CN102276842B - Preparation method of grafting and cross-linking type polymer for proton exchange membrane and proton exchange membrane - Google Patents
Preparation method of grafting and cross-linking type polymer for proton exchange membrane and proton exchange membrane Download PDFInfo
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- CN102276842B CN102276842B CN2011101353914A CN201110135391A CN102276842B CN 102276842 B CN102276842 B CN 102276842B CN 2011101353914 A CN2011101353914 A CN 2011101353914A CN 201110135391 A CN201110135391 A CN 201110135391A CN 102276842 B CN102276842 B CN 102276842B
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Abstract
The invention discloses a grafting and cross-linking type polymer for a proton exchange membrane and a preparation method of the proton exchange membrane. The synthesis of the polymer is as follows: (1) a hydrophobic main chain high-molecular polymer possessing side chain reaction activity is synthesized by a coupling reaction; (2) an oligomer containing reaction active end group is synthesized by a nucleophilic substitution reaction; (3) a quantitative reaction between the hydrophilic oligomer and the hydrophobic main chain high-molecular polymer is conducted to prepare a series of grafting and cross-linking type polymers with different structures. The grafting and cross-linking type proton exchange membrane is obtained by solvent casting method. According to the invention, the synthesis technology is simple, the sulfonation degree and the crosslinking degree are controllable, and the prepared proton exchange membrane has advantages of uniform structure, good dimension stability and high conductivity under the condition of low humidity.
Description
Technical field
The invention belongs to the preparing technical field of a class proton exchange membrane, particularly the preparation method of a class graft crosslinking type sulfonated polyether sulphone proton exchange membrane.
Background technology
Sulfonated polymer films has been widely used in fields such as fuel cell, chlorine industry, ion exchange resin, membrane separation technique and humidity sensors.
In Proton Exchange Membrane Fuel Cells, proton exchange membrane is one of key part.At present commercial available proton exchange membrane is the perfluorinated sulfonic acid polymeric membrane, and such as the Nafion series of DuPont company etc., this class film has high specific conductivity, the excellent advantages such as chemical stability.But fancy price, lower working temperature, the environmental problem that higher methanol permeability and fluorine material bring etc. has limited its commercial applications.Developing high performance non-fluorine type proton exchange membrane becomes the study hotspot in this field.Mainly concentrate at present the non-fluorine hydrocarbon macromolecular material of complete fragrant type aspect, the effort through more than ten years makes great progress, but from the practical application in fuel cell, also has larger gap.As aspect the weather resistance, 80
oUnder the service temperature of C, Nafion can reach more than 20,000 5 thousand hours, and under similarity condition, the fluorine-free sulfonated polymer films of report is no more than 10,000 hours at present; In addition, the specific conductivity when low humidity (＜50%) will be far below Nafion film etc.
Sulfonated polyether sulphone (SPAES) is the comparatively excellent sulfonated polymer films of a kind of performance, such as document 1(Fuel Cells, 2005,5:201) disclosed technology shows, has the advantages such as specific conductivity height, thermostability and chemical stability be better based on the proton exchange membrane of SPAES.The sulfonic acid group of this class material often all directly is connected on the main chain, obtaining higher specific conductivity must be based on self higher loading capacity (IEC) level, but when the IEC level was increased to a certain degree, often the consequent was that larger problem appears in the dimensional stability of mould material in water.For example 40% sulfonation degree SPAES is 130
oThe C high-temperature water was processed after 48 hours, and physical dimension increases more than 100%.In addition, yet there is larger problem in the stability to hydrolysis of SPAES film in water, and the measuring mechanical property result after condition is processed as mentioned above shows, the maximum elongation rate of it is disrumpent feelings point is down to 20% by 160%, Young's modulus is down to 56MPa by 89MPa, and showing has hydrolysis to occur in the water treatment procedure.Therefore, SPAES wants to be applied to fuel cell, and especially high-temperature fuel cell (～120
oC), must carry out the SPAES film on the structure a series of perfect.
