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Publication numberCN1362971 A
Publication typeApplication
Application numberCN 01800213
PCT numberPCT/US2001/004995
Publication date7 Aug 2002
Filing date15 Feb 2001
Priority date15 Feb 2000
Also published asCA2369696A1, CA2369696C, CN1142193C, EP1177221A1, EP1177221A4, US6780935, US6872781, US20030064267, US20040092661, WO2001060872A1
Publication number01800213.7, CN 01800213, CN 1362971 A, CN 1362971A, CN-A-1362971, CN01800213, CN01800213.7, CN1362971 A, CN1362971A, PCT/2001/4995, PCT/US/1/004995, PCT/US/1/04995, PCT/US/2001/004995, PCT/US/2001/04995, PCT/US1/004995, PCT/US1/04995, PCT/US1004995, PCT/US104995, PCT/US2001/004995, PCT/US2001/04995, PCT/US2001004995, PCT/US200104995
InventorsL黑达利, L比尔隆
Applicant阿托费纳化学股份有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Fluoropolymer resins containing ionic or ionizable groups and products containing the same
CN 1362971 A
Abstract  translated from Chinese
本文描述了一种共混聚合物,它包含至少一种带有至少一种离子基团或可离子化基团的丙烯酸类树脂或乙烯基树脂和至少一种热塑性氟聚合物。 Described herein is a polymer blend, which comprises at least one having at least one ionic group or ionizable group is an acrylic resin or vinyl resin and at least one thermoplastic fluoropolymer. 优选的共混聚合物是由两个用于各种用途(包括形成膜)的聚合物的紧密掺混物,该膜可用于蓄电池和燃料电池以及相似物。 Preferred polymer blends are used in various applications by two (including the formation of film) of the polymer blend closely, the film can be used for batteries and fuel cells as well as analogues. 本文还描述了该共混聚合物的制造方法。 Also described herein is a method for producing the polymer blend.
Claims(34)  translated from Chinese
1.共混聚合物,其特征在于它包括a)至少一种带有至少一种离子基团或可离子化基团的丙烯酸类树脂或乙烯基树脂或两者皆有;和b)至少一种热塑性氟聚合物,其中a)和b)是不同的。 1. The polymer blend, characterized in that it comprises a) at least one having at least one ionic group or ionizable group is an acrylic resin or vinyl resin or both; and b) at least one thermoplastic fluoropolymer, wherein a) and b) are different.
2.如权利要求1所述的共混聚合物,其特征在于所述的至少一种热塑性氟聚合物是共聚物。 2. The polymer blend according to claim, characterized in that said at least one thermoplastic fluoropolymer is a copolymer.
3.如权利要求1所述的共混聚合物,其特征在于所述的氟聚合物包括聚(偏二氟乙烯)。 The polymer blend according to claim, wherein the fluoropolymer comprises poly (vinylidene fluoride).
4.如权利要求1所述的共混聚合物,其特征在于所述的氟聚合物包括a)聚(偏二氟乙烯)和b)六氟丙烯、四氟乙烯、四氟氯乙烯、氟化乙烯、或它们的组合。 4. The polymer blend of claim 1, wherein the fluoropolymer comprises a) a poly (vinylidene fluoride) and b) hexafluoropropylene, tetrafluoroethylene, tetrafluoroethylene chloride, vinyl fluoride ethylene, or combinations thereof.
5.如权利要求1所述的共混聚合物,其特征在于所述的氟聚合物包括a)约30-100重量%的聚(偏二氟乙烯)和0-70重量%的至少一种带有至少一个氟原子的聚(烯烃)。 5. The polymer blend of at least one of claim 1, wherein the fluoropolymer comprises a) from about 30 to 100% by weight of poly (vinylidene fluoride), and 0-70 wt% of polyethylene with at least one fluorine atom (olefin).
6.如权利要求1所述的共混聚合物,其特征在于所述的离子基团或可离子化基团是磺化基团或膦酸化基团或两者皆有。 The polymer blend as claimed in one of the preceding claims, wherein said ionic group or ionizable group is a sulfonate groups or phosphonated group or both.
7.如权利要求1所述的共混聚合物,其特征在于所述的至少一种热塑性氟聚合物是核,而所述的至少一种带有至少一种离子基团或可离子化基团的丙烯酸类树脂局部覆盖所述的核。 7. The polymer blend of claim 1, wherein said at least one thermoplastic fluoropolymer is a core, and said at least one ionic group or ionizable group having at least one Local group acrylic resin covering the core.
8.如权利要求1所述的共混聚合物,其特征在于所述的至少一种带有至少一种离子基团或可离子化基团的丙烯酸类树脂或乙烯基树脂或两者皆有由下述物质聚合形成:带有至少一种丙烯酸或乙烯基或者两者皆有的单体、至少一种可共聚单体、至少一种带有至少一种官能团的单体、和至少一种带有离子基团或可离子化基团的单体,其中各单体互不相同。 8. The polymer blend of claim 1, wherein said at least one having at least one ionic group or ionizable group is an acrylic resin or vinyl resin or both Polymerization is formed from: having at least one or both of acrylic or vinyl monomers, at least one copolymerizable monomer, at least one monomer having at least one functional group, and at least one having an ionic group or ionisable monomer groups, wherein each monomer different from each other.
9.如权利要求8所述的共混聚合物,其特征在于所述的带有离子基团或可离子化基团的单体是磺化的或膦酸化的单体。 9. The polymer blend of claim 8, wherein said bearing ionic group or ionisable monomer groups are sulfonated or phosphonated monomer.
10.如权利要求1所述的共混聚合物,其特征在于所述的丙烯酸类树脂或乙烯基树脂是氟化的。 10. The polymer blend of claim 1, wherein the acrylic resin or vinyl resin is fluorinated.
11.如权利要求1所述的共混聚合物,其特征在于所述的丙烯酸类树脂或乙烯基树脂是共聚物。 11. The polymer blend of claim 1, wherein the acrylic resin or vinyl resin is a copolymer.
12.组合物,其特征在于它包含掺混的下列聚合产物:a)至少一种包含丙烯酸单元、乙烯基单元或两者皆有、以及至少一种离子基团或可离子化基团的聚合物;和b)至少一种热塑性氟聚合物,其中a)和b)是不同的。 12. A composition, characterized in that it comprises the polymerization product of the following blend of: a) at least one unit comprising acrylic acid, vinyl units, or both, and polymerizing at least one ionic group or ionizable group thereof; and b) at least one thermoplastic fluoropolymer, wherein a) and b) are different.
13.如权利要求12所述的组合物,其特征在于所述的丙烯酸单元或乙烯基单元是氟化的。 13. The composition according to claim 12, characterized in that the acrylic or vinyl units of the unit is fluorinated.
14.如权利要求12所述的组合物,其特征在于所述的至少一种聚合物是共聚物。 14. The composition according to claim 12, wherein said at least one polymer is a copolymer.
15.聚合离子膜,其特征在于它包括权利要求1所述的共混聚合物。 15. polymerizable ionic membrane, characterized in that it comprises a polymer blend of claim 1.
16.膜电极装置,其特征在于它包括权利要求15所述的聚合离子膜。 16. The membrane electrode assembly, characterized in that it comprises a polymeric ion-exchange membrane 15 of the Claim.
17.燃料电池,其特征在于它包括权利要求16所述的膜电极装置。 17. The fuel cell, characterized in that it includes a membrane electrode assembly according to claim 16.
18.燃料电池,它包括被聚合离子交换膜隔开的阳极室和阴极室,其特征在于所述的膜包含权利要求1所述的共混聚合物。 18. A fuel cell comprising an ion exchange membrane are polymerized separated anode and cathode compartments, characterized in that said polymer blend of a film comprising the claims.
19.如权利要求18所述的燃料电池,其特征在于所述的膜还包含至少一种填料。 19. The fuel cell according to claim 18, wherein said film further comprises at least one filler.
20.如权利要求18所述的燃料电池,其特征在于它还包括至少一种嵌入在所述的膜中的多孔支承层。 20. A fuel cell according to claim 18, characterized in that it further comprises at least one embedded in said porous membrane support layer.
21.如权利要求18所述的燃料电池,其特征在于所述燃料电池用液烃燃料工作。 21. A fuel cell according to claim 18, wherein said fuel cell using a liquid hydrocarbon fuel.
22.如权利要求18所述的燃料电池,其特征在于所述的燃料电池用甲醇燃料工作。 22. A fuel cell according to claim 18, wherein said fuel cell using methanol fuel work.
23.蓄电池,它包含被聚合离子交换膜隔开的阳极室和阴极室,其特征在于所述的膜包含权利要求1所述的共混聚合物。 23. The battery, which comprises an ion exchange membrane are polymerized separated anode compartment and a cathode compartment, wherein said membrane comprises a polymer blend of claim 1, wherein.
24.如权利要求1所述的组合物的制造方法,其特征在于它包括:a)至少一种含有丙烯酸或乙烯基单元的可聚合单体在至少一种能分散在介质中的氟聚合物分散液中进行接种乳液聚合反应。 24. The method for producing a composition according to claim 1, characterized in that it comprises: a) a polymerizable acrylic or vinyl monomers containing at least one unit of at least one type of dispersed fluoropolymer in the medium dispersion inoculated emulsion polymerization.
25.如权利要求24所述的方法,其特征在于所述的至少一种氟聚合物是共聚物。 25. The method of claim 24, wherein said at least one fluoropolymer is a copolymer.
26.如权利要求24所述的方法,其特征在于所述的氟聚合物包含聚(偏二氟乙烯)。 26. The method of claim 24, wherein said fluoropolymer comprises poly (vinylidene fluoride).
27.如权利要求24所述的方法,其特征在于所述的氟聚合物包括a)聚(偏二氟乙烯)和b)六氟丙烯、四氟乙烯、四氟氯乙烯、氟化乙烯、或它们的组合。 27. The method of claim 24, wherein the fluoropolymer comprises a) a poly (vinylidene fluoride) and b) hexafluoropropylene, tetrafluoroethylene, tetrafluoroethylene, vinyl chloride, vinyl fluoride, or a combination thereof.
28.如权利要求24所述的方法,其特征在于所述的氟聚合物包括a)约30-100重量%的聚(偏二氟乙烯)和0-70重量%的至少一种带有至少一个氟原子的聚(烯烃)。 28. The method of claim 24, wherein the fluoropolymer comprises a) from about 30 to 100% by weight of poly (vinylidene fluoride), and 0-70 wt% of at least one with at least one fluorine atom poly (olefin).
29.如权利要求24所述的方法,其特征在于所述的离子基团或可离子化基团是磺化基团或膦酸化基团或者两者皆有。 24 29. The method according to claim, wherein said ionic group or ionizable group is a sulfonate groups or phosphonated group or both.
30.如权利要求1所述的组合物的制备方法,其特征在于它包括掺混:a)至少一种含有丙烯酸单元、乙烯基单元或两者皆有、和至少一种离子基团或可离子化基团的聚合物;和b)至少一种热塑性氟聚合物,其中a)和b)是不同的。 30. A method for producing a composition according to claim 1, characterized in that it comprises mixing: a) at least one unit comprising acrylic acid, vinyl units, or both, and at least one ionic group or polymeric ionizable group; and b) at least one thermoplastic fluoropolymer, wherein a) and b) are different.
31.如权利要求30所述的方法,其特征在于所述的掺混通过熔融掺混或挤出掺混或溶剂掺混完成。 30 31. The method according to claim, characterized in that said blend by melt blending or extrusion blending or solvent blending is completed.
32.如权利要求30所述的方法,其特征在于a)聚合物由乳液聚合、本体聚合或溶液聚合制备。 30 32. The method according to claim, characterized in that a) polymer produced by emulsion polymerization, bulk polymerization or solution polymerization.
33.膜,其特征在于它包括权利要求1所述的组合物。 33. A film, characterized in that it comprises a composition according to claim 1.
34.组合物,其特征在于它包括a)至少一种含有可聚合的丙烯酸、或乙烯基的单体或者两者皆有、和至少一种带有至少一种离子基团或可离子化基团或者两者皆有的单体;b)在存在至少一种能分散在介质中的氟聚合物分散液的情况下聚合形成的聚合产物。 34. A composition, characterized in that it comprises a) at least one containing a polymerizable acrylic or vinyl monomers, or both, and at least one having at least one ionic group or ionizable group b) in the presence of the polymerization product of at least one can be dispersed in the medium the fluoropolymer dispersion where the polymerization is formed; group or both monomers.
Description  translated from Chinese
含有离子基团或可离子化基团的氟聚合物树脂和含有该树脂的产品 Fluoropolymer resin containing ionic groups or ionizable groups containing the resin product

