CN102417603B - High-proton-conductivity composition and preparation method thereof - Google Patents
High-proton-conductivity composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-proton-conductivity composition and a preparation method thereof. The high-proton-conductivity composition comprises modified aromatic hydrocarbon and fluorocarbon resin, wherein the modified aromatic hydrocarbon mixed solution is prepared from 97.5-65 wt% of aromatic hydrocarbon, 1-10 wt% of divinylbenzene (DVB), 0.5-5 wt% of benzoyl peroxide (BPO) and 1-20 wt% of N-methylpyrrolidone (NMP); and the fluorocarbon resin is at least one of polytetrafluoroethylene, polyvinylidene fluoride, perfluoroethylene-propylene copolymer, polyvinyl fluoride and ethylene-tetrafluoroethylene copolymer. Compared with the prior art, the high-proton-conductivity composition provided by the invention, the excellent proton conductivity and intensity can be achieved under the conditions that the amount of the added modified aromatic hydrocarbon does not exceed 10-40 wt% of the high-proton-conductivity composition.
Description
Technical field
The present invention relates to a kind of high-proton-conductivity composition and method of making the same, belong to polymeric material field.
Background technology
Fuel cell (FC) as the energy conversion system of environment sustainable development gradually highlighting its importance.In recent years along with broad development and the application of Proton Exchange Membrane Fuel Cells (PEMFC) in the high and new technology such as traffic, electronic product, aerospace field.Proton exchange membrane (PEM, proton exchange membrane) is one of most important parts in PEMFC.Its function is proton conducting, simultaneously the fuel of anode and the oxygenant of negative electrode separated, and be a kind of isolator of electronics.
Sulfonated polystyrene (SPS) proposed its preparation process in 1975 by Makowski, and application United States Patent (USP) (U.S.Patent, 3870841).Due to the base position of sulfonated reaction being provided on its phenyl ring of polystyrene, if after being made into the sulphonated polystyrene film, good ion exchange property [Bruce et al. is arranged, 1999], thus this research select assorted row's polystyrene (aPS) as the macromolecular material that is sulfonated.Therefore but the physical strength of aPS is relatively poor, easily causes the embrittlement phenomenon in the process of film forming, must seek the good and each side of physical strength and all show good macromolecular material as the base material of the sulfonated polystyrene (SaPS) of the row of mixing.That mentions on document comprises take SPS as proton exchange membrane: with SPS grafting pvdf membrane material [Sara and Robert, 1997; Hietala et al., 1998], it has good physical strength, thermostability, ionic conductivity and the advantage such as cheap; Matrix material [Amarilla et al., 2000] with SPS and dysprosium acid has good ionic conductivity.Learnt by these documents, the sulfonic acid group can make the sex expression of film material ionic conduction good, and polystyrene has the advantages such as stability is high and easy sulfonated, so SPS is that main proton exchange membrane is subject to fuel cell aspect attention in recent years gradually.