Introducing Grafting Structure is relatively more novel at present a kind of means, the polyether sulphone of the multiplex non-sulfonation of this class material is as main chain, sulfonic acid group then is introduced on the side chain, such as document 2(Advanced Functional Materials 2007,17,2823) disclose a kind of pass through commercial polyether sulphone (Udel) and n-Butyl Lithium reaction, then with to fluorobenzoyl chloride reacted, with the phenols reaction that contains sulfonic acid group, obtain the method for graft type sulfonated polyether sulphone again.The proton exchange membrane of Grafting Structure be easy to form microcosmic hydrophilic with the separating of hydrophobic region so that mould material can obtain higher specific conductivity a relatively low IEC level.But the same problem that exists is that the easier suction that this class mould material often shows is not so that its dimensional stability in water is still well improved.At this moment, introducing crosslinking structure on the basis of branched structure is to improve one of the effective ways of the stability of sulfonated polymer films again.
Summary of the invention
The object of the present invention is to provide a kind of graft crosslinking type polymkeric substance for proton exchange membrane and the preparation method of proton exchange membrane.
The technical solution that realizes the object of the invention is: a kind of graft crosslinking type polymkeric substance for proton exchange membrane, polymkeric substance has hydrophobic polyarylether, polyaryletherketone or polyether sulphone main chain and hydrophilic sulfonated polyether, polyaryletherketone or polyether sulphone graft side chain, simultaneously with graft side chain as linking agent;
This polymkeric substance is standby in order to the below legal system:
The first step is by changing dihalo thing (I) and the kind of dihalo thing (II) and the hydrophobic polymer main chain product P P that ratio obtains different structure, hard and soft property and chain length that adds; Be about to dry nickel catalyzator and non-proton type polar organic solvent and add in the reactor, after question response system color becomes scarlet, add the reaction of dihalo thing (I) and dihalo thing (II), wherein dihalo thing (I) is with the side chain reaction active groups; After reaction finishes, dilute and pour in the aqueous hydrochloric acid, separate out fibrous product, after filtration, after the washing, oven dry obtains non-sulfonated polymer main chain product;
Second step, obtain the full sulfonation oligopolymer of different chain lengths by the ratio that changes sulfonation dihalo thing monomer and dihydroxy compound monomer, and then by with the PP of different structure reaction, obtain the graft crosslinking type sulfonated polymer product P P-SPAES of different ions exchange capacity; Namely at first the sulfonation dihalo thing (III) of drying, dihydroxy compound (IV or V) are added in the reactor with non-proton type polar organic solvent, until completely dissolved, adding with respect to the excessive salt of wormwood of hydroxyl mole number as catalyzer, add dry toluene as azeotropic aqua, be down to room temperature after the reaction; Then with dried PP according to etc. stoichiometry add temperature reaction in the reaction solution; The dilution and slowly be poured into water, separate out fibrous product, after filtration, the washing after, the oven dry, obtain PP-SPAES;
In the 3rd step, above-mentioned polymer dissolution in non-proton type polar organic solvent, is watered and cast from the glass plate, behind air drying, film is peeled off from sheet glass, with dilute sulphuric acid or the exchange of dilute hydrochloric acid room temperature, be washed to neutrality, vacuum drying namely obtains proton type graft crosslinking type exchange membrane.
The present invention compared with prior art, its remarkable advantage:
(1) provide a kind of method of producing simply and easily graft crosslinking type sulfonation proton exchange membrane, this method is based on the hydrophobic backbone that coupling polymerization reaction preparation has certain hard and soft property; On the basis that has prepared hydrophilic oligomers, utilize the nucleophilic substitution reaction of the active group of hydrophilic oligomers active end group and hydrophobic main chain side chain, prepare graft crosslinking type high molecular polymer.
(2) compared with prior art, it is simple to have a synthesis technique, the advantage that sulfonation degree is controlled.Compare with existing random copolymerization film, on low IEC level, can prepare the proton exchange membrane with hydrophilic-hydrophobic micro phase separation structure, the proton exchange membrane that obtains simultaneously has the structure homogeneous, electric conductivity advantages of higher under good stability of the dimension, the low humidity.
(3) the graft crosslinking type sulfonation proton exchange membrane that can synthesize other similar structures simultaneously by identical mode satisfies the especially needs in the fields such as fuel cell, chlorine industry, ion exchange resin, membrane sepn and humidity sensor of relevant field.
