CN101735375A - Ionic polymer and application thereof as proton exchange fiber material - Google Patents
Ionic polymer and application thereof as proton exchange fiber material Download PDFInfo
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- CN101735375A CN101735375A CN200810159975A CN200810159975A CN101735375A CN 101735375 A CN101735375 A CN 101735375A CN 200810159975 A CN200810159975 A CN 200810159975A CN 200810159975 A CN200810159975 A CN 200810159975A CN 101735375 A CN101735375 A CN 101735375A
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Abstract
The invention relates to an ionic polymer and application thereof as proton exchange fiber material. The polymer contains a perfluoro polymer backbone and a branch chain connected with the polymer backbone, and has a structure shown in the following formula (I), in the formula (I) R is -CF3, -C2F5 or -C3F7, or -OCF3 or -OC2F5 or -OC3F7, x, y and z are respectively integers ranging from 1 to 10000, and x/(x+y+z) is equal to 85-97%, y/(x+y+z) is equal to 0.8-8%, z/(x+y+z) is equal to 0-10%, all the ratios are mol ratios, wherein m is 1 or 2 and n is an integer ranging from 1 to 6; the fluorine-containing polymer is subject to melting spinning by a general melting spinning device to prepare various types of polymer fiber, the polymer fiber is woven into a fiber mesh by weaving technology to be as reinforcement mesh material of proton exchange membrane and chlor-alkali ion membrane, thus achieving reinforcement and improving capacity in ion exchange.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of ionic polymer particularly and as the application of proton-exchange fiber material.
Background technology:
Owing to when the chlor-alkali perfluorinated ionic membrane is applied to the chlor-alkali groove, in assembling and use, all will bear certain mechanical shock, so the chlor-alkali film must have enough physical strengths, must strengthen, could life-time service.For take into account the conductivity of perfluorinated ionic membrane in electrolytic process, contend with by electrolytic solution form, concentration and temperature etc. change and be subjected to the impact of various stress, will strengthen framework material to be embedded in the film, can reach film enhanced purpose.In addition, in use, fuel cell membranes faces strength problem too, and preparation has the cluster ion exchange membrane that strengthens net, also is to improve effective ways expanding use range its work-ing life.
Facts have proved, by the various fabrics of fluorofibre braiding, reinforced effects the best of in the chlorine industry ionic membrane, using.The modified Teflon fortifying fibre is one of main raw of chlor-alkali ionic membrane, has same market demand amount with the chlor-alkali ionic membrane.Simultaneously, this enhancing netting gear has the chemical resistance and the very high intensity of excellent thermotolerance, excellence, almost can substitute all industrial employed filtering materials now.
In addition, because the ion-exchange membrane that perfluorochemical ion membrane in chlor-alkali industry and fuel cell are used all has suitable ion exchangeable, when introducing the enhancing framework material, to reduce its conductivity and ion-exchange capacity inevitably.And when not influencing enhancing framework material intensity, on the enhancing framework material, also introduce a certain amount of ion-exchange group, be an extraordinary solution.
CN1608734 discloses a kind of manufacture method of strong acid ion exchange fiber.This manufacture method comprises: 1. radiation grafting: polytetrafluoroethylene fiber is put into the vinylbenzene that volume percent is 10-70: 30-90: the homogeneous mixture solotion of methylene dichloride preparation, feeding nitrogen protects, after at room temperature using co-60 radiation 24-80 hour by radiation dose 15-30KGy, take out and clean, can get the tetrafluoroethylene grafted fibre; 2. grafted fibre sulfonation: the chlorsulfonic acid of gained tetrafluoroethylene grafted fibre being put into volume percent 30-40: 60-70: the homogeneous mixture solotion of tetrachloroethane preparation, under 90-100 ℃, carry out sulfonation reaction, the cooling afterwash, get final product described strong acid ion exchange fiber.Because the strong stability and the high compactness of polytetrafluoroethylene fiber itself, this method can only be carried out grafting at fiber surface; In addition because radiation grafted method is not great majority research or production unit all has ready conditions and carry out, so its versatility is subjected to certain restriction.
Summary of the invention
For this reason, at the deficiencies in the prior art, the invention provides a kind of polymkeric substance based on tetrafluoroethylene, promptly a kind of side chain has the fluorine resin of sulfonic acid group, this polymkeric substance by three kinds of fluorochemical monomer polymerizations under certain condition after sulfonation form, have advantage cheap and easy to get.The present invention also provides and contains the ion exchange fiber material that this side chain has the fluorine resin of sulfonic acid group.