Fluorocarbon resin mainly contains following several by resinous principle: tetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), fluorinated ethylene propylene copolymer (FEP), fluorinated ethylene propylene (PVF), ethylene tetrafluoroethylene copolymer (ETFE).Wherein, the PTFE film is the kind that is most widely used, account for the share in whole U.S.'s fluoro-containing copolymer film market 51%, a large amount of insulating material, the wrapping material of electrical condenser and numerous areas such as escapement of transformer that are used for insulation tape, electronics and the electric installation of airplane spare parts, circuit card, windmill assembly, electric wire and cable, average growth rate per annum reached 6.3% in recent years.Compare with the fluoro-containing copolymer film of other kinds, the shortcoming of PTFE film maximum is that the high difficulty of processing of stickiness is large, and the modified ptfe film has overcome this defective to a certain extent, thereby has substituted the PVDF film in fuel cell field.The PVDF film is the fastest kind of growing up in fluoro-containing copolymer film, and the American market average growth rate per annum reaches 7.6%.At present, PVDF film and PVC and PE film are laminated with, can when guaranteeing its performance, reduce the cost of product.In addition, PVDF film and other films have compatible preferably, and the popularization of multilayer film is when keeping its performance, and is more economical.The development in PVDF film market mainly has benefited from the generally use of lithium cell.At present, the fast development of mobile phone, notebook computer, portable type electronic product, solar panel, building and automobile decoration film and semicon industry has promoted being widely used of this kind film.In addition, pvdf membrane also is used for the fields such as fuel cell, aircraft inside gadget and business automation equipment just more and more.The FEP film has good flame retardant resistance, insulativity, easily by advantages such as dye colorings, but it also has weakness: the one, cost is high, the 2nd, under melting state its erosion resistance a little less than.The FEP film is mainly used in the fields such as transportation, chemical industry processing, solar cell plated film, indication material, circuit card, flat cable and motorway direction board.The PVF film is similar with pvdf membrane, is also fastest-rising film kind, and the American market average growth rate per annum is up to 7.6%.Therefore the compatibility that has height due to PVF film and other types film is widely used in the manufacturing of multilayer film.At present E.I.Du Pont Company is globally unique PVF film supplier, and its brand name is Tedlar.This kind film is mainly used in the primer of photovoltaic cell.The development of PVF film and photovoltaic cell industry are closely related, and equilibrium of supply and demand degree also depends on the development of photovoltaic industry to a great extent.Etfe film is mainly used in the film photovoltaic cell material, the lagging material of greenhouse and horticultural facility.In addition, other fluoro-containing copolymer films also have voltalef (PCTFE) and ethene one chlorotrifluoroethylene (ECTFE is called for short F30).Owing to having good barrier properties, these two kinds of films are mainly used in the medical packaging field.The fluorocarbon resin macromolecule membrane has good mechanical properties as a kind of novel fluoro-carbon thermoplastics, and heat and chemical stability are a kind of good proton exchange membrane materials.Demand for high-molecular electrolyte fuel battery, proton exchange membrane must have good ionic conductivity, physical strength, heat and the suction water-swellable of chemical stability with appropriateness, and wherein perviousness and the diffustivity of the gas that reacts of participation or methyl alcohol must be low.Can obtain take the polyelectrolyte of fluorocarbon resin skeleton as the basis if introduce ionic group in this polymkeric substance, and modal a kind of Nafion film of producing for Dupont company.Although business-like Nafion117 proton exchange membrane has good tolerance at present, but because the specification of selling at exorbitant prices and thickness and conductance is restricted, and too high [the Pivovar et al. of the perviousness of methyl alcohol, 1999], therefore be necessary to seek a kind of cheap and can produce in a large number the new film material suitable with its each side performance.Gore﹠amp; Associated company borrows its PTFE porous-film aspect advantage, the Nafion/PTFE that is applicable to fuel cell is carried out a large amount of research and development, and it is in patent CN1,134,288C, US5,547,551, US5,599,614, US RE37, the composite membrane method of Nafion/PTFE is disclosed in 307 and US6,613,203; DuPont company is at patent US5, discloses the composite membrane method of Nafion/PTFE in 795,668 and US6,110,333; Chinese Academy of Sciences Dalian chemical physics place patent CN1 at home discloses the composite membrane method of Nafion/PTFE in 146,186A.
the prepared high-proton-conductivity composition tool process apparatus of the present invention is cheap, processing procedure is easy, non-environmental-pollution, it is Siemens/cm that proton conduction property can be controlled in 0.0168～0.0519S/cm(), the production unit funds are cheap, be applicable to a large amount of productions of industry, the amount of following process and broad range of applicability and the modification aromatic hydrocarbons that adds is in 5～40% of the weight ratio that is no more than the high-proton-conductivity composition, can reach the proton conduction effect of excellence, and keep the main characteristic of former polymer base material, proton conduction property 0.0055S/cm(than present commercially available Nafion117 is Siemens/cm), therefore the prepared high-proton-conductivity composition of the present invention can be applicable to present fuel cell, sea water desaltination, mobile phone, notebook computer, portable type electronic product, solar panel, the fast development of building and automobile decoration film and semicon industry has promoted being widely used of this kind film.