Description of drawings
Fig. 1 is the synthesis step of graft crosslinking type sulfonated polymer and the technical process for preparing proton exchange membrane with this polymkeric substance.
Fig. 2 is the specific conductivity-relative humidity variations result of embodiment of the invention 1-6 proton exchange membrane, is reference with Nafion112 simultaneously.The result shows that the proton exchange membrane that the present invention obtains has higher specific conductivity at low humidity (≤70%), approaches with Nafion112, in IEC 〉=1.65 and relative humidity 〉=85% the time, its specific conductivity is greater than Nafion112.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
The present invention is used for the graft crosslinking type polymkeric substance of proton exchange membrane, by regulating with the dihalo thing (I) of side chain reactive functional and the chain length that does not change non-sulfonation main chain with dihalide (II) proportioning of side chain reactive functional, simultaneously by regulating sulfonation dihalo thing (III), the mol ratio of dihydroxy compound (IV or V), perhaps change the structure of III and IV or V, obtain different types of graft crosslinking type sulfonated polymer through polyreaction, form the proton type polymkeric substance with this different sorts graft crosslinking type sulfonated polymer through proton exchange again.Fig. 1 is seen in the technical process of preparation.Its step is as follows:
The first step, the preparation of non-sulfonation main chain (PP)
Catalyzer (NiBr with drying
2, PPh
3With the Zn powder) mix in the adding reactor with non-proton type polar organic solvent, after question response system color becomes scarlet, add a certain proportion of dihalo thing (I) and dihalo thing (II), wherein dihalo thing (I) is with the side chain reaction active groups.60-140
oC reaction 1-24 hour.After reaction finished, dilution was also slowly poured in the 2M aqueous hydrochloric acid, separates out fibrous product, and after filtration, after the washing, oven dry obtains non-sulfonated polymer main chain product.By changing dihalo thing (I) and the kind of dihalo thing (II) and the non-sulfonated polymer main chain product that ratio obtains different structure and chain length that adds.Wherein the part with functional group mainly provides rigid element, and rest part mainly provides flexible unit.
Second step, the preparation (PP-SPAES) of graft crosslinking type sulfonation proton exchange membrane
Sulfonation dihalo thing (III), the dihydroxy compound (IV or V) of drying are added in the reactor with non-proton type polar organic solvent, until completely dissolved, adding with respect to the salt of wormwood of the excessive 10-30 % of hydroxyl mole number as catalyzer, add dry toluene as azeotropic aqua, be down to room temperature behind the high temperature temperature reaction certain hour.Then with dried PP according to etc. stoichiometry add in the reaction solution, be warming up to 90-180
oC reaction 4-48 hour.The dilution and slowly be poured into water, separate out fibrous product, after filtration, the washing after, the oven dry, obtain PP-SPAES.Obtain the full sulfonation oligopolymer of different chain lengths by the ratio that changes sulfonation dihalo thing monomer and dihydroxy compound monomer, so by with the PP reaction of different structure, obtain the PP-SPAES of different ions exchange capacity.With above-mentioned polymer dissolution in containing the non-proton type polar organic solvent of dehydrated crosslinking agent, water and cast from the glass plate, behind air drying, film is peeled off from sheet glass, through about 1-5M hydrochloric acid or 0.5-2.5M sulfuric acid exchange 24-72h, wash with water to neutrality, vacuum drying obtains proton type graft crosslinking type exchange membrane.
The non-proton type polar organic solvent that can be used as reaction has: methyl-sulphoxide, METHYLPYRROLIDONE, N,N-dimethylacetamide and DMF.
In the graft crosslinking type proton exchange membrane preparation method of the present invention, term " loading capacity " (being IEC) refers to the mmole number of sulfonic acid group in every gram polymkeric substance.Adopt in the present invention Theoretical Calculation and volumetry to measure.The thickness of graft crosslinking type sulfonation proton exchange membrane is 10-1000 μ m, and sulfonation degree is 30-70%.Theoretical IEC is 1.0-3.5 meq/g, preferred 1.3-2.5 meq/g.
Dihalo thing monomer (I) with active function groups of the present invention comprises following structure:
In the formula (I), X is Cl, Br or I.
In the formula (I),
A kind of in the lower array structure:
Dihalo thing monomer (II) without the active function groups structure of the present invention comprises following structure:
In the formula (II), X is Cl, Br or I.
