ketone) block polybutadiene copolymer, FT-IR (KBr): 3030 (phenyl ring, C-H), 291 7 (CH
3), 1640 (C=O), 1593,1495 (phenyl ring), 1236 (aryl oxides), 1040 (S=O, SO
3), 840 (phenyl ring para-orientation), accompanying drawing 2 are nucleus magnetic hydrogen spectrums of this embodiment sulfonated polyether sulphone block polybutadiene copolymer,
1H NMR (DMSO, 400MHz): δ=6.92-7.90 (phenyl ring), 5.5 (CH=CH), 3.3 (CH-SO
3Na), 1.8-2.0 (CH
2), 1.68 (6H, CH
3).
Embodiment 2
(a) take by weighing 4,4 '-difluoro benzophenone 4.360g (0.020mol), 4,4-dihydroxyl phenylbenzene HFC-236fa 7.056g (0.021mol), salt of wormwood 3.174g (0.023mol), add in the three-necked bottle, it is dissolved in 40g N-methyl-2-than in pyrrolidone (NMP) and the 17g toluene and stir, under nitrogen environment, is warming up to 160 ℃ then, react after 4 hours, rise to 190 ℃ of reactions 16 hours again.Reaction is finished postcooling to room temperature, behind the B suction filtration, the liquid that obtains is poured in the 150g methyl alcohol, stir fast simultaneously, precipitated in a large number, filter cake is washed 2 times with methyl alcohol, be placed in 80 ℃ of deionized waters heating then and stirred three hours, suction filtration obtains the polyaryletherketone 9.554g of terminal hydroxy group, productive rate 90.2% again;
(b) take by weighing 1.440g terminal hydroxy group polyaryletherketone, it is dissolved in 32g 1,1,2, in the 2-tetrachloroethane, at room temperature stir to dissolving fully, add the 0.203g p-phthaloyl chloride then, and in reaction soln, drip the 0.15g pyridine, be warming up to 100 ℃, reacted 1 hour, elevated temperature to 150 ℃ reaction is 19 hours again, obtains the polyphenylene oxide ketone of acid chloride end groups;
(c) take by weighing hydroxy-terminated polybutadienes 0.840g and be dissolved in 16g 1,1,2, in the 2-tetrachloroethane, at room temperature stir to dissolving fully, contain 1,1,2 of 1.440g acid chloride end groups polyaryletherketone to its adding then, the solution of 2-tetrachloroethane, drip the 0.15g pyridine at last, be warming up to 100 ℃, reacted 12 hours.After reaction is finished, be cooled to room temperature, pour in the 150g methyl alcohol and precipitate, the filter cake that suction filtration obtains is washed 2 times with methyl alcohol, with 80 ℃ of deionization poach suction filtration after 3 hours, obtains poly (aryl ether ketone) block polybutadiene copolymer;
(d) with 2g by 4; the poly (aryl ether ketone) block polybutadiene copolymer of 4-dihydroxyl phenylbenzene HFC-236fa preparation is dissolved in the N of 47.25g; in N '-dimethyl formamide and stir, drip 10g acetyl sulphonate then, 75 ℃ of reactions 12 hours down; after reaction finishes; product evaporates 20gN with underpressure distillation, and N '-dimethyl formamide pours solution in the methyl alcohol of 230g then; NaOH solution 10g with 20% regulates PH to 7-8; the precipitation that obtains behind the suction filtration was used twice of 50g methanol wash and vacuum-drying 24 hours again, at last product was heated in 80 ℃ of deionized waters and stirred 3 hours, and it is sulfonated polyether sulphone block polybutadiene copolymer 1.732g that suction filtration obtains target product; (wherein the polymerization degree is n=56; m1=39, m2=12, p=17); productive rate is 86.3%; FT-IR (KBr): 3030 (phenyl ring, C-H), 2917 (CH3); 1640 (C=O); 1593,1495 (phenyl ring), 1242 (aryl oxides); 1040 (S=O, SO
3) 840 (phenyl ring para-orientation), 1188,737 (C-F); 1H NMR (DMSO, 400MHz): δ=6.84-7.90 (phenyl ring), 5.5 (CH=CH), 3.3 (CH-SO3Na), 1.8-2.0 (CH2), 1.68 (6H, CH3).