The invention provides the fluorine resin that a kind of side chain has sulfonic acid group, this polymkeric substance contains a kind of main polymer chain and the side chain that is connected with main polymer chain, and its main chain is a perfluoroalkyl, it is characterized in that, has the general formula shown in the formula (I):
R is-CF in the formula
3,-C
2F
5,-C
3F
7,-OCF
3,-OC
2F
5Or-OC
3F
7X, y, z are respectively 1～10000 integer; And x/ (x+y+z)=85～97%, y/ (x+y+z)=0.8～8%, z/ (x+y+z)=0～10% is mol ratio; Wherein, m is 1 or 2, and n is the integer of 1-6.
Side chain of the present invention has the fluorine resin of sulfonic acid group, in its branched structure formula, and group-(CF2)
n-SO
3H is connected to contraposition, ortho position or a position of the chemical bond that is connected with main chain in the phenyl ring.
Preferably, to have the number-average molecular weight of the fluorine resin of sulfonic acid group be 80000-1000000 to side chain; The loading capacity that side chain has the fluorine resin of sulfonic acid group is 0.05-0.50mmol/g.
The present invention also provides side chain to have the preparation method of the fluorine resin of sulfonic acid group, comprises the following steps:
1) with tetrafluoroethylene, tetrafluoroethylene derivative and α, β, β-trifluorostyrene causes copolymerization through free radical and obtains precursor polymer in the presence of dispersion agent, water and initiator; Described dispersion agent is the perfluoroalkyl ethers dispersion agent that contains the trimeric cyanamide structure; Tetrafluoroethylene, α, β, the feed ratio of β-trifluorostyrene and tetrafluoroethylene derivative is 85～97: 0.8～8: 0～10, mol ratio;
2) in the presence of catalyzer and in the nitrogen atmosphere, in anhydrous solvent,, isolate the polymkeric substance of the sulfoalkylization that obtains, acidifying then with precursor polymer and the sulfoalkyl reagent contact reacts that step 1) obtains; Obtain having the fluorine resin of sulfonic acid group.
Preferably, the described tetrafluoroethylene derivative of step 1) is selected from R 1216, perfluor 1-butylene, perfluor 1-amylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether or perfluoro propyl vinyl ether.
The described perfluoroalkyl ethers dispersion agent that contains the trimeric cyanamide structure of step 1) is the melamine derivative that a class has the perfluoroalkyl ethers chain link, and its general molecular formula is:
A+b=2 wherein, b is 0 or 1, and c is 1～10 integer.
Preferably, the described initiator of step 1) is selected from Diisopropyl azodicarboxylate or dibenzoyl peroxide.
Preferably, step 2) precursor polymer and the catalytic temperature of reaction of sulfoalkyl reagent are 0-200 ℃ in, and the time of reaction is 1-200 hour.
Step 2) catalyzer described in is selected from one or more in aluminum trichloride (anhydrous), Anhydrous Ferric Chloride, solid phosphoric acid, hydrogen fluoride, the pure aluminium silicate; Step 2) reagent of sulfoalkyl described in is selected from 1,3-perfluoropropane sultone, 1,4-perfluorinated butane sultone, 1,5-perflenapent sultone, 1, one or more in the 6-perflexane sultone; Step 2) anhydrous solvent is selected from anhydrous chloroform, anhydrous ethylene dichloride, anhydrous cyclohexane, anhydrous dimethyl Asia sough (DMSO), anhydrous N in, in dinethylformamide (DMF), anhydrous N,N-dimethylacetamide (DMAc), anhydrous N-Methyl pyrrolidone (NMP), anhydrous propanone, anhydrous pimelinketone, the anhydrous oil of mirbane one or more.
Step 2) mol ratio of sulfoalkyl reagent, catalyzer, the polymkeric substance that contains phenyl ring and anhydrous solvent is 1 in: (0.1～5): (0.01～2): (4～25).
Step 2) described acidifying, can adopt any known method to carry out, can use any known acid or acidic solution, example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid etc., concentration to acidic solution does not have special requirement, and the dilute solution or the strong solution of acid all can meet the requirements of acidizing effect.
The present invention also provides side chain to have the application of the fluorine resin of sulfonic acid group, this fluorine resin adopts general apparatus for melt spinning to carry out each polymer fiber of melt-spinning system, polymer fiber is woven into fibrous reticulum by textile technology, as the enhancing net materials of proton exchange membrane and chlor-alkali ionic membrane.