In the formula (II),
A kind of in the lower array structure:
,
In the formula (II), a kind of in the lower array structure:
,
,
,
,
.
The sulfonation dihalo thing monomer (III) of the full sulfonation block oligomers of preparation of the present invention comprises following structure:
In the formula (III), X is F, Cl or Br.
In the formula (III),
A kind of in the lower array structure:
In the formula (III), M is H, Na or K.
Sulfonation dihalo thing (III) can be produced by sulfonation reaction by corresponding non-sulfonation dihalo thing.Such as document 1(Fuel Cells, 2005, the 5:201) technology of report can be by 4, and the sulfonation of 4 '-dichloro (fluorine) sulfobenzide produces 3,3 '-disulfonic acid-4,4 '-dichloro (fluorine) sulfobenzide disodium salt.
The structure of dihydroxy compound of the present invention is as follows:
，
In the formula (IV),
A kind of in the following structure:
In the second step polymerization process, the reactive halogen functional group in the non-sulfonation main chain (
) with full sulfonation block oligomers in equate as the mole number of the hydroxyl of END CAPPED GROUP.
Below in conjunction with embodiment the present invention is described in further details.
Abbreviation explanation among the embodiment:
DCFB:?2,5-dichloro-4’-fluorobenzophenone
DCFPB:?2,5-dichloro-4’-fluorophenoxylbenzophenone
BCPPF:?2,2’-bis[4-(4-chlorobenzoyl)]phenoxyl?perfluoropropane
BCBPB:?4,4’-bis[4-(4-chlorobenzoyl)]phenoxyl?benzidine
SDFDPS:?3,3’-disulfo-4,4’-difluorodiphenyl?sulfone?sodium?salt
BP?:?biphenol
DHPS:?4,4’-dihydroxyphenyl?sulfone
DMSO:?dimethyl?sulfoxide
DMAc:?N,N’-Dimethylacetamide
NMP:?1-Methyl-2-pyrrolidinone
The polymkeric substance method for expressing is PP (a/b)-SPAES (n), and wherein SPAES is expressed as the full sulfonation segment of polyether sulphone; A/b represents the mol ratio of two kinds of dihalo things in the main chain system; N represents full sulfonation chain length.
Embodiment 1: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/3)-SPAES (5) (
M (1))
The preparation of PP (1/3) polymkeric substance: will fully dry 0.072 g (0.323 mmol) NiBr
2, 0.601 g (2.292 mmol) PPh
3Add in the there-necked flask with 1.212 g (18.53 mmol) Zn, add 7.5 mL DMAc, after reacting about 20 min, the catalyst solution color becomes dark red, adds 0.315 g (1.169 mmol) DCFB and 2.685 g (3.508 mmol) BCPPF this moment.Be warming up to 80
oThe C reaction was down to room temperature after 8 hours.Product is poured in about 200 mL (10 %) HCl solution, separated out fibrous product, after fully washing, 80
oC vacuum-drying in lower 24 hours obtains yellow product.This product is dissolved among the 25 mL DMAc, filters away residual Zn powder and insolubles, filtrate is separated out to 200 mL IPA.To product filter, after the alcohol wash, 80
oC vacuum-drying in lower 24 hours obtains final polymer P P (1/3).
The preparation of PP (1/3)-SPAES (5) polymkeric substance: 0.579 g (1.263 mmol) SDFDPS and 0.282 g (1.156 mmol) BP that will be fully dry add in the four-hole boiling flask, add 4.3 mL DMSO, until completely dissolved, add 0.241 g (1.743 mmol) salt of wormwood and 4.0 mL dry toluenes as the entrainer of water.Be warming up to 140
oC reaction 4 hours, then the water that produces in the reaction be warming up to 170 by removing with the toluene azeotropic
oThe C reaction was down to room temperature after 2 hours.PP (1/3) product 1.195 g (0.505 mmol) and 9.4 mL DMSO in the adding after the step oven dry until completely dissolved, add 9.0 mL toluene as entrainer.Be warming up to 140
oC reaction 8 ~ 10 hours.Reaction is poured into to about 200 mL water after finishing cooling, separates out fibrous product, after the washing repeatedly, 80
oVacuum-drying 24 h obtain final polymer P P (1/3)-SPAES (5) under the C.