发明背景本发明涉及聚合树脂,并特别涉及含有离子基团和/或可离子化基团的聚合树脂,它们可用于各种产品,如聚合电解质膜和其它热塑性物品。 BACKGROUND OF THE INVENTION The present invention relates to a polymeric resin, and particularly relates to compositions containing an ionic group and / or ionizable group polymerizable resin, they can be used in various products, such as polymeric electrolyte membrane and other thermoplastic materials. 本发明还涉及这些树脂的制造方法和它们的用途。 The present invention also relates to a method of producing these resins and their use.

全氟碳离子交换膜提供了高度的阳离子迁移,并已被广泛用作离子交换膜。 Perfluorocarbon ion exchange membrane to provide a high degree of ion transport, and has been widely used as an ion exchange membrane. 聚合离子交换膜可称作固相聚合物电解质或聚合物交换膜(PEM)。 Polymerization may be referred to the ion exchange membrane or solid polymer electrolyte polymer exchange membrane (PEM). 最常用并可市购的膜是NafionTM和AciplexTM聚合物。 The most commonly used and commercially available membrane is NafionTM and AciplexTM polymers. 但是据报道和文献记载,这些膜适于用气体燃料工作,但不适于用液体燃料工作,这主要是由于燃料渗透(crossover)使电池性能下降。 However, it was reported and documented, these membranes suitable for use gaseous fuel, but not suitable for working with liquid fuel, which is mainly due to fuel permeation (crossover) of the battery performance. 膜的耐化学性和机械强度对于燃料电池的应用来说是重要的性能。 Chemical resistance and mechanical strength of the film is an important performance for fuel cell applications. 的确,膜通常要承受高差压和其它条件。 Indeed, the film is generally subject to high differential pressure and other conditions. 而且,当膜极薄如小于100微米时,机械强度变得尤为重要。 Moreover, when the film is very thin, such as less than 100 micrometers, the mechanical strength becomes particularly important. 另外,如果用于燃料或蓄电池,膜处于温度可高达150℃的强酸性介质中,并存在金属离子和溶剂。 Also, if a fuel or a battery, the film is at a temperature up to 150 ℃ strongly acidic medium, and the presence of metal ions and a solvent. 该环境需要膜具有耐化学性。 This environment requires film having chemical resistance.

目前,许多含氟膜具有下列的一个或多个缺点:i)液体通过膜的高渗透;ii)氟化聚合物和其它聚合物的不均匀掺混导致性能降低;iii)液体燃料存在时耐化学性不足;iv)需要高磺化度才能适当起作用;v)缺乏磺化基团的不均匀分配;和/或vi)机械性能差。 Currently, many fluorine-containing film has one or more of the following disadvantages: i) high liquid permeation through the membrane; nonuniform blending ii) fluorinated polymer and other polymers result in decreased performance; iii) the presence of liquid fuel resistant lack of chemistry; iv) require a high degree of sulfonation to work properly; v) lack of uneven distribution of sulfonated groups; poor and / or vi) mechanical properties.

de Nora等的美国专利N0.4,295,952涉及的阳离子膜具有部分磺化的苯乙烯、二乙烯基苯和2-乙烯基吡啶、4-乙烯基吡啶和/或丙烯酸中的至少一种所形成的三元聚合物。 tristyryl cation membrane de Nora et al U.S. Patent N0.4,295,952 involves having partially sulfonated, divinylbenzene and 2-vinylpyridine, 4-vinylpyridine and / or at least one of the formed acrylic acid Yuan polymers.

Enrenberg等的美国专利No.5,679,482涉及结合了含离子基团离子导电膜的燃料电池。 Enrenberg etc. U.S. Patent No.5,679,482 relates to a combination of an ionic group-containing ion conductive membrane of a fuel cell. 形成该膜的聚合物含有用磺化试剂磺化的苯乙烯。 The film forming polymer with a sulfonating agent comprising sulfonated styrene. 单体或聚合物上都可发生磺化。 Can occur on sulfonated monomers or polymers.

美国专利No.5,795,668描述了一种燃料电池,它含有使用NafionTM类聚合物的增强聚合物离子交换膜(PEM)的蓄电池。 U.S. Patent No.5,795,668 describes a fuel cell, comprising using NafionTM polymer reinforced polymer ion exchange membrane (PEM) of the battery. 该PEM基于氟化多孔支承层和增强离子交换膜,当量约为500-2000,优选的离子交换容量为0.5-2毫当量/克干树脂。 The PEM based on fluorinated porous supporting layer and enhanced ion exchange membrane equivalent weight of about 500-2000, preferably of the ion exchange capacity of 0.5 meq / g dry resin. 该多孔支承层由某些PTFE(聚四氟乙烯)和PTFE共聚物制成。 The porous supporting layer made of some PTFE (polytetrafluoroethylene) and a copolymer made of PTFE. 该膜是侧链含有-CF2CF2SO2F的全氟聚合物。 The film is a side chain containing -CF2CF2SO2F perfluoropolymer. 从文献中已知,Nafion类聚合物在甲醇燃料电池中会发生机械性断裂并有液体渗透的问题。 Is known from the literature, Nafion polymer in a methanol fuel cell will have a mechanical fracture and liquid penetration problem.

Rusch的WO 97/41168涉及含有离子交换树脂的多层离子交换复合膜,该树脂如氟化或非氟化的聚苯乙烯基材的磺酸盐和磺化的聚四氟乙烯。 Rusch of WO 97/41168 relates to a multilayer composite ion-exchange membrane containing an ion exchange resin, the resin such as fluorinated or non-fluorinated polystyrene sulfonates and sulfonated substrate polytetrafluoroethylene.

Al的WO 98/20573描述了含有高度氟化的锂离子交换聚合物电解质膜(PEM)的燃料电池。 The WO 98/20573 Al describes a lithium ion exchange polymer electrolyte membrane (PEM) fuel cell comprising a highly fluorinated. 该PEM基于用疏质子溶剂吸液的离子交换膜。 The PEM-based solvent with an aprotic liquid-absorbent ion-exchange membrane.