Preferably, this resin can be by melt extruding spinning, prepare the fluorine-contained polymerisate fibre material with ion exchanging function in 200-400 ℃ of scope; It melt extrudes at least 350 ℃ of die head temperatures; Spinning speed is 0.75～750m/min; Spinning equipment adopts the Langaloy material at high temperature and the part that contacts with resin during spinning, prevents to introduce foreign ion and pollute fiber in resin;
Fluorine resin of the present invention, it is fluoropolymer with ion exchanging function, can be prepared into filamentary material by general spining technology with ion exchanging function, be woven into fibrous reticulum by common textile technology, the enhancing net materials of the battery proton exchange membrane that acts as a fuel and chlor-alkali ionic membrane reaches enhancing and improves ion-exchange capacity simultaneously.
The polymerization process of polymkeric substance proposed by the invention, its unique distinction be, the mixing solutions of selecting the perfluoroalkyl ethers that contains the trimeric cyanamide structure and water for use is as dispersing agent.The fluoropolymer of preparing with this this dispersing agent system has ion exchanging function, can carry out spinning by the mode that melt extrudes and prepare fortifying fibre.
The perfluoroalkyl ethers dispersion agent that contains the trimeric cyanamide structure provided by the present invention is the melamine derivative that a class has the perfluoroalkyl ethers chain link, and its general molecular formula is:
A+b=2 wherein, b is respectively 0,1, and c is 1～10 integer.
The perfluoroalkyl ether solvents that this class contains the trimeric cyanamide structure has very high boiling point, and this kind solvent has good solvability to monomer and product, its decomposition temperature surpasses 350 ℃, can solve having a strong impact on that solvent evaporates causes in the polymerization, and improves monomeric transformation efficiency.
The above-mentioned preparation that has the melamine derivative of perfluoroalkyl ethers chain link can be selected any one method of this area for use, and the preparation of the melamine derivative about the perfluoroalkyl ethers chain link of the present invention is referring to 200510044978.90.
The present invention is made respectively go out have a low ion exchange capacity fluoropolymer, can be at present general apparatus for melt spinning extruding spinning, under pressure molten polymer is extruded by the spinning die head after by apparatus for melt spinning and to be formed the fusion tow polymer melt, after drawing-off, oriented crystalline, cooling, formation has low ion exchange capacity, high strength fibre.As the enhancing net materials of proton exchange membrane and chlor-alkali ionic membrane, can increase the useful area of cation permeation film, corresponding reduction membrane resistance and bath voltage have well solved the technical barrier of present this area.
The invention has the beneficial effects as follows and adopt relatively inexpensive starting material monomer to be prepared precursor polymer, precursor polymer obtains the polymkeric substance that the present invention proposes after sulfonation.This manufacturing process has avoided the high perfluoroalkyl vinyl ether of use cost as the monomer of introducing ion-exchange group, and use common α instead, β, β-trifluorostyrene, in that the side chain that contains phenyl ring is just arranged after the polymerization, on side chain, introduce sulfonic acid group simply with ion exchanging function by method of sulfonating on main polymer chain.The fluoropolymer of resulting tool ion exchanging function, can be prepared into filamentary material by general spining technology with ion exchanging function, be woven into fibrous reticulum by common textile technology, the enhancing net materials of the battery proton exchange membrane that acts as a fuel and chlor-alkali ionic membrane reaches enhancing and improves ion-exchange capacity simultaneously.
Embodiment:
The measuring method of the loading capacity of polymkeric substance provided by the invention (IEC) adopts alkali formula titration measuring, and determination step is: 1. with polymkeric substance provided by the invention 120 ℃ of following vacuum-dryings 6 hours; 2. the M (gram) that dried polymkeric substance provided by the invention weighed, and immerse in the certain density sodium hydroxide solution of 50mL, under 50 ℃, stirred or leave standstill 24 hours, to carry out ion-exchange fully; 3. be indicator with phenolphthalein, get 20mL soak solution (must not sucking-off resin particle), with the finite concentration hydrochloric acid soln to its titration, the consumption of record hydrochloric acid soln; 4. calculate loading capacity or proton exchange capacity by following formula:
c
1: the volumetric molar concentration of standard caustic soda solution, the mol/L of unit;
c
2: the volumetric molar concentration of hydrochloric acid standard solution, the mol/L of unit;
V: the volume of the hydrochloric acid standard solution that the titration sodium hydroxide solution spends, Unit;
M: the quality of perfluorinated sulfonic resin in the tool plug Erlenmeyer flask, the g of unit.
Following embodiment will the present invention is described in further detail, but the invention is not restricted to these specific exampless.Example 1-6 has described the preparation and the sulfonation of various polymkeric substance; Example 7 and 8 has been described the preparation that sulfonated polymer is applied to ion exchange fiber material.