Get this polymkeric substance 1.4 g join be made into 5%(w/v among the DMSO) solution, after stirring and dissolving is filtered, water and cast from the glass plate, in constant temperature oven 60
oDry 10 hours of C is warming up to 120
oDry 10 hours of C.Rear embathing 48 hours peeled off in the film immersion in water, then with hydrochloric acid solution exchange 72 hours, washed 48 hours.Then film is fixed on and moves in the vacuum drying oven 120 on the stainless steel stent
oC was down to room temperature in dry 2 hours and takes out, and obtained the proton type sulfonated polymer films
M (1)
Its performance data sees Table 1, and the specific conductivity under the different relative humidity is seen Fig. 2.Table 1 has shown the fundamental property of table 1 inventive embodiments 1-6 graft crosslinking type sulfonation proton exchange membrane.As can be seen from Table 1, with direct cross-linking type SPAES film M (01) and straight chain type SPAES film M (02)) compare, under similar IEC condition, water-intake rate and the dimensional change numerical value of graft crosslinking type proton exchange membrane have had obvious decline.
Embodiment 2: the preparation of graft crosslinking type sulfonation proton exchange membrane PP-1 (1/3)-SPAES (5)
In embodiment 1
M (1)The preparation method similar, difference is to change the monomer DCFB among the embodiment 1 into DCFPB, the monomer consumption is 0.421 g.
Embodiment 3: the preparation of graft crosslinking type sulfonation proton exchange membrane PP-2 (1/3)-SPAES (5)
In embodiment 1
M (1)The preparation method similar, difference is to change the monomers B CPPF among the embodiment 1 into BCBPB, the monomer consumption changes 2.154 g into, reaction solvent changes NMP into.
Embodiment 4: the preparation of graft crosslinking type sulfonation proton exchange membrane PP-3 (1/3)-SPAES (5)
In embodiment 1
M (1)The preparation method similar, difference is to change the monomer DCFB among the embodiment 1 into DCFPB, consumption is 0.421 g, BCPPF changes BCBPB into, the monomer consumption is 2.154 g, reaction solvent changes NMP into.
Embodiment 5: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/3)-SPAES (10) (
M (2))
In embodiment 1
M (1)The preparation method similar, difference is that the monomer consumption is different: SDFDPS 0.731 g, BP 0.327 g, PP (1/3) 0.755 g obtains the proton type sulfonated polymer films
M (2)
Its performance data sees Table 1, and the specific conductivity under the different relative humidity is seen Fig. 2.
Embodiment 6: the preparation of graft crosslinking type sulfonation proton exchange membrane PP-1 (1/3)-SPAES (10)
In embodiment 5
M (2)The preparation method similar, difference is to change the monomer DCFB among the embodiment 5 into DCFPB, the monomer consumption changes 0.421 g into.
Embodiment 7: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/3)-SPAES-1 (10)
In embodiment 5
M (2)The preparation method similar, difference is to change the monomer DFDPS among the embodiment 5 into DHPS, consumption is 0.440 g.
Embodiment 8: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/5)-SPAES (10) (
M (3))
In embodiment 2
M (2)The preparation method similar, difference is that catalyzer and monomer consumption are different: NiBr
20.067 g, PPh
30.565 g, Zn 1.139 g, DCFB 0.197 g, BCPPF 2.803 g, SDFDPS 0.780 g, BP 0.349 g, PP (1/5) 1.250 g obtains the proton type sulfonated polymer films
M (3)
Its performance data sees Table 1, and the specific conductivity under the different relative humidity is seen Fig. 2.
Embodiment 9: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/5)-SPAES (15) (
M (4))
In embodiment 8
M (3)The preparation method similar, difference is that the monomer consumption is different: SDFDPS 0.982 g, BP 0.426 g, PP (1/5) 1.049 g obtains the proton type sulfonated polymer films
M (4)
Its performance data sees Table 1, and the specific conductivity under the different relative humidity is seen Fig. 2.