Summary of the invention
An object of the present invention is to provide a kind of composition of high-proton-conductivity.
Another object of the present invention is to provide a kind of preparation method of composition of high-proton-conductivity.
Another purpose of the present invention is to provide a kind of preparation method of high-proton-conductivity molded article.
In order to realize the foregoing invention purpose, the invention provides following technical scheme:
A kind of preparation method of high-proton-conductivity composition comprises the steps:
A) take fluorocarbon resin and the N,N-dimethylacetamide solution that weight ratio is 1%～20%:1%～20%, horizontal positioned is 0.5 hour～4 hours in 90 ℃～150 ℃ lower loft drier, with the film that obtains in 120 ℃～180 ℃ hot pressing 0.1 hour～4 hours;
B) film that step a) is made is placed in modification aromatic hydrocarbons mixing solutions (aromatic hydrocarbons, divinylbenzene, dibenzoyl peroxide, N-Methyl pyrrolidone weight ratio are 97.5～68:1～10:0.5～2:1～20), soaked 1 hour～10 hours at 25 ℃～80 ℃, obtain the composition film of modification aromatic hydrocarbons and fluorocarbon resin;
C) the modification aromatic hydrocarbons that step b) is made and the composition film of fluorocarbon resin are placed in vulcanizing press 90 ℃～150 ℃ lower hot pressing 6 hours～12 hours;
D) the modification aromatic hydrocarbons that step c) is made and the composition film of fluorocarbon resin immersed in chlorosulfonic acid solution (concentration is 5%～20%) 12 hours～48 hours;
E) the modification aromatic hydrocarbons that step c) is made and the composition film of fluorocarbon resin boiled 12 hours～48 hours in 25 ℃～80 ℃ with a certain amount of deionized water, the weight ratio that gets modification aromatic hydrocarbons and fluorocarbon resin is 5～40:95～60, and thickness is 30 microns～250 microns and has the modification aromatic hydrocarbons of high-proton-conductivity and the composition film of fluorocarbon resin.
So-called high-proton-conductivity composition, referring to proton conductivity tests according to the GB/T20042.3-2009 testing standard, the measuring mechanical property method is tested described method with reference to GB/T1040.3-2006, and generally the proton conductivity as proton exchange membrane is Siemens/cm about 0.1～0.0001S/cm() scope.
Above-mentioned modification aromatic hydrocarbons and the weight ratio of fluorocarbon resin are 10～40:90～60, and preferably, the weight ratio of modification aromatic hydrocarbons and fluorocarbon resin is 5～30:95～70.
In the modification aromatic hydrocarbons mixing solutions of above-mentioned step b), aromatic hydrocarbons, divinylbenzene, dibenzoyl peroxide, N-Methyl pyrrolidone weight ratio are 97.5～68:1～10:0.5～2:1～20, preferably, in modification aromatic hydrocarbons mixing solutions, aromatic hydrocarbons, divinylbenzene, dibenzoyl peroxide, N-Methyl pyrrolidone weight ratio are 90～66:4～10:1～4:5～20, and mass concentration is 95%～99%.The described aromatic hydrocarbons of step b) is the hydrocarbon polymer that contains benzene ring structure, divides from the number of phenyl ring, can be divided at least a in mononuclear aromatics, polycyclic aromatic hydrocarbons and condensed-nuclei aromatics, and mass concentration is 95%～99%.The described chlorsulfonic acid of step d), mass concentration are 5%～20%
Described mononuclear aromatics is selected from substituted benzene, as toluene, ethylbenzene, vinylbenzene, optimization styrene.Described condensed ring aromatic hydrocarbon, as naphthalene, anthracene, phenanthrene etc., as thick dinaphthyl, 9,10-dimethylanthracene, 1,2,9, the 10-tetramethyl-is luxuriant and rich with fragrance, 1, and 2-benzanthrenes etc. are preferred 9, the 10-dimethylanthracene.Described polynuclear aromatics, as biphenyl, tritane etc., preferred tritane.