WO 98/22898描述了含有聚苯乙烯磺酸和聚(偏二氟乙烯)的聚合膜,它在直接甲醇燃料电池(DMFC)的应用中可降低甲醇的渗透。 WO 98/22898 describes a polymeric film containing polystyrene sulfonic acid and poly (vinylidene fluoride), which is in the direct methanol fuel cell (DMFC) applications can reduce the infiltration of methanol. 但是,所述的聚合物混合方法不能提供可接受的掺混物,并且磺化步骤复杂。 However, the polymer mixture according to the method does not provide an acceptable blend, and sulfonation steps are complicated.

Holmberg等(J.材料化学(Material Chem).(1996 6(8),1309)描述了质子导电膜的制造方法,它通过光照将苯乙烯接枝到PVDF薄膜上,然后用氯磺酸磺化。本发明中,因为磺化基团可用磺化单体引入,所以不需要磺化步骤。 Holmberg, etc. (J. Materials Chemistry (Material Chem). (1996 6 (8), 1309) describes a method for producing a proton conducting membrane, it is through the light styrene grafted onto PVDF film and then sulfonated with chlorosulfonic acid In the present invention, because the sulfonate groups introduced into the sulfonated monomer can be used, so no sulfonation step.

因此,需要克服一项或更多项这些局限性,并要发展能用于液体燃料电池的膜。 Therefore, the need to overcome one or more of these limitations, and the film can be used to develop a liquid fuel cell. 更为特别的是,需要发展能和其它聚合物紧密混合的氟聚合物,以及直接由氟聚合物的水分散液制造膜的方法。 More specifically, the need to develop energy-fluoro intimately mixed polymers and other polymers, and a method of manufacturing the liquid film is directly fluoropolymer dispersion by water. 而且,需要提供组合物和合成方法以及使用含有磺化的或其它官能团的氟聚合物的水分散液的方法。 Further, a need to provide compositions and methods and the use of synthetic methods sulfonated fluoropolymer, or other functional group-containing aqueous dispersion. 此外,需要提供更容易且对环境无害的方法。 In addition, the need to provide easier and environmentally friendly approach. 除此之外,本领域的技术人员还优选具有更高耐化学性和机械强度的聚合电解质膜。 In addition, those skilled in the art will also preferably have a higher chemical resistance and mechanical strength of the polyelectrolyte membrane.

发明概述所以,本发明的目的是提供含有离子官能团的氟聚合物。 SUMMARY OF THE INVENTION Therefore, an object of the invention to provide a fluoropolymer-containing ionic functional groups.

本发明的另一个目的是提供具有高耐化学性和/或机械强度的聚合电解质膜。 Another object of the present invention is to provide a high chemical resistance and / or mechanical strength of the polymeric electrolyte membrane.

本发明的另一个目的是提供可形成聚合电解质膜成分的聚合物,它能避免上述的一项或更多项缺点,如避免液体通过膜的高渗透率。 Another object of the present invention is to provide polymerization of the polymer electrolyte membrane component may be formed, which avoids one or more of the above disadvantages, such as avoiding high liquid permeability through the membrane.

本发明的另一个目的是提供可直接由聚合物的水分散液制成的膜。 Another object of the present invention is to provide a film directly from the aqueous dispersion of a polymer made.

本发明的另一个目的是提供无需单独磺化步骤的含有离子基团或可离子化基团的氟聚合物。 Another object of the present invention is to provide a separate sulfonation step without fluoropolymer containing an ionic group or ionizable group.

下面将分几部分描述本发明的附加目的和优点,这些部分从描述中是明显的,或可以通过实施本发明来理解。 The following sub-sections describe the present invention, together with additional objects and advantages, these parts are evident from the description, or may be understood by implementing the present invention. 通过将本书面描写和附加权利要求中各结合和特别指出的要素,可了解并达到本发明的目的和其它优点。 This written description and by the appended claims and each combination particularly pointed out in the elements, can understand and achieve the object and other advantages of the present invention.

为达到这些和其它优点,并根据本文所体现和描述的本发明目的,本发明涉及含有至少一种丙烯酸类树脂和/或乙烯基树脂和至少一种热塑性氟聚合物所形成的共混聚合物,其中丙烯酸和/或乙烯基树脂带有至少一种离子基团或可离子化基团,如磺化基团。 To achieve these and other advantages and in accordance embodied and described herein, object of the present invention, the present invention relates to a polymer blend comprising at least one acrylic resin and / or vinyl resin and at least one thermoplastic fluoropolymer formed wherein the acrylic and / or vinyl resin having at least one ionic group or ionizable group such as sulfonate groups.

本发明还涉及一种组合物,它包括掺混下列组分的聚合产物:a)至少一种含有丙烯酸和/或乙烯基单元和至少一种离子基团或可离子化基团的聚合物;和b)至少一种热塑性氟聚合物,其中a)和b)是不同的。 The present invention also relates to a composition, which comprises blending the polymerization product of the following components: a) acrylic and / or vinyl polymer unit and at least one ionic group or ionizable group containing at least one; and b) at least one thermoplastic fluoropolymer, wherein a) and b) are different.

本发明还涉及一种组合物,它包括下列的聚合产物:a)至少一种含有可聚合的丙烯酸和/或乙烯基的单体和至少一种含有至少一种离子基团或可离子化基团或者两者皆有的单体;b)存在能分散在介质中的至少一种氟聚合物。 The present invention also relates to a composition, which comprises the polymerization product of: a) containing at least one polymerizable acrylic and / or vinyl monomer and at least one comprising at least one ionic group or ionizable group group, or both, monomer; b) can be dispersed in a medium the presence of at least one fluoropolymer.

而且,本发明还涉及制造上述组合物的优选方法,它包括下列步骤:a)至少一种含有可聚合的丙烯酸和/或乙烯基的单体和至少一种含有至少一种离子基团或可离子化基团的单体,在至少一种能分散在介质中的聚合物分散液中进行接种乳液聚合。 Moreover, the present invention also relates to a preferred method of making the above-described composition, comprising the steps of: a) containing at least one polymerizable acrylic and / or vinyl monomer and at least one comprising at least one ionic group or ionizable group of the monomer, at least one type of polymer dispersed in a medium inoculated dispersion emulsion polymerization.

本发明还涉及下列物质的掺混物:a)至少一种含有丙烯酸和/或乙烯基单体和至少一种离子基团或可离子化基团的聚合物;和b)至少一种热塑性氟聚合物,其中a)和b)是不同的。 The present invention also relates to a blend of the following substances: a) acrylic and / or vinyl monomer and polymer of at least one ionic group or ionizable group comprising at least one; and b) at least one thermoplastic fluorine polymer, wherein a) and b) are different.

本发明还涉及含有本发明组合物的聚合离子交换膜,并且涉及含有本发明的膜的燃料电池和蓄电池。 The present invention also relates to a polymerizable composition of the invention comprising an ion exchange membrane, and to a film of the present invention comprises a fuel cell and battery.

另外,本发明涉及包含上述膜的膜电极装置,并涉及使用该膜电极装置的燃料电池。 Further, the present invention relates to a membrane electrode assembly including the membrane, and the membrane electrode device involves the use of a fuel cell.

需要了解的是,前面的概述和下面的详述都仅是示范性和解释性的,旨在根据权利要求提供对本发明的进一步解释。 Need to understand that the preceding description and the following detailed description are merely exemplary and explanatory and are intended to provide further explanation of the invention according to claim.

发明详述本发明涉及一种聚合物的掺混物,它含有至少一种氟聚合物和带有至少一种离子基团或可离子化基团(如磺化的或膦酸化的基团)的至少一种丙烯酸和/或乙烯基树脂或聚合物。 DETAILED DESCRIPTION The present invention relates to a polymer blend comprising at least one fluoropolymer and having at least one ionic group or ionizable groups (such as the sulfonated or phosphonated group) at least one acrylic and / or vinyl resin or polymer.

本发明组合物的特征在于,它是下列物质掺混后得到的产物:a)至少一种含有丙烯酸或乙烯基单元或者两者皆有和含有至少一种离子基团或可离子化基团的聚合物,和b)至少一种热塑性氟聚合物,其中a)和b)各不相同。 The composition of the present invention is that it is a product obtained after mixing the following materials: a) containing at least one acrylic or vinyl units, or both and containing at least one ionic group or ionizable group polymer, and b) at least one thermoplastic fluoropolymer, wherein a) and b) are different.

本发明还涉及一种组合物,它包含a)至少一种含有可聚合的乙烯基和/或丙烯酸的单体和至少一种含有至少一种离子基团或可离子化基团或这两者皆有的单体的聚合产物,其中聚合反应在至少一种能分散在介质中的氟聚合物分散液存在的情况下发生。 The present invention also relates to a composition comprising a) at least one compound containing a polymerizable vinyl and / or acrylic acid and at least one monomer containing at least one ionic group or ionizable group or both polymerization product of all these monomers, wherein the polymerization occurs in at least one case capable of being dispersed in a medium present in the fluoropolymer dispersion.