Embodiment 10: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/7)-SPAES (10) (
M (5))
In embodiment 9
M (4)The preparation method similar, difference is that catalyzer and monomer consumption are different: NiBr
20.065 g, PPh
30.548 g, Zn 1.105 g, DCFB 0.143 g, BCPPF 2.857 g, SDFDPS 0.559 g, BP 0.250 g, PP (1/7) 1.234 g obtains the proton type sulfonated polymer films
M (5)
Its performance data sees Table 1, and the specific conductivity under the different relative humidity is seen Fig. 2.
Embodiment 11: the preparation of graft crosslinking type sulfonation proton exchange membrane PP (1/7)-SPAES (15) (
M (6))
In embodiment 10
M (5)The preparation method similar, difference is that the monomer consumption is different: SDFDPS 0.716 g, BP 0.310 g, PP (1/7) 1.054 g obtains the proton type sulfonated polymer films
M (6)
Its performance data sees Table 1, and the specific conductivity under the different relative humidity is seen Fig. 2.
Embodiment 12: the preparation of graft crosslinking type sulfonation proton exchange membrane PP-1 (1/7)-SPAES (15)
In embodiment 11
M (6)The preparation method similar, difference is to change the monomer DCFB among the embodiment 11 into DCFPB, the monomer consumption is 0.326 g.
Except above embodiment, the compound monomer of listed other structure during specification sheets formula (I) reaches (II), all can adopt the same manner to prepare PP(a/b) polymkeric substance, other compound monomer that specification sheets formula (III), (IV) enumerate in reaching (V), all can adopt identical method and PP(a/b) synthesize the graft crosslinking type polymer materials with specification sheets indication, and prepare thus novel graft crosslinking type sulfonation proton exchange membrane.
Comparative example 1:SPAES60 crosslinking polymer proton exchange membrane (
M (02)) preparation, theoretical IEC=2.42 meq/g.
With 2.051g (4.475mmol) SDFDPS, 1.138g (4.475mmol) DFDPS, 1.542 g (8.278mmol) BP and 0.056g (0.448mmol) THB (Sodium (Trihydroxy) phenylborate) join in the four-hole boiling flask that is equipped with magnetic stirring apparatus, water-and-oil separator and reflux condensing tube, constant pressure funnel and import and export of nitrogen, add 24 mL DMSO, until completely dissolved, add 1.422 g Anhydrous potassium carbonates and 12 mL dry toluenes.Be warming up to 140
oC reaction 4 hours, the water that produces in the reaction is by removing with the toluene azeotropic.Then be warming up to 165
oC drips 12 mL dry toluenes by constant pressure funnel.Reacted 8 hours.Reaction finishes rear add about 20mlDMAc dilution, cooling, pours into to about 500 mL pure water, separates out fibrous product, after fully washing, and 100
oC vacuum-drying in 24 hours gets the sulfonated polymer product of direct cross-linking type.Take by weighing SFDFDPS/DFDPS-THB (5/5-5%) polymkeric substance 2.0g, add 50 mL DMSO, heating for dissolving.After the filtration, be cast on the sheet glass.80
oC, 100
oC, 120
oThen C dry 2 hours respectively rises to 140
oDry 20 hours of C.Take out, be soaked in water and peel off, embathed in the water 24 hours, then the hydrochloric acid solution with 2M exchanges 72 hours, after the taking-up, washes 48 hours.Take out, 150
oDry 2 hours of C obtains the proton type sulfonated polymer films
M (01)
Its performance data sees Table 1.
Comparative example 2:SPAES40 straight chain type proton exchange polymer membrane (
M (01)) preparation, theoretical IEC=1.72 meq/g.
The preparation of SPAES40 polymkeric substance: with fully dry 1.100 g (2.40 mmol) SDFDPS, 0.915 g (3.60 mmol) DFDPS, 1.117 g (6.00 mmol) BP adds in the four-hole boiling flask, add 16 mL DMSO, until completely dissolved, add 0.953 g (6.90 mmol) salt of wormwood and 8.0 mL dry toluenes as the entrainer of water.Be warming up to 140
oC reaction 4 hours, then the water that produces in the reaction be warming up to 165 by removing with the toluene azeotropic
oC drips 8.0 mL dry toluenes by constant pressure funnel.Reacted 30 hours.Reaction finishes rear add about 17 mL DMSO dilution, cooling, pours into to about 200 mL ethanol, separates out fibrous product, after fully washing, and 100
oC vacuum-drying in lower 24 hours gets the sulfonated polymer product of straight chain type.This sulfonated polymer product exchanges through hydrochloric acid, obtains proton type sulfonated polymer SPAES40.