Fluorocarbon resin described above is preferably at least a in tetrafluoroethylene, poly(vinylidene fluoride), fluorinated ethylene propylene copolymer, fluorinated ethylene propylene and ethylene tetrafluoroethylene copolymer.
Described tetrafluoroethylene is at room temperature a white solid, and density is about 2.2 g/ccs, and its fusing point is 327 ° of C.Described poly(vinylidene fluoride) is at room temperature a white powder, and density is about 1.74～1.77 g/ccs.Its fusing point is 156～162 ° of C.Described fluorinated ethylene propylene copolymer is that tetrafluoroethylene and R 1216 copolymerization form, and is at room temperature a white solid, and density is about 2.15 g/ccs.Its fusing point is 156～162 ° of C.Described fluorinated ethylene propylene is white powder partially crystalline polymkeric substance, fusing point 190-200 ° C, and 210 ° of decomposition temperatures are more than C, life-time service temperature-100-150 ℃.Described ethylene tetrafluoroethylene copolymer is tetrafluoroethylene and ethene, and copolymerization forms, and is a kind of resistant to elevated temperatures fluoroplastics, and the use temperature scope is-60～180 ° of C
The number average number-average molecular weight of above-mentioned fluorocarbon resin is 50,000～1,000,000, is preferably 200,000～800,000.
Behavior is melted in crystallization and roasting that the measuring method employing T.Suwa in 1973 of number-average molecular weight etc. utilize dsc (DSC) to study tetrafluoroethylene (PTFE), heat of crystallization and its molecular weight of finding polymer melt are closely related, and try to achieve the number-average molecular weight M of tetrafluoroethylene
nWith heat of crystallization △ H
cBetween the pass be M
n=2.1 * 10
10* △ H
c -5.16, M wherein
nBe number-average molecular weight, △ H
cHeat of crystallization for tetrafluoroethylene.
In above-mentioned high-proton-conductivity composition, can also comprise acceptable auxiliary agent or filler.Auxiliary agents such as softening agent, thermo-stabilizer, photostabilizer, oxidation inhibitor, fire retardant, lubricant, tinting material, and some inert fillers.
Between above-mentioned five steps, can insert the step that some sneak into other materials of not mentioning in above-mentioned steps, perhaps in any one above-mentioned step, the material of sneaking into can also comprise other materials of not mentioning in above-mentioned steps.The material of sneaking into need be acceptable auxiliary agent or filler etc.
The present invention also provides a kind of preparation method of molded article of high-proton-conductivity composition in addition, that is utilize above-mentioned high-proton-conductivity composition or utilize the prepared high-proton-conductivity composition of above-mentioned preparation method, by dip coating moulding, spraying method moulding, spread coating moulding, the electrophoretic method moulding in lamination method blow molding, the moulding of coextrusion casting film, Coextrusion Blow Moulding, dull and stereotyped compression moulding, hollow blow molding, coating.
The extrusion equipment that the method utilization of above-mentioned moulding is general just can be implemented, and simple being conducive to commercially produces.Can machine-shaping be the molded article of the shapes such as container, film, flat board or tubulose by the modification aromatic hydrocarbons of aforesaid method preparation and the composition of fluorocarbon resin, main characteristic, the processing procedure that this molded article has electric conductivity that effect improves molecular composite material, keep original polymer base material is easy, low environment pollutes, and has wide range of applications.Described polymer composite can be aliphatics or aromatic hydrocarbons base polymer.
The molded article that above-mentioned preparation method obtains can be the shapes such as container, film, flat board or tubulose.
High-proton-conductivity composition provided by the present invention compared with prior art, the amount of the modification aromatic hydrocarbons that adds in the situation that be no more than the high-proton-conductivity composition weight ratio 5～40%, just can reach the proton conductivity of excellence and the effect of intensity, and in conjunction with closely, guaranteed the main mechanical characteristics of polymer base material between modification aromatic hydrocarbons and body material fluorocarbon resin.