本发明的聚合物共混物可以是上述或说明书全文所述的由两种聚合物形成的任何类型混合物。 Polymer blends of the present invention may be any type or specification of the above mixture is formed from two polymers. 优选的共混聚合物是两聚合物的均质掺混物。 A preferred polymer blend is a homogeneous blend of the two polymers. 例如,共混聚合物可以是其中一个聚合物至少部分覆盖在另一个聚合物上的共混聚合物。 For example, a polymer blend wherein the polymer may be at least partially covers the other polymers in polymer blends. 优选的氟聚合物被丙烯酸或乙烯基树脂所覆盖,或由至少一种含可聚合乙烯基或丙烯酸的单体和至少一种带有至少一种离子基团或可离子化基团或者两者皆有的单体形成的聚合物作为外壳。 The preferred fluoropolymer is an acrylic or vinyl resin is covered, or from at least one polymerizable vinyl or acrylic-containing monomer and at least one having at least one ionic group or ionizable group or both Jie polymer formed from monomers as the shell. 如前所述,优选实施方式中丙烯酸或乙烯基树脂可部分覆盖或全部覆盖氟聚合物。 As described above, the preferred embodiment acrylic or vinyl resins may be partially or fully cover the fluorocarbon polymer. 虽然除物理附着以外的附着也在本发明范围内,包括化学附着,但丙烯酸类树脂和氟聚合物间的附着优选是物理附着。 Although attachment other than physical attachment are also within the scope of the present invention, including chemical attachment, but the attachment of the acrylic resin and the fluoropolymer is preferably between physical attachment. 在优选的实施方式中,颗粒的粒度一般约为90-500纳米,更优选为约50-300纳米,其中氟聚合物量约为5-95重量%,丙烯酸或乙烯基树脂量约为95-5重量%。 In a preferred embodiment, the size of the particles is generally about 90-500 nm, more preferably about 50 to 300 nm, wherein the fluoropolymer is about 5-95 wt%, acrylic or vinyl resin is about 95-5 % by weight. 优选的氟聚合物含量约为40-80重量%,丙烯酸或乙烯基树脂为约20-60重量%。 Preferred fluoropolymer content of about 40-80% by weight of acrylic or vinyl resin is from about 20-60 wt%.

关于氟聚合物,该氟聚合物可以是均聚物或其它类聚合物,并可以是氟聚合物的混合物或氟聚合物和非氟聚合物的混合物。 About fluoropolymer, the fluoropolymer may be a homopolymer or other polymers, and can be a mixture of fluoropolymers or a mixture of the fluoropolymer and a non fluoropolymer. 优选使用热塑性氟聚合物。 Preferably a thermoplastic fluoropolymer. 优选地,该氟聚合物或氟聚合物的混合物可以是任何能和其它成分形成共混聚合物的氟聚合物,这些成分包括存在的其它聚合物。 Preferably, the polymer or mixture of the fluorine-containing polymer may be any fluorine polymer and other components can be formed of a polymer blend, these ingredients include other polymer is present. 优选的氟聚合物是聚(偏二氟乙烯)聚合物,如聚(偏二氟乙烯)均聚物。 Preferred fluoropolymer is a poly (vinylidene fluoride) polymers, such as poly (vinylidene fluoride) homopolymer. 氟聚合物的其它例子包括、但不限于含有至少一个氟原子的聚(烯烃),如聚六氟丙烯、聚四氟乙烯、聚(氟乙烯)、或它们的混合物。 Other examples of fluoropolymers include, but are not limited to at least one fluorine atom-containing poly (olefin), such as poly hexafluoropropylene, polytetrafluoroethylene, poly (vinyl fluoride), or mixtures thereof. 更优选的氟聚合物是含约30-100重量%偏二氟乙烯和0-70重量%的至少一种带至少一个氟原子的聚(烯烃)形成的聚合组合物,聚(烯烃)如六氟丙烯、四氟乙烯、三氟乙烯(VF3)、四氟氯乙烯、和/或氟乙烯。 More preferably a fluorine-containing polymer is from about 30-100% by weight of vinylidene fluoride and 0-70 wt% of at least one polymerizable composition having at least one fluorine atom of the poly (olefin) is formed of poly (olefin), such as six hexafluoropropylene, tetrafluoroethylene, trifluoroethylene (VF3), tetrafluoroethylene vinyl chloride, and / or vinyl fluoride. 优选地,可包括均聚物、共聚物、三元共聚物、低聚物和其它类聚合物的氟聚合物的分子量优选为约80,000-700,000MW,并且更优选为约100,000-500,000MW。 Preferably, may comprise a homopolymer, the molecular weight of the fluoropolymer copolymers, terpolymers, oligomers, and other types of polymer is preferably about 80,000-700,000MW, and more preferably from about 100,000-500,000MW. 氟聚合物可用美国专利Nos.3,051,677;3,178,399;3,475,396;3,857,827;和5,093,427中所述的技术制备,在此引入其全文以作参考。 Fluoropolymers available U.S. Patent Nos.3,051,677; 3,178,399; 3,475,396; 3,857,827; and 5,093,427 were prepared as described, incorporated in its entirety by reference.

关于丙烯酸类树脂或聚合物,该聚合物或树脂优选含有或带有一个或更多个离子基团或可离子化基团。 On an acrylic resin or polymer, the polymer or resin preferably contains or carries one or more ionic group or ionizable group. 丙烯酸类树脂的例子包括丙烯酸、甲基丙烯酸、这些酸的酯或丙烯腈的聚合物(包括共聚物、三元共聚物、低聚物和相似物)。 Examples of acrylic resin include acrylic acid, methacrylic acid, esters of these acids, or acrylonitrile polymers (including copolymers, terpolymers, oligomers, and similar objects). 丙烯酸类树脂可由可聚合的含乙烯基的单体形成,该单体包括、但不限于丙烯酸烷酯、甲基丙烯酸烷酯及其它。 Acrylic resin may be a vinyl group-containing polymerizable monomer is formed, the monomers include, but are not limited to alkyl acrylates, alkyl methacrylates and other. 丙烯酸类树脂还可含有其它重复单元和不同的丙烯酸烷酯、甲基丙烯酸烷酯、丙烯酸、甲基丙烯酸和丙烯腈的组合。 The acrylic resin composition may further contain other repeating units and various alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid and acrylonitrile. 对本发明来说,丙烯酸类树脂可以包括其它聚合单体,或者可以是两种或更多种不同丙烯酸类树脂的混合物,或还包括非丙烯酸类树脂,如乙烯基单体和苯乙烯单体。 For the present invention, the acrylic resin may include other polymerizable monomers, or may be a mixture of two or more different acrylic resin, or further comprising a non-acrylic resins, such as vinyl monomer and styrene monomer.

此外,丙烯酸类树脂含有至少一种离子基团(如磺酸根或膦酸根)或可离子化基团(如磺化的或膦酸化的基团或磺酰基)。 In addition, an acrylic resin containing at least one ionic group (e.g., sulfonate or phosphonate) or ionizable groups (e.g., group or a sulfonyl group of sulfonated or phosphonated). 可离子化基团是能形成离子的基团如,环氨基酸、磺内酯、马来酸酐、硫醇、硫化物、磷酸酯(Phosphalanes)和相似物。 Ionizable groups are capable of forming an ionic group such as, cyclic amino acids, sultones, maleic anhydride, thiol, sulfide, phosphate (Phosphalanes) and analogues. 这些基团可以用任何方式成为丙烯酸类树脂的部分,如在一种或多种含离子基团或可离子化基团的单体存在的情况下掺混丙烯酸类树脂。 These groups can be used in any way to become part of an acrylic resin, acrylic resin, such as blending in the case of one or more monomers containing ionic groups or ionizable groups exist. 或者,用于形成丙烯酸类树脂的一种或多种单体可以含有离子基团或可离子化基团。 Alternatively, one or more monomers for forming the acrylic resin may contain an ionic group or ionizable group.

除上述关于丙烯酸类树脂的成分以外,丙烯酸类树脂还可含有任何类型的官能团或还在一种或多种任选带有任何类型的官能团的附加单体存在的情况下形成,只要这些单体和丙烯酸类树脂的总体形成相容即可。 In addition to the above components on the acrylic resin, an acrylic resin may also contain any type of functional group or also one or more optional additional monomers with the case of forming any type of functional group is present, as long as these monomers and the overall compatibility of acrylic resin can be formed.

如前所述,优选的丙烯酸类树脂是若干单体的聚合产物,其中一种单体含有离子基团或可离子化基团,另一种含有丙烯酸类树脂的丙烯酸单元。 As described above, the preferred acrylic resin is a polymerization product of several monomers, where one monomer containing an ionic group or ionizable group, another acrylic resin containing acrylic acid units. 更优选的是,丙烯酸类树脂由下列物质聚合形成:(1)丙烯酸烷酯,(2)甲基丙烯酸烷酯,(3)一种或多种与(1)和(2)不同的可共聚单体,(4)一种或多种含有至少一个官能团的单体,(5)含有离子基团或可离子化基团的单体,如磺化的或膦酸化的单体。 More preferably, the acrylic resin is formed by polymerization of the following materials: (1) acrylic acid alkyl ester, (2) alkyl methacrylates, (3) one or more of (1) and (2) different copolymerizable monomer, (4) one or more monomers containing at least one functional group, (5) a monomer containing an ionic group or ionizable group, such as monomers of sulfonated or phosphonated.

丙烯酸酯(1)的例子包括,例如,丙烯酸乙酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸丙酯、丙烯酸异丁酯、丙烯酸戊酯、丙烯酸2-乙基己酯、丙烯酸己酯、丙烯酸氟代烷酯、和它们的混合物。 Examples of acrylate (1) include, for example, ethyl acrylate, methyl acrylate, butyl acrylate, propyl acrylate, isobutyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, fluorine substituting alkyl esters, and mixtures thereof.

甲基丙烯酸酯(2)的例子包括,例如甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸丙酯、甲基丙烯酸异丁酯、甲基丙烯酸戊酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸己酯、甲基丙烯酸氟代烷酯、和它们的混合物。 Examples of methacrylic acid ester (2) include, for example, ethyl methacrylate, methyl methacrylate, butyl methacrylate, propyl methacrylate, isobutyl methacrylate, methyl acrylate, pentyl acrylate, methyl yl acrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, fluorinated alkyl esters, and mixtures thereof.