Take by weighing dry straight chain sulfonated polymer SPAES40 2.0 g, join and be made into 5%(w/v among the DMSO) solution, after stirring and dissolving is filtered, water and cast from the glass plate, in constant temperature oven 80
oDry 1 hour of C is warming up to 120
oDry 20 hours of C.After temperature is down to room temperature, is soaked in water and peels off, embathed in the water 48 hours, then with hydrochloric acid solution exchange 72 hours, washed 48 hours.Take out, 150
o Dry 2 hours of C obtains the proton type sulfonated polymer films
M (02)
Its performance data sees Table 1.
The fundamental property of table 1 graft crosslinking type sulfonation proton exchange membrane
a0.5 wt% DMSO solution (containing 1 % LiCl), 35
oC;
b60
oC;
cIn the water, be of a size of benchmark during with 70% relative humidity, in the water of certain temperature after the balance, the plane of film and the size changing rate of thickness direction.
△ lAnd
△ tRepresent respectively in-plane and thickness direction.
dThe product information of DuPont.
Claims (6)
1. graft crosslinking type polymkeric substance that is used for proton exchange membrane, it is characterized in that: polymkeric substance has hydrophobic polyarylether, polyaryletherketone or polyether sulphone main chain and hydrophilic sulfonated polyether, polyaryletherketone or polyether sulphone graft side chain, simultaneously with graft side chain as linking agent;
This polymkeric substance is standby in order to the below legal system:
The first step is by changing dihalo thing (I) and the kind of dihalo thing (II) and the hydrophobic polymer main chain product P P that ratio obtains different structure, hard and soft property and chain length that adds; Be about to dry nickel catalyzator and non-proton type polar organic solvent and add in the reactor, after question response system color becomes scarlet, add the reaction of dihalo thing (I) and dihalo thing (II), wherein dihalo thing (I) is with the side chain reaction active groups; After reaction finishes, dilute and pour in the aqueous hydrochloric acid, separate out fibrous product, after filtration, after the washing, oven dry obtains non-sulfonated polymer main chain product;
Second step, obtain the full sulfonation oligopolymer of different chain lengths by the ratio that changes sulfonation dihalo thing monomer and dihydroxy compound monomer, and then by with the PP of different structure reaction, obtain the graft crosslinking type sulfonated polymer product P P-SPAES of different ions exchange capacity; Namely at first the sulfonation dihalo thing (III) of drying, dihydroxy compound (IV or V) are added in the reactor with non-proton type polar organic solvent, until completely dissolved, adding with respect to the excessive salt of wormwood of hydroxyl mole number as catalyzer, add dry toluene as azeotropic aqua, be down to room temperature after the reaction; Then with dried PP according to etc. stoichiometry add temperature reaction in the reaction solution; The dilution and slowly be poured into water, separate out fibrous product, after filtration, the washing after, the oven dry, obtain PP-SPAES;
In the 3rd step, above-mentioned polymer dissolution in non-proton type polar organic solvent, is watered and cast from the glass plate, behind air drying, film is peeled off from sheet glass, with dilute sulphuric acid or the exchange of dilute hydrochloric acid room temperature, be washed to neutrality, vacuum drying namely obtains proton type graft crosslinking type exchange membrane;
It is as follows with dihalo thing monomer (I) structure of active function groups to prepare non-sulfonation main chain:
In the formula (I), X is Cl, Br or I;
-Y is a kind of in the lower array structure:
Dihalo thing monomer (II) structure without the active function groups structure is as follows:
In the formula (II), X is Cl, Br or I;
-Y-is a kind of in the lower array structure :-CO-,-SO
2-;
-M-is a kind of in the lower array structure :-,-CO-,-SO
2-,
Sulfonation dihalo thing monomer (III) structure of preparation wetting ability sulfonation oligopolymer is as follows:
In the formula (III), X is F, Cl or Br;
-Y-is a kind of in the lower array structure:
-，-O-，-S-，-CO-，-SO
2-，?
