CN101273092A - Conductive polymers - Google Patents

Conductive polymers Download PDF

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Publication number
CN101273092A
CN101273092A CNA2006800357436A CN200680035743A CN101273092A CN 101273092 A CN101273092 A CN 101273092A CN A2006800357436 A CNA2006800357436 A CN A2006800357436A CN 200680035743 A CN200680035743 A CN 200680035743A CN 101273092 A CN101273092 A CN 101273092A
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conductive polymer
ion conductive
group
solid ion
alkyl
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爱恩·大卫·布罗泽斯顿
约翰·林德里·班考夫特
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Ionic Polymer Solutions Ltd
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Ionic Polymer Solutions Ltd
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    • C08L79/02—Polyamines
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    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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    • C08K5/10—Esters; Ether-esters
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    • C08K5/1575—Six-membered rings
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    • H01M8/1018—Polymeric electrolyte materials
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    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

There is provided a solid ionically conductive polymer having repeat units of a quaternary ammonium and including a plasticiser in an amount sufficient to render the polymer non-crystalline thereby increasing conductivity.

Description

Conductive polymers
The present invention relates to solid ion conductive polymer, comprise its structure and fuel cell, and relevant production method and purposes.
People are very interested in the manufacturing and the purposes of conductive polymers.Known ionic conductive polymer widely might the most famous example be that height is fluoridized (ion-exchange) resin (RTM) wherein.It is the conducting film that conducts electricity by cation conductive that height is fluoridized (ion-exchange) resin (RTM).Obtained great business success though height is fluoridized (ion-exchange) resin (RTM), still had some problems relevant with this material.Especially, height is fluoridized (ion-exchange) resin (RTM) and is only being expanded, could obtain useful specific conductivity during hydration status, and in this state, the volume ratio of material acquisition its volume under the hydration status is about not big 10 times.Therefore, height is fluoridized hydration that (ion-exchange) resin (RTM) film need continue playing conducting film, and at high temperature, and for example under greater than 100 ℃ temperature, it can not carry out conduction work.
International publication application WO00/06610, WO00/06533, WO00/06658, WO01/36510, WO01/40874 and the WO01/74919 that its all the elements are incorporated as reference here discloses the base polymer available from the compound polymerization that has one or more dialkylenes (dienyl) end group in a large number.This polymkeric substance has or has indicated various useful and infusive character, and one of its character of consideration is specific conductivity.Yet the specific conductivity that further studies show that disclosed polymkeric substance in these documents is not best specific conductivity.In fact, the inventor has been found that increases various polymkeric substance significantly, comprise in the above-mentioned international publication application the specific conductivity of common disclosed polymer type be possible.
Therefore, the present invention provides the improvement to the above-mentioned existing conductive polymers of discussing in its some embodiments at least.And the present invention can provide the useful method of using conductive polymers, and the class conductive polymers by anionic conduction is provided.
According to a first aspect of the invention, the invention provides solid ion conductive polymer, it has the quaternary amine repeating unit and comprises softening agent, and it is non-crystalline that the amount of described softening agent is enough to make polymkeric substance to become, and therefore increases specific conductivity.
Do not need hydration, just can obtain to fluoridize the suitable specific conductivity of specific conductivity of (ion-exchange) resin (RTM) with height.Do not wish to be bound by any theory, think that the crystallinity deviation has increased the ion migration efficient between the repeating unit.