Embodiment 3
(a) take by weighing 4,4 '-difluoro benzophenone 4.360g (0.020mol), 4,4-'-biphenyl diphenol 3.906g (0.021mol), salt of wormwood 3.174g (0.023mol), add in the three-necked bottle, it is dissolved in 37.52g N, in N '-N,N-DIMETHYLACETAMIDE and the 17g toluene and stir, then under nitrogen environment, be warming up to 160 ℃, react after 4 hours, rise to 190 ℃ of reactions 16 hours again.Reaction is finished postcooling to room temperature, behind the B suction filtration, the liquid that obtains is poured in the 150g dehydrated alcohol, stir fast simultaneously, precipitated in a large number, filter cake is washed 2 times with ethanol, be placed in 80 ℃ of deionized waters heating then and stirred three hours, suction filtration obtains the polyaryletherketone 6.152g of terminal hydroxy group, productive rate 82.6% again;
(b) take by weighing 1.120g terminal hydroxy group polyaryletherketone, it is dissolved in 32g 1,1,2, in the 2-tetrachloroethane, at room temperature stir to dissolving fully, add the 0.203g p-phthaloyl chloride then, and in reaction soln, drip the 0.15g pyridine, be warming up to 100 ℃, reacted 1 hour, elevated temperature to 150 ℃ reaction is 19 hours again, obtains the polyphenylene oxide ketone of acid chloride end groups;
(c) take by weighing hydroxy-terminated polybutadienes 0.840g and be dissolved in 16g 1,1,2, in the 2-tetrachloroethane, at room temperature stir to dissolving fully, contain 1,1,2 of 1.120g acid chloride end groups polyaryletherketone to its adding then, the solution of 2-tetrachloroethane, drip the 0.15g pyridine at last, be warming up to 100 ℃, reacted 12 hours.After reaction is finished, be cooled to room temperature, pour in the 150g ethanol and precipitate, the filter cake that suction filtration obtains is washed 2 times with ethanol, with 80 ℃ of deionization poach suction filtration after 3 hours, obtains poly (aryl ether ketone) block polybutadiene copolymer;
(d) with 2g by 4; the poly (aryl ether ketone) block polybutadiene copolymer of 4-'-biphenyl diphenol preparation is dissolved in the tetrahydrofuran (THF) of 44.3g and stirs; drip 10g acetyl sulphonate then; reacted 12 hours down at 75 ℃; after reaction finished, product evaporated the 20g tetrahydrofuran (THF) with underpressure distillation, then solution is poured in the ethanol of 230g; NaOH solution 10g with 20% regulates PH to 7-8; the precipitation that obtains behind the suction filtration was used twice of 50g washing with alcohol and vacuum-drying 24 hours again, at last product was heated in 80 ℃ of deionized waters and stirred 3 hours, and it is sulfonated polyether sulphone block polybutadiene copolymer 1.496g that suction filtration obtains target product; (wherein the polymerization degree is n=34; m1=41, m2=10, p=24); productive rate is 74.6%; FT-IR (KBr): 3030 (phenyl ring, C-H), 2917 (CH3); 1640 (C=O); 1581,1490 (phenyl ring), 1230 (aryl oxides); 1040 (S=O, SO
3), 840 (phenyl ring para-orientation), 998,965 (C-H); 1H NMR (DMSO, 400MHz): δ=6.98-7.86 (phenyl ring), 5.5 (CH=CH), 3.3 (CH-SO3Na), 1.8-2.0 (CH2), 1.68 (6H, CH3).
Claims (4)
1. sulphonated poly (aryl ether ketone) block polybutadiene copolymer is characterized in that repeated structural unit is shown below:
Wherein the polymerization degree is respectively, n=20-100, m
1=1-80, m
2=1-40, p=5-50.