可共聚单体(3)的例子包括,例如,共轭二烯烃(如1,3-丁二烯、异戊二烯)、芳香族烯基化合物(如苯乙烯、α-甲基苯乙烯、卤化苯乙烯)、二乙烯基烃化合物(如二乙烯基苯)、和它们的混合物。 The copolymerizable monomer (3) include, for example, a conjugated diene (e.g. butadiene, isoprene), aromatic alkenyl compounds (e.g. styrene, α- methyl styrene, halogenated styrene), divinyl hydrocarbon compounds (e.g., divinyl benzene), and mixtures thereof.

带官能团的单体(4)包括、但不限于α、β-不饱和羧酸(如丙烯酸、甲基丙烯酸、富马酸、巴豆酸、衣康酸);乙烯基酯化合物、酰氨化合物(如丙烯酰胺、甲基丙烯酰胺、N-甲基甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-烷基丙烯酰胺、N-烷基丙烯酰甲胺、N-二烷基甲基丙烯酰胺、N-二烷基丙烯酰胺);含有羟基的单体(如甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸二甘醇乙醚酯);含有环氧基团的单体(如丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯);含有硅醇的单体(如甲基丙烯酸γ-三甲氧基硅烷酯、甲基丙烯酸γ-三乙氧基硅烷酯);含醛的单体(如丙烯醛)、烯基氰化物(如丙烯腈、甲基丙烯腈)。 Monomers with functional groups (4) include, but are not limited to α, β- unsaturated carboxylic acid (e.g. acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid); vinyl ester compound, an amido compound ( such as acrylamide, methacrylamide, N- methyl acrylamide, N- methylol acrylamide, N- alkyl acrylamide, N- alkyl acryloyl methylamine, N- dialkylformamide acrylamide, N- dialkyl acrylamide); hydroxyl-containing monomer (such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, diethylene glycol ether esters ); the epoxy group-containing monomer (e.g. glycidyl acrylate, glycidyl methacrylate); silanol-containing monomer (such as methacrylic acid γ- trimethoxysilane methacrylate, γ- three silane esters); aldehyde-containing monomers (e.g., acrolein), alkenyl cyanides (e.g. acrylonitrile, methacrylonitrile). (4)中包括的单体能够发生交联。 (4) includes a monomer capable of crosslinking. 能发生交联的可共聚单体例子包括异丁基甲基丙烯酰胺、甲基丙烯酸缩水甘油酯、二甲基丙烯酸二甘醇酯、和甲基丙烯酸三甲氧基硅烷酯。 Examples of copolymerizable monomers capable of crosslinking include isobutyl methyl acrylamide, glycidyl methacrylate, diethylene glycol dimethacrylate, and methacrylic acid esters trimethoxysilane. 交联对于改进机械性能和耐溶剂性是需要的。 Crosslinking for improving the mechanical properties and solvent resistance are required.

对于一些专门应用,可用低分子量的可共聚聚合物或低聚物。 For some specialized applications, the available low molecular weight polymers or oligomers may be copolymerized. 而且,如果使用丙烯酸烷酯(1)和甲基丙烯酸烷酯(2)的混合物,应该将它们的比例适当调节至达到所需性能。 Further, if the alkyl acrylate (1) and the alkyl methacrylate (2) of the mixture, their proportions should be adjusted appropriately to achieve desired properties.

含有至少一种离子基团或可离子化基团的单体(5)例子包括、但不限于磺基丙基丙烯酰胺、乙烯基磺酸、甲基丙烯酸磺基丙酯、甲基丙烯酸磺基乙酯。 Containing at least one ionic group or ionisable monomer groups (5) include, but are not limited to-sulfopropyl acrylamide, vinyl sulfonic acid, sulfo propyl methacrylate, methyl acrylate, sulfo ethyl ester. 这些单体优选以它们的酸形式使用或以它们的盐衍生物形式使用。 These monomers are preferably used in their acid form or in their salt derivatives thereof. 例如,在接种乳液聚合反应中,磺化单体可在第一阶段或第二阶段掺入或两个阶段都掺入。 For example, the seed emulsion polymerization reaction, the sulfonated monomer can be incorporated or are incorporated in two stages in the first stage or the second stage. 离子基团量优选为约500-2500EW,更优选为约800-1100EW。 Ionic groups is preferably from about 500-2500EW, more preferably about 800-1100EW. 其中EW是当量和每份磺化单元的聚合物克数。 Wherein EW is the equivalent weight in grams of the polymer and sulfonation per unit.

含有可聚合乙烯基和/或丙烯酸的单体混合物的聚合反应可单独进行并然后掺混入氟聚合物,或在氟聚合物存在的情况下聚合。 Containing a polymerizable vinyl and / or acrylic monomer mixture and the polymerization reaction can be carried out separately and then blended into the fluoropolymer, or the polymerization in the case of the presence of the fluoropolymer. 含乙烯基和/或丙烯酸的单体的聚合反应可用溶液聚合、本体聚合、乳液聚合、或其它已知的聚合方法进行。 Vinyl-containing and / or acrylic monomer polymerization can be solution polymerization, bulk polymerization, emulsion polymerization, or other polymerization methods known means.

如果含可聚合乙烯基和/或丙烯酸离子的单体混合物单独进行聚合,再掺混入氟聚合物,可用常规方法进行掺混,包括、但不限于溶液掺混、挤出掺混、胶乳掺混和相似方法。 If the polymerizable vinyl group-containing and / or acrylic monomer mixture ions separately polymerized and then blended into the fluoropolymer, blended using conventional methods, including, but not limited to, solution blending, extrusion blending, and blending the latex similar methods. 对于溶液掺混,聚合物可溶解或分散在溶剂中。 For solution blending, the polymer can be dissolved or dispersed in a solvent. 用于氟聚合物的溶剂可以和用于丙烯酸/乙烯基聚合物的溶剂相同或不同。 Solvent for the fluoropolymer and a solvent may be used for the acrylic / vinyl polymer of the same or different. 例如,掺混可涉及两种溶剂溶液/分散液,或加入到溶剂溶液/分散液的粉末,或在相同溶剂中的两种聚合物,或任何其它组合。 For example, blending may involve two solvent solutions / dispersions, or added to the solvent solution / dispersion of a powder, or the two polymers in the same solvent, or any other combination. 所用的典型溶剂包括四氢呋喃、丙酮、二甲基亚砜、二甲基甲酰胺、N-甲基吡咯烷酮。 Typical solvents used include tetrahydrofuran, acetone, dimethylsulfoxide, dimethylformamide, N- methylpyrrolidone. 对于熔融挤出掺混,一般温度范围约在100-300℃之间,优选约150-250℃。 For melt extrusion blending, generally a temperature range between about 100-300 ℃, preferably about 150-250 ℃. 原料可挤出成球状或薄膜状。 Extrudable materials into a ball or a film. 在胶乳掺混的情况下,可用各种常规方法进行混合:可将丙烯酸/乙烯基胶乳和氟聚合物胶乳混合,或可将丙烯酸/乙烯基聚合物分散或溶解在氟聚合物胶乳中,或用其它已知的混合方法。 In the case of latex blended, various conventional mixing methods: can be acrylic / vinyl latex and latex mixing fluoropolymer, or may be an acrylic / vinyl polymers dispersed or dissolved in the fluoropolymer latex, or Other known mixing method. 混合可涉及两种以上的胶乳。 Mixing may involve two or more latex. 要将每种胶乳的数量和性质都调节到能获得所需的物理和化学性能以及所需的EW。 To the number and nature of each latex are adjusted to get the desired physical and chemical properties and the desired EW. 在水性膜(如,由直接胶乳浇铸来制备)的情况下,可调节一种或多种胶乳的粒度和含固量来得到所需性能。 In aqueous film (e.g., be prepared by direct casting latex), the latex can be adjusted one or more of the particle size and solid content to obtain the desired properties.

如前所述,本发明组合物优选由接种聚合形成。 As described above, the present invention is preferably formed from a composition of seed polymerization. 接种聚合可在和常规乳液聚合相同的条件下进行。 Seed polymerization may be conducted under the same conditions and conventional emulsion polymerization. 优选在接种胶乳中加入表面活性剂、聚合反应引发剂、链转移剂、pH调节剂和最后是溶剂和螯合剂,并且反应在足够的压力、温度和时间的合适反应条件下进行,如在大气压下以约20-150℃的典型温度(更优选为约40-80℃)反应约0.5-6小时。 Inoculation latex is preferably added in the surfactant, polymerization initiator, chain transfer agent, pH adjusting agents, and finally the solvent and the chelating agent, and the reaction under suitable reaction conditions sufficient pressure, temperature and time will be, as in the atmospheric pressure at a typical temperature (more preferably about 40-80 ℃) about 20-150 ℃ reaction for about 0.5 to 6 hours.

使用氟聚合物作为晶种的乳液聚合可根据标准方法进行:起初用单体分散液进行的分批聚合反应;半连续聚合反应,其中部分单体混合物连续进料或分批进料;以及连续聚合反应,其中单体混合物在反应过程中连续进料或分批进料入氟聚合物水分散液。 Fluorine polymers can be according to standard procedures as a seed emulsion polymerization: monomer dispersion was initially carried out batchwise polymerization reaction; semi-continuous polymerization, wherein part of the monomer mixture was continuously fed or fed-batch; and continuous polymerization reaction, wherein the monomer mixture is continuously fed into or fed-batch fluoropolymer aqueous dispersion during the reaction.