M is H, Na or K;
The structure of dihydroxy compound (IV or V) is a kind of in the following monomer:
In the formula (IV) ,-X-is a kind of in the following structure:
-，-O-，-S-，-CO-，-SO
2-，?
2. the preparation method of a graft crosslinking type proton exchange polymer membrane is characterized in that step is as follows:
The first step, nickel catalyzator and the non-proton type polar organic solvent of drying are added in the reactor, after question response system color becomes scarlet, add the reaction of dihalo thing (I) and dihalo thing (II), wherein dihalo thing (I) is with the side chain reaction active groups; After reaction finishes, dilute and pour in the aqueous hydrochloric acid, separate out fibrous product, after filtration, after the washing, oven dry obtains non-sulfonated polymer main chain product;
Second step, at first sulfonation dihalo thing (III), the dihydroxy compound (IV or V) with drying adds in the reactor with non-proton type polar organic solvent, until completely dissolved, adding with respect to the excessive salt of wormwood of hydroxyl mole number as catalyzer, add dry toluene as azeotropic aqua, be down to room temperature after the reaction; Then with dried PP according to etc. stoichiometry add in the reaction solution temperature reaction; Dilution also is poured into water, and separates out fibrous product, and after filtration, after the washing, oven dry obtains the graft crosslinking type sulfonated polymer product P P-SPAES of different ions exchange capacity;
In the 3rd step, above-mentioned polymer dissolution in non-proton type polar organic solvent, is watered and cast from the glass plate, behind air drying, film is peeled off from sheet glass, with dilute sulphuric acid or the exchange of dilute hydrochloric acid room temperature, be washed to neutrality, vacuum drying namely obtains proton type graft crosslinking type exchange membrane;
It is as follows with dihalo thing monomer (I) structure of active function groups to prepare non-sulfonation main chain:
In the formula (I), X is Cl, Br or I;
-Y is a kind of in the lower array structure:
-F，?
Dihalo thing monomer (II) structure without the active function groups structure is as follows:
In the formula (II), X is Cl, Br or I;
-Y-is a kind of in the lower array structure :-CO-,-SO
2-;
-M-is a kind of in the lower array structure :-,-CO-,-SO
2-,
Sulfonation dihalo thing monomer (III) structure of preparation wetting ability sulfonation oligopolymer is as follows:
In the formula (III), X is F, Cl or Br;
-Y-is a kind of in the lower array structure:
-，-O-，-S-，-CO-，-SO
2-，?
M is H, Na or K;
The structure of dihydroxy compound (IV or V) is a kind of in the following monomer:
In the formula (IV) ,-X-is a kind of in the following structure:
-，-O-，-S-，-CO-，-SO
2-，?
3. the preparation method of graft crosslinking type proton exchange polymer membrane according to claim 2, it is characterized in that: non-proton type polar organic solvent is methyl-sulphoxide, METHYLPYRROLIDONE, N, the mixing of one or more in N-N,N-DIMETHYLACETAMIDE or the DMF; Nickel catalyzator consist of a certain proportion of NiBr2, PPh3 and Zn powder.
4. the preparation method of graft crosslinking type proton exchange membrane according to claim 2, it is characterized in that: in the first step, reacted 1-24 hour at 60-140 ℃ after adding dihalo thing (I) and dihalo thing (II), dihalo thing (I) is 1:1～30 with the mol ratio of dihalo thing (II).
5. the preparation method of graft crosslinking type proton exchange membrane according to claim 2, it is characterized in that: the mol ratio of sulfonation dihalo thing and dihydroxy compound is 1:1～2 in the second step; Adding with respect to the salt of wormwood of the excessive 10-30% of hydroxyl mole number as catalyzer; Add dry toluene and be down to room temperature 60-140 ℃ of reaction after 1-10 hour after as azeotropic aqua; With dried PP according to etc. stoichiometry add in the reaction solution, be warming up to 90-180 ℃ of reaction 4-48 hour.
6. the preparation method of graft crosslinking type proton exchange membrane according to claim 2 is characterized in that: the temperature in the 3rd step when air drying is 60-140 ℃, and dilute sulphuric acid is 0.5-2.5M, and dilute hydrochloric acid is 1-5M, and room temperature swap time is 24-72 hour.
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