2. the preparation method of sulphonated poly (aryl ether ketone) block polybutadiene copolymer as claimed in claim 1 is characterized in that the preparation method is as follows: followingly all represent with mass parts
(a) with 1-2 part diphenol monomer and 1 part 4,4 '-difluoro benzophenone at room temperature is dissolved in the mixed organic solvents of 5-30 part, under nitrogen environment, be warming up to 160 ℃, react after 1-4 hour, rise to 190 ℃ of reactions 14-20 hour again, after reaction finishes, reaction product is cooled to room temperature, behind the B suction filtration, filtrate is poured in 25-70 part methyl alcohol or the alcohol solvent, stir fast simultaneously, generate precipitation, behind the suction filtration filter cake is placed in 80 ℃ of deionized waters heating and stirred 2-5 hour, suction filtration obtains the polyaryletherketone of terminal hydroxy group again; Wherein mixed organic solvents is N-N-methyl-2-2-pyrrolidone N-and toluene or N, N '-N,N-DIMETHYLACETAMIDE and toluene, and N-N-methyl-2-2-pyrrolidone N-wherein, N, the mass ratio of N '-N,N-DIMETHYLACETAMIDE and toluene is 1.5: 1-4: 1;
(b) 5-10 part terminal hydroxy group polyaryletherketone is dissolved in 100-500 part 1,1,2, in the 2-tetrachloroethane, add 1-5 part terephthalyl chloride then, and in reaction soln, drip 1-5 part pyridine, be warming up to 100 ℃, reacted 1-5 hour, and elevated temperature to 150 ℃ backflow 10-30 hour again, obtained the polyaryletherketone of acid chloride end groups;
(c) 1-5 part hydroxy-terminated polybutadienes is added 15-50 part 1,1,2, in the 2-tetrachloroethane, at room temperature stir, contain 1 of 2-10 part acid chloride end groups polyaryletherketone to its adding then to dissolving fully, 1,2, the solution of 2-tetrachloroethane adds 0.2-1 part pyridine at last again as catalyzer, be warming up to 100 ℃, reacted 6-24 hour, and after reaction is finished, be cooled to room temperature, pour in 500-1500 part methyl alcohol or the ethanol and precipitate, the filter cake that suction filtration obtains is washed 2 times with 20-40 part methyl alcohol or ethanol, with 80 ℃ of deionization poach suction filtration after 2-5 hour, obtains poly (aryl ether ketone) block polybutadiene copolymer;
(d) 1 part of poly (aryl ether ketone) block polybutadiene copolymer is dissolved in the tetrahydrofuran (THF) or the N of 15-40 part; in N '-dimethyl formamide and stir; drip the acetyl sulphonate of 0.5-10 part then; reacted 5-24 hour down at 40 ℃-100 ℃; after reaction finishes; 7-20 part tetrahydrofuran (THF) or N are removed in underpressure distillation; N '-dimethyl formamide; then solution is poured in the methyl alcohol or alcohol solvent of 100-200 part; solution with 5-20 part 20%NaOH is regulated PH to 7-8; the precipitation that obtains behind the suction filtration is used twice of 20-40 part methyl alcohol or washing with alcohol and vacuum-drying 12-24 hour again; product heats in 80 ℃ of deionized waters and stirred 2-5 hour the most at last, and it is sulphonated poly (aryl ether ketone) block polybutadiene copolymer that suction filtration obtains target product.
3. the preparation method of sulphonated poly (aryl ether ketone) block polybutadiene copolymer according to claim 2 is characterized in that the diphenol monomer is 4,4-dihydroxy-diphenyl propane, 4,4-dihydroxyl phenylbenzene HFC-236fa or 4,4-'-biphenyl diphenol.
4. the preparation method of sulphonated poly (aryl ether ketone) block polybutadiene copolymer according to claim 2 is characterized in that the structure of hydroxy-terminated polybutadienes is shown below:
Wherein, polymerization degree m=20-100.
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| KR101202331B1 (en) * | 2006-02-20 | 2012-11-16 | 삼성에스디아이 주식회사 | A multiblock copolymer, a method for preparing the multiblock copolymer, a polymer electrolyte membrane prepared from the multiblock copolymer, a method for preparing the polymer electrolyte membrane and a fuel cell employing the polymer electrolyte membrane |
| CN101698706B (en) * | 2009-10-29 | 2011-07-27 | 上海交通大学 | Block copolymer of polyetheretherketone and sulfonated polybutadiene and preparation method thereof |
| CN101696274B (en) * | 2009-10-29 | 2011-07-27 | 上海交通大学 | Total sulfonating segmented copolymer of polyether-ether-ketone and polybutadiene and preparation method thereof |
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