表面活性剂可以是阴离子、阳离子、和/或非离子表面活性剂、和/或两性表面活性剂。 The surfactant can be anionic, cationic, and / or non-ionic surfactants, and / or amphoteric surfactants. 表面活性剂可单独使用,或结合使用两种或更多种。 Surfactants may be used alone, or in combination of two or more. 阴离子表面活性剂的例子包括高级醇硫酸酯盐(如,烷基磺酸钠、烷基苯磺酸钠、琥珀酸钠、琥珀酸二烷酯磺酸钠、烷基二苯基醚二磺酸钠)。 Examples of anionic surfactants include higher alcohol sulfuric ester salts (e.g., sodium alkyl sulfonate, sodium alkylbenzene sulfonate, sodium succinate, dialkyl succinate sulfonate, alkyl diphenyl ether disulfonic acid sodium). 阳离子表面活性剂的例子包括氯化烷基吡啶或氯化烷基铵。 Examples of cationic surfactants include alkyl chloride, alkyl pyridinium chloride or ammonium. 非离子表面活性剂包括聚氧乙烯基烷基苯基醚、聚氧乙烯基烷基酯、聚氧乙烯基烷基酯、聚氧乙烯基烷基苯基酯、甘油酯、脱水山梨醇烷基酯、和它们的衍生物。 Non-ionic surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl esters, polyoxyethylene alkylphenyl esters, glycerol esters, sorbitan alkyl esters, and derivatives thereof. 两性表面活性剂的例子包括月桂基甜菜碱。 Examples of amphoteric surfactants include lauryl betaine. 也可用能和上述单体发生共聚的反应性乳化剂(如,苯乙烯磺酸钠、烷基磺酸钠、芳基烷基磺酸钠和相似物)。 Can also be used and the above-mentioned monomer copolymerizable reactive emulsifier (e.g., sodium styrene sulfonate, alkyl sulfonate, arylalkyl sulfonate and analogues). 表面活性剂的通常用量为每100重量份总氟聚合物颗粒中约0.05-5重量份,虽然也可用其它用量。 Surfactant is generally used in an amount, per 100 parts by weight of the total fluoropolymer particles in about 0.05 to 5 parts by weight, although other dosage.

任何在约20-100℃的温度时能在水介质中产生适于自由基聚合反应的自由基的引发剂种类都优选用作聚合反应引发剂。 Any suitable free-radical polymerization reaction to produce the kind of the radical initiator at a temperature of about 20-100 ℃ in an aqueous medium are preferably used as the polymerization initiator. 它们可单独使用,也可和还原剂(如,亚硫酸氢钠(sodium hydrogenobisulfite)、硫代硫酸钠、亚硫酸氢钠(sodiumhydrogenosulfite))结合使用。 They may be used alone, and also reducing agent (e.g., sodium bisulfite (sodium hydrogenobisulfite), sodium thiosulfate, sodium bisulfite (sodiumhydrogenosulfite)) in combination. 例如,过硫酸盐和过氧化氢可用作水溶性引发剂,而异丙基苯过氧化氢、过氧碳酸二异丙酯、过氧化苯甲酰、2,2'-偶氮二甲基丁腈、2,2'-偶氮二异丁腈、1,1'-偶氮二环己烷-1-腈、异丙苯过氧化氢可用作油溶性引发剂。 For example, persulfate and hydrogen peroxide may be used as water-soluble initiators, and cumene hydroperoxide, diisopropyl peroxy carbonate, benzoyl peroxide, 2,2'-azobis-methyl- nitrile, 2,2'-azobisisobutyronitrile, 1,1'-azobis cyclohexane-1-carbonitrile, cumene hydroperoxide can be used as oil-soluble initiator. 优选的引发剂包括2,2'-偶氮二甲基丁腈和1,1'-偶氮二环己烷-1-腈。 Preferred initiators include 2,2'-azobis methylbutyronitrile and 1,1'-azobis cyclohexane-1-carbonitrile. 油溶性引发剂优选溶解在单体混合物或少量溶剂中。 Oil-soluble initiator is preferably dissolved in the monomer mixture or a small amount of solvent. 引发剂用量优选为每100重量份所加单体混合物中约0.1-2重量份。 The amount of initiator is preferably added per 100 parts by weight of the monomer mixture from about 0.1 to 2 parts by weight.

任何合适类型的链转移剂都可用,优选是不会严重延缓反应的那种。 Any suitable type of chain transfer agent are available, preferably not seriously retard the kind of reaction. 可用的链转移剂包括,例如硫醇(如十二烷基硫醇、辛基硫醇)、卤代烃(如四氯化碳、氯仿)、黄原酸酯(xanthogen)(如二硫代黄原酸二甲酯(dimethylxanthogendisulfide))和相似物。 Available chain transfer agents include, for example, mercaptans (such as dodecyl mercaptan, octyl mercaptan), a halogenated hydrocarbon (e.g. carbon tetrachloride, chloroform), xanthate (xanthogen) (e.g. dithiobis Xanthan dimethyl (dimethylxanthogendisulfide)) and analogues. 链转移剂的用量通常为每100重量份所加单体混合物中约0-5重量份。 The chain transfer agent is usually added per 100 parts by weight of the monomer mixture, about 0-5 parts by weight.

在反应过程中可加入少量溶剂以帮助单体鼓胀晶种颗粒(并因此在分子水平增加混合),并改进薄膜形成。 During the reaction, a small amount of solvent may be added to help bulging seed particles of the monomer (and thus increasing the mixing at the molecular level) and improve film formation. 溶剂的加入量应该在具有可加工性、对环境无害、生产安全,和/或不削弱防火性能的范围内。 Amount of solvent should have processability, environmentally friendly, internal safety, and / or range does not impair the performance of the fire. 所用的溶剂包括丙酮、甲乙酮、N-甲基吡咯烷酮、甲苯、二甲基亚砜和相似物。 The solvent used include acetone, methyl ethyl ketone, N- methylpyrrolidone, toluene, dimethyl sulfoxide and analogues.

本发明的一项优点是通过含离子基团或可离子化基团的单体任选地和其它单体在氟聚合物水分散液存在的情况下进行共聚反应,来向氟聚合物引入至少一种离子或可离子化部分,如磺化部分。 An advantage of the present invention is prepared by containing an ionic group or ionisable monomers optionally with other monomeric groups copolymerization reaction in the case of the presence of the fluoropolymer aqueous dispersion, and be introduced to the fluoropolymer, at least an ionic or ionizable moiety, such as sulfonated portions. 因此,本发明中,离子或可离子化官能团通过聚合反应以化学键连到聚合物主链上,因此避免了接枝技术。 Accordingly, the present invention, the ionic or ionizable functional groups by polymerization is chemically attached to the polymer backbone, thus avoiding graft technology.

另外,本发明可以使两种或更多种聚合物在水分散液中紧密掺混,优选使用接种聚合法。 Further, the present invention enables two or more polymers in a closely blended aqueous dispersion, seed polymerization method is preferably used. 因此,所得的树脂是至少一种氟聚合物和至少一种带离子基团或可离子化基团的聚合物所形成的紧密掺混物。 Thus, the resulting resin is at least one fluoropolymer and a polymeric group with at least one ionic group or ionizable intimate blend formed. 因此,就无需接枝技术和对环境不利的溶剂溶液了。 Therefore, there is no need grafting techniques and environmentally unfriendly solvent solution of the. 此外,由于单体上已带有离子基团或可离子化基团如磺化基团,所以无需用酸如硫酸和磺酸或它们的衍生物来进行树脂的后磺化。 Further, since the monomer ionic group or ionizable group such as sulfonate groups have with, it is not necessary with an acid such as sulfuric acid and sulfonic acids or derivatives thereof is performed after the sulfonated resin. 另外,由于单体上的离子基团或可离子化基团是优选聚合的,它沿着聚合物主链的分配易于用本领域已知的常规方法来控制,如注射加入、连续进料、晚加入和相似方法。 Further, since the ionic group or ionisable group-containing monomer is preferably polymerized on, it is easy to conventional methods known in the art distribution along the polymer backbone to control, such as injection is added, continuous feed, Late join and similar methods. 因此,所得的分布在由共混聚合物形成的薄膜中的离子基团或可离子化基团比以前更易控制。 Thus, the resulting distribution of the film formed by the polymer blend of an ionic group or ionizable group is easier to control than before. 因此,就能达到对各种性质如均一性、无规性、不均一性和相似性质的调整。 Therefore, we can achieve a variety of properties such as homogeneity, random sex, uneven and adjust a similar nature.

另外,由于上述这些各种优点,本发明的用途可包括、但不限于膜、燃料电池、涂料、离子交换树脂、油回收、生物膜、蓄电池和相似物。 In addition, since these various advantages, use of the present invention may include, but are not limited to membrane, fuel cells, coatings, ion exchange resins, oil recovery, biological membranes, batteries, and analogues.

聚合离子膜可由本发明的共混聚合物制得。 Polymeric ion-exchange membrane polymer blends of the present invention may be prepared. 可用传统的制膜方法来制备聚合离子膜,如熔体挤出、溶剂浇铸和相似方法。 By conventional film forming method to the preparation of polymeric ion-exchange membrane, such as melt extrusion, solvent casting, and similar methods. 可用本发明的膜制得膜电极装置,并且制备使用该膜电极装置的燃料电池。 The present invention can be used to give film-made membrane electrode assembly, and a fuel cell prepared using the membrane electrode device.