Embodiment 1:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent, α, β, β-trifluorostyrene 4.5g and 0.2g peroxidation benzene first formyl, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, R 1216 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 4.35%, and the R 1216 weight percentage is 5.05%, and the tetrafluoroethylene weight percentage is 90.60%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous oil of mirbane and 12.2 grams 1 again, 3-perfluoropropane sultone.After polystyrene resin fully dissolves, slowly add 14.7 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.
The IEC value of this polymkeric substance is 0.08mmol/g.
Embodiment 2:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent, α, β, β-trifluorostyrene 4.5g and 0.2g peroxidation benzene first formyl, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluoroethylvinyl ether 7g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 4.35%, and the perfluoroethylvinyl ether weight percentage is 5.65%, and the tetrafluoroethylene weight percentage is 90.00%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous N,N-dimethylacetamide (DMAc) and 12.2 grams 1 again, 4-perfluorinated butane sultone.After polymer resin fully dissolves, slowly add 14.7 gram Anhydrous Ferric Chlorides again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.
The IEC value of this polymkeric substance is 0.11mmol/g.
Embodiment 3:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent, α, β, β-trifluorostyrene 9.5g and 0.2g peroxidation benzene first formyl, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluor 1-butylene 7g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 7.45%, and perfluor 1-butylene weight percentage is 3.35%, and the tetrafluoroethylene weight percentage is 89.20%.
(2) sulfonation is handled
Add the polymer powder that obtains in the 13 gram steps (1) in the four-hole boiling flask that is connected with nitrogen protection, add again to sough (DMSO) in 50 milliliters of anhydrous dimethyl Asias and 12.2 restrain 1,2-R 116 sultone.After fluoropolymer resin fully dissolves, slowly add 14.7 gram pure aluminium silicate again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.
The IEC value of this polymkeric substance is 0.43mmol/g.
Embodiment 4:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent, α, β, β-trifluorostyrene 8.7g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluor 1-butylene 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 6.75%, and perfluor 1-butylene weight percentage is 4.33%, and the tetrafluoroethylene weight percentage is 89.92%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add in 50 milliliters of anhydrous pimelinketone again and 12.5 grams 1,2-R 116 sultone.After fluoropolymer resin fully dissolves, slowly add 14.7 gram anhydrous hydrogen fluorides again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.
The IEC value of polymkeric substance is 0.32mmol/g.
Embodiment 5:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent, α, β, β-trifluorostyrene 7.7g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluoro methyl vinyl ether 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 6.55%, and the perfluoro methyl vinyl ether weight percentage is 3.62%, and the tetrafluoroethylene weight percentage is 89.83%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous oil of mirbane and 12.5 grams 1 again, 2-R 116 sultone.After fluoropolymer resin fully dissolves, slowly add 14.7 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 50 ℃ then, and reaction was carried out 100 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.
The IEC value of polymkeric substance is 0.31mmol/g.
Embodiment 6:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as a minute routine powder/solvent, α, β, β-trifluorostyrene 8.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluoro propyl vinyl ether 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 5.65%, and the perfluoro propyl vinyl ether weight percentage is 4.43%, and the tetrafluoroethylene weight percentage is 89.92%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous N-Methyl pyrrolidone (NMP) and 12.5 grams 1 again, 2-R 116 sultone.After fluoropolymer resin fully dissolves, slowly add 14.7 gram anhydrous solid phosphoric acid again.Under the condensing reflux state, keeping temperature of reaction is 180 ℃ then, and reaction was carried out 2 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.
The IEC value of polymkeric substance is 0.26mmol/g.
Embodiment 7:
Main chain perfluoro polymer material among the embodiment 1 has been carried out melt-spinning, adopt the single screw extrusion machine monofilament to extrude, 350 ℃ of 320 ℃ of screw extrusion press temperature of melt zone temperature, 405 ℃ of nozzle plate temperature, 500 meters/minute of drawing speeds, adopt traditional batching with winding apparatus to collect the fiber of extruding, the filament strength of fiber surpasses 30MPa, and the control drawing speed makes filament denier between 50～200 dawn.
Embodiment 8:
More than synthetic have the loading capacity fluoropolymer and all can adopt the spinning processes of embodiment 7 to carry out spinning to prepare the polymer fiber that satisfies service requirements, these fibers can further be woven into polymeric web by Weaving method, and various mould materials are strengthened.