High-proton-conductivity composition provided by the present invention, the fast development that is specially adapted to present fuel cell, sea water desaltination, mobile phone, notebook computer, portable type electronic product, solar panel, building and automobile decoration film and semicon industry has promoted being widely used of this kind film.
Embodiment
Below in conjunction with embodiment, further set forth the present invention:
The divinylbenzene of using in embodiment (DVB), dibenzoyl peroxide (BPO), N-Methyl pyrrolidone (NMP) are analytical pure, and mass concentration is 95%～98%; Chlorsulfonic acid is analytical pure, and mass concentration is 5%～20% to carry out also can adopting divinylbenzene, dibenzoyl peroxide, N-Methyl pyrrolidone, the chlorsulfonic acid of other concentration in the concrete process of implementing those skilled in the art.
The comparative example 1
Utilize the vulcanizing press forming machine to mold fluorocarbon resin and be about 40 micron films, by the character requirement of material requested, their proton conductivity and tensile strength are measured.Described fluorocarbon resin is polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer (CAS9011-17-0 of U.S. Sigma aldrich; D1.77).
The comparative example 2
Select commercially available high proton conduction constituent as reference, by the character requirement of material requested, their proton conductivity and tensile strength are measured.Described high proton conduction constituent is that Dupont is produced Nafion117.
Embodiment 3～6
The preparation of the composition of modification aromatic hydrocarbons and fluorocarbon resin
With fluorocarbon resin and N, after the N-dimethylacetamide solution carries out solution film forming, after being placed in modification aromatic hydrocarbons mixing solutions and carrying out polyreaction, obtain the composition film work in-process of modification aromatic hydrocarbons and fluorocarbon resin, after carrying out sulfonation reaction with chlorsulfonic acid, be neutral with a certain amount of deionized water diafiltration to filtrate, thickness is 40 microns and has the modification aromatic hydrocarbons of high-proton-conductivity and the composition film of fluorocarbon resin.Aromatic hydrocarbons, divinylbenzene, dibenzoyl peroxide, N-Methyl pyrrolidone weight ratio are 90:4:1:5.
Design parameter sees Table 1.
Table 1
Embodiment 7
Comparative example 1, comparative example 2, modification aromatic hydrocarbons that embodiment 3～6 makes and the composition sheet material of fluorocarbon resin are carried out respectively the test of proton conductivity and tensile strength.Test result sees Table 2.The proton conductivity testing method according to GB/T20042.3-2009 and tensile strength with reference to the described method of GB/T1040.3-2006.
Table 2 film proton conductivity and tensile strength test
As can be seen from Table 2, in proton conductivity comparative example 1 without proton conduction property, the multiplying power of improving of the composition sample of embodiment 3～6 is 3～10 times of comparative example 2.
As can be seen from Table 2, the composition of modification aromatic hydrocarbons and fluorocarbon resin has aobvious proton conductivity to the film proton conduction, make anode (negative pole) the hydrogen proton that produces directly to pass proton exchange membrane and arrive negative electrode (positive pole), and electronics can only could arrive negative electrode by external circuit.Just produced direct current when electronics flows to negative electrode by external circuit, take anode as with reference to the time, cathode potential is 1.23V.All has aobvious improvement with respect to fluorocarbon resin and commercially available high-proton-conductivity constituent.
When the aromatic hydrocarbons in embodiment 3～6, divinylbenzene, dibenzoyl peroxide, when the N-Methyl pyrrolidone weight ratio is 80:8:2:10, the numerical value of the effect of enforcement and embodiment 3 is suitable, and deviation is within 3%.
High-proton-conductivity composition provided by the present invention compared with prior art, the amount of the modification aromatic hydrocarbons that adds in the situation that be no more than the high-proton-conductivity composition weight ratio 5～40%, just can reach excellent proton conduction effect, and in conjunction with closely, guaranteed the main mechanical characteristics of polymer base material between modification aromatic hydrocarbons and body material fluorocarbon resin.
High-proton-conductivity composition provided by the present invention, the fast development that is specially adapted to present fuel cell, sea water desaltination, mobile phone, notebook computer, portable type electronic product, solar panel, building and automobile decoration film and semicon industry has promoted being widely used of this kind film.