更详细地说,本发明的组合物专门用于燃料电池、蓄电池和相似物。 More particularly, compositions of the invention are designed for fuel cells, batteries and similar objects. 燃料电池和蓄电池中所用的设计和成分可以和常规燃料电池和蓄电池相同,不同的是使用了本发明的组合物来形式聚合离子交换膜。 Design and composition of the fuel cells and batteries can be used in conventional fuel cells and batteries and the same, except that the composition of the present invention to form polymerization ion exchange membrane. 因此,可在本发明中用美国专利No.5,795,668和PCT刊物No.WO 98/22989和WO 98/20573中所述的制造燃料电池和蓄电池的设计和方法,本文全部引入以作参考。 Accordingly, the present invention can be used in the U.S. Patent No.5,795,668 and PCT publication No.WO 98/22989 and WO 98/20573 in the manufacture of the fuel cell and battery design and methods, incorporated by reference herein in its entirety. 所述的膜可单独使用,或和常规填料如二氧化硅和相似物一起使用。 The film may be used alone or with conventional fillers such as silica and analogues used together. 燃料电池可以使用液体或气体燃料,如像甲醇这样的液体烃。 The fuel cell can use liquid or gaseous fuels, such as liquid hydrocarbons such as methanol. 本发明的燃料电池能在大范围操作条件下运行。 A fuel cell of the present invention can be run over a wide range of operating conditions. 本发明的燃料电池可以有多孔支承层和离子交换树脂,其中离子交换树脂至少承载在多孔支承层的一侧上。 A fuel cell of the present invention may have a porous support layer and an ion-exchange resin, wherein the ion exchange resin is carried on at least one side of the porous support layer. 本发明可用于直接甲醇燃料电池或其它燃料电池中。 The present invention can be used in direct methanol fuel cells or other fuel cells. 本发明燃料电池优选地具有低燃料渗透、高导电性和/或高机械强度。 A fuel cell of the present invention preferably has a low fuel permeability, high conductivity and / or high mechanical strength. 膜厚可以是常规的,但优选为约1-10密耳,更优选为约3-5密耳。 The film thickness may be conventional, but is preferably about 1 to 10 mils, more preferably about 3-5 mils. 另外,膜优选具有约500-2500的当量,更优选为约800-1100。 Further, the film preferably has an equivalent weight of about 500-2500, more preferably about 800-1100. 多孔支承层可由任何常规材料如含氟聚合物或其它含烃聚合物如聚烯烃制得。 The porous support layer may be any conventional material such as a fluoropolymer or other hydrocarbon containing polymers such as polyolefins prepared. 多孔支承层的的常规参数是孔径、孔隙率和厚度。 General Parameters of the porous supporting layer is a pore size, porosity and thickness. 本发明的燃料电池优选具有优异的电性能和相对低的电阻。 The fuel cell of the invention preferably have excellent electrical properties and relatively low resistance.

本发明将通过下述实施例进一步阐述,下述实施例仅用来作为本发明的示范。 The invention will be further illustrated by the following examples, embodiments are merely exemplary of the present invention is used as follows.

实施例所有表中如果没有另外指出,单体量和晶种颗粒以重量份计。 EXAMPLES All of the table unless otherwise stated, the amount of monomer and seed particles in parts by weight.

本发明组合物用下述材料和反应条件制得。 Compositions of the present invention is represented by the following materials and reaction conditions are obtained.

原料:聚偏二氟乙烯(PVDF)晶种胶乳是根据美国专利No.4,569,978(本文全部引入以作参考)中所述方法制备的PVDF均聚物晶种胶乳(seed latex)。 Starting materials: polyvinylidene fluoride (PVDF), a seed latex is based on U.S. Patent No.4,569,978 (incorporated herein in its entirety by reference) PVDF in the homopolymer prepared seed latex (seed latex). 树脂如果和胶乳分离,它在230℃时的熔体流动粘度范围为17-23(泊103),由ASTM D3835以100秒-1的剪切速率使用带120锥角入口的15/1:L/D毛细管确定,并且232℃时的熔体流速为7-15克/10分钟,由ASTM D1238确定。 If the separation of the resin and the latex, which has a melt flow at 230 ℃ viscosity in the range of 17-23 when (poises 103), by ASTM D3835 at a shear rate of 100 sec -1 using the cone angle of 120 with the inlet of 15/1 : L / D capillary is determined, and a melt flow rate of 232 ℃ when 7-15 g / 10 min, determined by ASTM D1238. 单体(Elf-Atochem,Aldrich)、引发剂(Aldrich,DuPont)、表面活性剂(Aldrich)和缓冲剂(Aldrich)无需进一步纯化即可使用。 Monomer (Elf-Atochem, Aldrich), initiator (Aldrich, DuPont), a surfactant (Aldrich) and buffers (Aldrich) was used without further purification. 丙烯酸/乙烯基聚合物的单独制备方法是:在1升容器中加入500克水、0.5克NaHCO3、4克月桂基硫酸铵30重量%和0.5克过硫酸铵。 Separate preparation of the acrylic / vinyl polymer is: 500 g of water in a 1 liter vessel, 0.5 g NaHCO3,4 g of sodium lauryl sulfate and 0.5 g of 30 wt% ammonium persulfate. 用氮气对反应器排气20分钟后,将50克包括甲基丙烯酸异丁酯(5克)、甲基丙烯酸甲酯(40克)、丙烯酸丁酯(20克)、甲基丙烯酸磺基丙酯(35克)和巯基丙酸异辛酯(0.4克)的单体混合物倒入反应器内。 The reactor was vented with nitrogen for 20 minutes, 50 g of isobutyl methacrylate comprising (5 g), methyl methacrylate (40 g), butyl acrylate (20 g), methacrylic acid sulfopropoxy ester (35 g) and isooctyl mercaptopropionate (0.4 g) of the monomer mixture was poured into the reactor. 将反应器加热到70℃,并在达到该温度后20分钟后将单体混合物余量以60克/小时的速率加入反应器内。 The reactor was heated to 70 ℃, and after reaching this temperature for 20 minutes the amount of remaining monomer mixture was 60 g / hr added to the reactor. 然后反应进行60分钟,在此之后冷却反应器。 Then the reaction for 60 minutes, after which the reactor was cooled. 接着用氮气对反应器排气30分钟,然后过滤胶乳。 Then the reactor was vented with nitrogen for 30 minutes and then filtered latex. 甲基丙烯酸异丁酯甲基丙烯酸甲酯和丙烯酸丁酯都购自Elf Atochem的商品名Norsocryl。 Isobutyl methacrylate methyl methacrylate and butyl acrylate were purchased from Elf Atochem tradename Norsocryl.

由接种乳液聚合来制备共混聚合物所用的方法:预装料,清洗:将Vazo 67(CAS#13472-08-07,2,2'-偶氮二(2-甲基丁腈))0.3克、月桂基硫酸钠1克和晶种胶乳(PVDF,28重量%固体)400克预装入500毫升装有冷凝器、高纯度氩和单体进口以及机械搅拌器的四颈锅中。 By seed emulsion polymerization method to prepare polymer blends used: pre-material, cleaning: the Vazo 67 (CAS # 13472-08-07,2,2'- azobis (2-methylbutyronitrile)) 0.3 g, 1 g sodium lauryl sulfate and the seed latex (PVDF, 28 wt% solids) 400 g preload 500 ml equipped with a condenser, high purity argon, and a mechanical stirrer and an inlet for monomer four-necked kettle. 通过添加数滴稀HNO3水溶液将混合物的pH值调节到酸性环境。 By adding a few drops of a dilute HNO3 solution pH of the mixture was adjusted to an acidic environment.

反应时间:将反应器加热到75℃,并将单体混合物(甲基丙烯酸甲酯(MMA)46克和甲基丙烯酸磺基丙酯3克)以适当速率用注射泵装入到反应器中。 Reaction time: the reaction was heated to 75 ℃, and the monomer mixture (methyl methacrylate (MMA) 46 克 sulfo propyl methacrylate and 3 g) using a syringe pump at an appropriate rate charged to the reactor . 任选地预装入一部分单体混合物。 Optionally preloaded part monomer mixture. 当加料完毕时,保持反应温度和搅拌120分钟使残余的单体聚合。 When the addition was complete, maintaining the reaction temperature and stirred for 120 minutes so that the residual monomer is polymerized. 然后将介质冷却到室温,排气,并回收最终胶乳。 The medium is then cooled to room temperature, the exhaust gas, and recovering the final latex. 最终无凝结物胶乳的含固量为35重量%。 No condensation final latex solid content of 35 wt%.

表1列出了含磺化单体的氟聚合物树脂的代表性合成数据。 Table 1 lists the data representative synthesis of a sulfonated monomer containing fluoropolymer resin. 氟聚合物晶种树脂与丙烯酸单体之比为70/30重量%。 Ratio of fluoropolymer seed resin and acrylic monomers of 70/30% by weight.