Claims (9)
1. a side chain has the fluorine resin of sulfonic acid group, and this polymkeric substance contains a kind of main polymer chain and the side chain that is connected with main polymer chain, and its main chain is a perfluoroalkyl, it is characterized in that, has the general formula shown in the formula (I):
R is-CF in the formula
3,-C
2F
5,-C
3F
7,-OCF
3,-OC
2F
5Or-OC
3F
7X, y, z are respectively 1～10000 integer; And x/ (x+y+z)=85～97%, y/ (x+y+z)=0.8～8%, z/ (x+y+z)=0～10% is mol ratio; Wherein, m is 1 or 2, and n is the integer of 1-6;
2. side chain as claimed in claim 1 has the fluorine resin of sulfonic acid group, it is characterized in that, the number-average molecular weight that side chain has the fluorine resin of sulfonic acid group is 80000-1000000; The loading capacity that side chain has the fluorine resin of sulfonic acid group is 0.05-0.50mmol/g;
3. the preparation method with fluorine resin of sulfonic acid group as claimed in claim 1 comprises the following steps:
1) with tetrafluoroethylene, tetrafluoroethylene derivative and α, β, β-trifluorostyrene causes copolymerization through free radical and obtains precursor polymer in the presence of dispersion agent, water and initiator, and described dispersion agent is the perfluoroalkyl ethers dispersion agent that contains the trimeric cyanamide structure; Tetrafluoroethylene, α, β, the feed ratio of β-trifluorostyrene and tetrafluoroethylene derivative is 85～97: 0.8～8: 0～10, mol ratio;
2) in the presence of catalyzer and in the nitrogen atmosphere, in anhydrous solvent,, isolate the polymkeric substance of the sulfoalkylization that obtains, acidifying then with precursor polymer and the sulfoalkyl reagent contact reacts that step 1) obtains; Obtain having the fluorine resin of sulfonic acid group;
4. the preparation method with fluorine resin of sulfonic acid group as claimed in claim 3, it is characterized in that the described tetrafluoroethylene derivative of step 1) is selected from R 1216, perfluor 1-butylene, perfluor 1-amylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether; The described initiator of step 1) is selected from Diisopropyl azodicarboxylate or dibenzoyl peroxide;
5. the preparation method with fluorine resin of sulfonic acid group as claimed in claim 3 is characterized in that step 2) in precursor polymer and the catalytic temperature of reaction of sulfoalkyl reagent be 0-200 ℃, the time of reaction is 1-200 hour;
6. the preparation method with fluorine resin of sulfonic acid group as claimed in claim 3 is characterized in that step 2) described in catalyzer be selected from aluminum trichloride (anhydrous), Anhydrous Ferric Chloride, solid phosphoric acid, hydrogen fluoride, the pure aluminium silicate one or more; Step 2) reagent of sulfoalkyl described in is selected from 1,3-perfluoropropane sultone, 1,4-perfluorinated butane sultone, 1,5-perflenapent sultone, 1, one or more in the 6-perflexane sultone; Step 2) anhydrous solvent is selected from anhydrous chloroform, anhydrous ethylene dichloride, anhydrous cyclohexane, anhydrous dimethyl Asia sough (DMSO), anhydrous N in, in dinethylformamide (DMF), anhydrous N,N-dimethylacetamide (DMAc), anhydrous N-Methyl pyrrolidone (NMP), anhydrous propanone, anhydrous pimelinketone, the anhydrous oil of mirbane one or more;
7. the preparation method with fluorine resin of sulfonic acid group as claimed in claim 3, it is characterized in that step 2) in the mol ratio of sulfoalkyl reagent, catalyzer, the polymkeric substance that contains phenyl ring and anhydrous solvent be 1: (0.1～5): (0.01～2): (4～25);
8. the described side chain of claim 1 has the application of the fluorine resin of sulfonic acid group, this fluorine resin adopts general apparatus for melt spinning to carry out each polymer fiber of melt-spinning system, polymer fiber is woven into fibrous reticulum by textile technology, as the enhancing net materials of proton exchange membrane and chlor-alkali ionic membrane;
9. the described side chain of claim 8 has the application of the fluorine resin of sulfonic acid group, it is characterized in that, this resin can be by melt extruding spinning, prepare the fluorine-contained polymerisate fibre material with ion exchanging function in 200-400 ℃ of scope; It melt extrudes at least 350 ℃ of die head temperatures; Spinning speed is 0.75～750m/min; Spinning equipment adopts the Langaloy material at high temperature and the part that contacts with resin during spinning, prevents to introduce foreign ion and pollute fiber in resin.
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