Having used specific embodiment in this specification sheets sets forth the present invention, it is the preferred embodiment of the present invention, should be pointed out that for one of ordinary skill in the art, may will change in implementation process in specific embodiments and applications according to thought of the present invention.Therefore, the content of this specification sheets record should not be construed as limitation of the present invention.
Claims (8)
1. high-proton-conductivity composition, comprise modification aromatic hydrocarbons and fluorocarbon resin, described modification aromatic hydrocarbons is comprised of by 97.5～65:1～10:0.5～5:1～20 aromatic hydrocarbons, divinylbenzene (DVB), dibenzoyl peroxide (BPO), N-Methyl pyrrolidone (NMP) weight ratio;
The weight ratio of described modification aromatic hydrocarbons and fluorocarbon resin is 10～40:90～60;
Described aromatic hydrocarbons is at least a in polycyclic aromatic hydrocarbons and condensed-nuclei aromatics, and mass concentration is 95%～99%.
2. high-proton-conductivity composition according to claim 1, described modification aromatic hydrocarbons, it is characterized in that, aromatic hydrocarbons, divinylbenzene (DVB), dibenzoyl peroxide (BPO), N-Methyl pyrrolidone (NMP) weight ratio are 90～66:4～10:1～4:5～20.
3. high-proton-conductivity composition according to claim 1, is characterized in that, described divinylbenzene (DVB), dibenzoyl peroxide (BPO), N-Methyl pyrrolidone (NMP), and mass concentration is 95%～99%.
4. high-proton-conductivity composition according to claim 1, is characterized in that, described fluorocarbon resin is at least a in tetrafluoroethylene, poly(vinylidene fluoride), fluorinated ethylene propylene copolymer, fluorinated ethylene propylene and ethylene tetrafluoroethylene copolymer.
5. high-proton-conductivity composition according to claim 1, is characterized in that, the number-average molecular weight of described fluorocarbon resin is 50,000～1,000,000.
6. high-proton-conductivity composition according to claim 1, is characterized in that, also comprises acceptable auxiliary agent or filler.
7. the preparation method of a high-proton-conductivity composition, comprise the steps:
A) take fluorocarbon resin and the N,N-dimethylacetamide solution that weight ratio is 1%～20%:1%～20%, horizontal positioned is 0.5 hour～4 hours in 90 ℃～150 ℃ lower loft drier, with the film that obtains in 120 ℃～180 ℃ hot pressing 0.1 hour～4 hours;
B) film that step a) is made is placed in modification aromatic hydrocarbons mixing solutions, in described modification aromatic hydrocarbons mixing solutions, aromatic hydrocarbons, divinylbenzene, dibenzoyl peroxide, N-Methyl pyrrolidone weight ratio are 97.5～68:1～10:0.5～2:1～20, soaked 1 hour～10 hours at 25 ℃～80 ℃, obtain the composition film of modification aromatic hydrocarbons and fluorocarbon resin;
C) the modification aromatic hydrocarbons that step b) is made and the composition film of fluorocarbon resin are placed in vulcanizing press 90 ℃～150 ℃ lower hot pressing 6 hours～12 hours;
D) the modification aromatic hydrocarbons that step c) is made and the composition film of fluorocarbon resin immersed in chlorosulfonic acid solution 12 hours～48 hours;
E) the modification aromatic hydrocarbons that step c) is made and the composition film of fluorocarbon resin boiled 12 hours～48 hours in 25 ℃～80 ℃ with a certain amount of deionized water, the weight ratio that gets modification aromatic hydrocarbons and fluorocarbon resin is 5～40:95～60, and thickness is 30 microns～250 microns and has the modification aromatic hydrocarbons of high-proton-conductivity and the composition film of fluorocarbon resin.
8. the preparation method of high-proton-conductivity composition according to claim 7, is characterized in that, the described chlorsulfonic acid of step d) is characterized in that, mass concentration is 5%～20%.
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