表1 Table 1

BA=丙烯酸丁酯AM=丙烯酰胺SPM=甲基丙烯酸磺基丙酯SSA=苯乙烯磺酸VSA=乙烯基磺酸 AM = BA = butyl acrylate, acrylamide SPM = sulfo propyl methacrylate SSA = styrene vinyl sulfonic acid VSA =

DEGMA=甲基丙烯酸二乙二醇酯由溶剂浇铸制备的聚合离子膜的描述将10克先前制备的聚合物(组成:70重量%PVDF均聚物和30重量%离子聚合物)在烘箱中以100℃干燥至少2小时。 DEGMA = describe polymerizable ionic membrane diethylene glycol methacrylate ester prepared by solvent casting 10 g of the previously prepared polymer (composition: 70 wt% PVDF homopolymer and 30 wt% ionomer) in an oven at 100 ℃ dry for at least 2 hours. 然后将聚合物和50克磷酸三乙酯混合以得到清澈的粘性溶液。 The polymer and 50 g of triethyl phosphate were mixed to give a clear viscous solution. 用约20密耳厚的刀片将该溶液浇铸到玻璃底物上。 With about 20 mil thick blade and the solution was cast onto a glass substrate. 然后以140℃烘焙该溶液60分钟,从而产生约4-6密耳厚的透明薄膜。 Then the solution was 140 ℃ baked for 60 minutes to produce a transparent film of about 4-6 mils thick.

由胶乳浇铸来制备的聚合离子膜的描述将0.15克Triton X405 30重量%水溶液在恒定搅拌下加入到30克用接种聚合(30重量%固体)制备的胶乳中。 The latex prepared by casting the membrane will describe the polymerization 0.15 g Triton X405 30 wt% aqueous solution was added under constant stirring to seed polymerization using a latex (30 wt% solids) prepared in 30 g. 然后将1.5克磷酸三乙酯在恒定搅拌下滴入胶乳中。 Then 1.5 g of triethyl phosphite was added dropwise under constant stirring latex. 将配制好的胶乳在使用前静置至少3小时。 The prepared latex was allowed to stand at least three hours prior to use. 用约25密耳厚的刀片将该薄膜浇铸到Q铝板上,再以220℃烘焙10分钟,从而产生约4密耳厚的均一薄膜。 The film with a razor blade to about 25 mil thick cast onto aluminum Q, then 220 ℃ baked 10 minutes, resulting in about 4 mil thick uniform films.

水吸收量(分别用甲醇、或水/甲醇混合物)测量如下:以100℃真空干燥该膜至少3小时,小心称重,然后将其浸在水(甲醇、或水/甲醇混合物)中350小时。 Water uptake (respectively with methanol, or water / methanol mixture) was measured as follows: to 100 ℃ vacuum drying the film at least three hours, carefully weighed, then immersed in water (methanol, or water / methanol mixture) and 350 hours . 然后擦拭薄膜并再次称重。 Then wipe the film and weighed again.

甲醇渗透量测量如下:将膜放置在购自Nalgene的带有接受器的塑料滤片支架2室间。 Methanol permeation amount was measured as follows: The film is placed between available from Nalgene plastic filter holder with a receptacle chamber 2. 上室中放置3M甲醇水溶液,而下室填满去离子水。 Placed in the upper chamber 3M aqueous methanol, while the lower chamber fills with deionized water. 定时从下室中取出样本,并用气相色谱法测量甲醇含量。 Samples were periodically removed from the chamber, and measuring the methanol content by gas chromatography.

酸通过膜的扩散量测量如下:将薄膜放置在购自Nalgene的带有接受器的塑料滤片支架2室间。 The amount of the acid diffusion through the membrane was measured as follows: The film was placed between available from Nalgene plastic filter holder with a receptacle chamber 2. 上室中放置1M HCl水溶液,而下室填满去离子水。 Placed in the upper chamber 1M HCl aqueous solution, and the lower chamber fills with deionized water. 定时从下室中取出样本,并用pH滴定法测量酸含量。 Samples were periodically removed from the chamber, and measuring the acid content by pH titration.

表2:水和甲醇吸收量以及甲醇渗透量的代表性数据。 Table 2: absorption of water and methanol, and methanol permeation amount of representative data.

5-10密耳薄膜(100-250微米) 5-10 mil film (100-250 microns)

a)表1的组合物b)克液体/克聚合物,350小时处理后c)环境温度d)薄膜滴定+元素分析表3:质子扩散的代表性数据实验:储备水溶液的pH=1.4。 a) The composition of Table 1 b) grams of liquid / gram of polymer, c) ambient temperature d) Elemental analysis film titration + 350 hours after treatment Table 3: proton diffusion experiment representative data: pH = 1.4 aqueous solution reserves. 实验全程中保持恒定。 Remains constant throughout the experiment. 测试进行24小时以上。 Tests over 24 hours.

从表2和3可见,本发明的膜在水和甲醇吸收以及甲醇渗透方面显示出高效。 From Table 2 and 3 that the film of the present invention shows high efficiency in the absorption of water and methanol, and methanol penetration.

另外可见,尽管磺化基团数较低,本发明中的质子运输效力更高。 Also visible, despite the lower number of sulfonate groups, the present invention is higher in proton transport effect.

在本实施例中,使用下表4中所述的氟聚合物制备出另外的聚合离子膜。 In the present embodiment, the fluoropolymer in claim 4 further polymerization the membrane prepared using the following table. 这些聚合物可用上述的技术和原料,并根据所指出的不同点来制备。 These polymers can be used the above-described techniques and materials, and prepared according to the indicated differences. 然后对共混聚合物进行所述的溶剂浇铸或胶乳浇铸。 Then blending said polymer latex is solvent cast or cast. 测量水渗透量和电导率。 Measuring the amount of water penetration and conductivity. 如表5所示,本发明厚度为2-3密耳的薄膜都是导电的(如用本发明膜获得的质子导电率)。 As shown in Table 5, the present invention having a thickness of 2-3 mils are conductive film (such as film of the present invention obtained in proton conductivity).

表4 Table 4

表5:电导率结果。 Table 5: Conductivity results. 所有薄膜都厚2-3密耳 All films are 2-3 mils thick

a水吸收量(重量%)。 a water absorption (wt%). 将干膜在沸水中浸泡2小时,然后在25℃小心称重。 The dry film is immersed in boiling water for 2 hours, then carefully weighed at 25 ℃.

水吸收量由下式给出:水吸收量=100(湿重-干重)/干重b胶乳浇铸薄膜由配制好的胶乳制得。 Water absorption is given by: water uptake = 100 (wet weight - dry weight) / dry weight b latex cast film prepared by the preparation of a good latex. 胶乳如下配制:在50克胶乳(25%固体)中缓缓加入1克Triton X-405。 The latex was formulated as follows: 50 g of the latex (25% solids) was slowly added 1 g Triton X-405. 然后在恒定的轻微搅拌下缓慢加入2.5克磷酸三乙酯,在使用前静置至少60分钟。 Was then slowly added 2.5 g of triethyl phosphate at a constant slight stirring, allowed to stand for at least 60 minutes before use. 接着过滤该胶乳。 The latex is then filtered. 以80℃浇铸和烘焙5-10分钟,并以220℃进行10-15分钟。 To 80 ℃ cast and baked for 5-10 minutes, and 10-15 minutes to 220 ℃. 溶剂浇铸薄膜由干燥粉末分散到溶剂套组(通常是DMSO/水90/10)中制备。 Film by solvent casting dry powder is dispersed in a solvent kit (usually DMSO / water 90/10) were prepared. 最终分散液含有20-30%的固体。 Final dispersion contains 20-30% solids. 分散液以220℃浇铸和烘焙15-20分钟。 Dispersion was 220 ℃ cast and baked for 15-20 minutes. 所有薄膜都厚2-3密耳。 All films are 2-3 mils thick.

c2 105和1赫兹间的AC阻抗用Gamry仪器(恒电位仪-恒电流仪-ZRAPC4/750和电化学阻抗光谱学EIS300软件)测量。 c2 105 Hz and an AC impedance between using Gamry Instruments (potentiostat - galvanostat -ZRAPC4 / 750 and electrochemical impedance spectroscopy EIS300 software) measurements. 使用4探头结构,所给出的数值是在25℃和100%相对湿度下获得的。 Structure using four probes, the value is given at 25 ℃ and 100% relative humidity obtained.

d Nafion薄膜(7密耳厚)购自Aldrich。 d Nafion film (7 mils thick) were purchased from Aldrich. 在和上述相同的条件下测量。 Measured under the same conditions as above.

根据本文所揭示的本发明的说明和实施,本发明的其它实施方式对本领域的技术人员来说是明显的。 According to the specification and practice of the invention disclosed herein, the other embodiments of the present invention to those skilled in the art is apparent. 说明书和实施例仅用来作为示范,而下述确定了本发明的实际范围和主旨。 Instructions and examples are used as a model, and the following identified actual scope and spirit of the invention.

Referenced by
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CN103391804A *17 Feb 201213 Nov 2013阿科玛股份有限公司Fluoropolymer gas separation films
Classifications
International ClassificationC08L33/00, C08L27/12, B01D71/32, C08L41/00, C08L67/06, C08L57/00, C08F259/08, C08J5/22, C08L101/04, H01M2/16, C08F8/44, C08F2/00, H01M8/10, C08L27/16, C08L33/06, H01M8/02
Cooperative ClassificationY02P70/56, H01M8/1044, C08L41/00, H01M8/1039, H01M2300/0082, C08F8/44, H01M2/1653, C08F259/08, C08J5/225, H01M8/1023, C08L67/06, C08L27/16, C08L33/064, H01M8/1081, C08J2327/16
European ClassificationC08L67/06, C08L27/16, C08F259/08, C08L33/06B2, H01M8/10E2B2, H01M8/10E2D, H01M8/10E2P8, H01M8/10E2F2, C08F8/44, H01M2/16C3, C08J5/22B2B2B
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