Softening agent can exist as the additive of polymkeric substance.Preferred this softening agent is a propylene carbonate.Polymkeric substance can contain the plasticiser additive between 5 and 60% weight.In order to produce the polymkeric substance with reasonable mechanical strength, preferably, polymkeric substance contains the plasticiser additive between 5 and 30% weight.In order to obtain higher specific conductivity, polymkeric substance can contain the plasticiser additive between 25 and 60% weight.Usually, such polymkeric substance has shown poorer a little mechanical property, but this is an acceptable, even is contemplated to be so in some applications.In some instances, polymkeric substance can contain the plastic additive greater than 60% weight.As alternative scheme, polymkeric substance can be a self-plasticization.Polymkeric substance can be self-plasticizations by a large amount of modes.This polymkeric substance can comprise negatively charged ion, and this negatively charged ion exists as the counter ion of quaternary amine, and this negatively charged ion can be as softening agent.In alternative embodiment, quaternary amine itself is as the self-plasticization agent.Usually, bigger negatively charged ion and/or cationic quaternary amine make polymkeric substance unlikely adopt crystal configuration.
Polymkeric substance can contain a large amount of different softening agent.
Polymkeric substance can conduct electricity by anionic conduction.Having been found that to provide the anionic electroconductive polymkeric substance, and this conductive polymers has shown the specific conductivity suitable with the H+ conducting film.As alternative technical scheme, polymkeric substance can conduct electricity by cation conductive, and this cation conductive can be a proton conduction.
Advantageously, polymkeric substance is formed by the monomeric polymerization that comprises one group of sub-molecular formula (I)
Figure A20068003574300081
R wherein 2And R 3Be independently selected from (CR 7R 8) n, perhaps group CR 9R 10, CR 7R 8CR 9R 10Or CR 9R 10CR 7R 8, wherein n is 0,1 or 2, R 7And R 8Be independently selected from hydrogen, halogen or alkyl, and R 9Or R 10One of be hydrogen, another is an electron-withdrawing group, perhaps R 9And R 10Form electron-withdrawing group together, and
R 4And R 5Be independently selected from CH or CR 11, R wherein 11It is electron-withdrawing group;
Dotted line is represented the existence of key or is not had X 1Be group CX 2X 3, wherein the dotted line key that it connected does not exist and group CX 2, the dotted line key that wherein it connected exists, Y 1Be group CY 2Y 3, wherein the dotted line key that it connected does not exist and group CY 2, the dotted line key that wherein it connected exists, and X 2, X 3, Y 2And Y 3Be independently selected from hydrogen, fluorine or other substituting group;
R 1Be selected from hydrogen, halogen, nitro or alkyl, replaced by functional group alternatively or insert;
R 12Be selected from hydrogen, halogen, nitro or alkyl, replaced by functional group alternatively or insert, perhaps
Figure A20068003574300082
With
Z is the negatively charged ion of electric charge m.
Preferably, polymkeric substance is formed by the polymerization of dialkylene (dienyl) quaternary amine, is most preferably formed by the parent material polymerization that comprises one group of sub-molecular formula (II):
Figure A20068003574300091
R wherein 2And R 3Be independently selected from (CR 7R 8) n, perhaps group CR 9R 10, CR 7R 8CR 9R 10Or CR 9R 10CR 7R 8, wherein n is 0,1 or 2, R 7And R 8Be independently selected from hydrogen, halogen or alkyl, and R 9Or R 10One of be hydrogen, another is an electron-withdrawing group, perhaps R 9And R 10Form electron-withdrawing group together, and
R 4And R 5Be independently selected from CH or CR 11, R wherein 11It is electron-withdrawing group;
Dotted line is represented the existence of key or is not had X 1Be group CX 2X 3, wherein the dotted line key that it connected does not exist and group CX 2, the dotted line key that wherein it connected exists, Y 1Be group CY 2Y 3, wherein the dotted line key that it connected does not exist and group CY 2, the dotted line key that wherein it connected exists, and X 2, X 3, Y 2And Y 3Be independently selected from hydrogen and fluorine;
And, R 1Be hydrogen or alkyl, Z is the negatively charged ion of electric charge m.
Here used statement " not existing under the situation of solvent basically " means not to be had the solvent existence or has the solvent that is not enough to complete solubilising reagent, but can have a spot of thinner so that reagent flows.
The condition that polymerization takes place comprises the existence of radiation effect or electron beam, heating or chemical initiator.Under the situation that does not have solvent basically, be fit to produce the polymerization of radiation or electron beam-induced.
Preferably, R 7And R 8Be independently selected from fluorine, chlorine or alkyl or H.Under the situation of alkyl, methyl most preferably.
Possibly, X 2, X 3, Y 2And Y 3In at least one or all are substituting groups except hydrogen or fluorine.X 2, X 3, Y 2And Y 3In preferably at least one or all are the alkyl that replace alternatively possibly.In this embodiment, preferably, X 2, X 3, Y 2And Y 3In at least one, and most preferably all are the alkyl that replace alternatively.More preferred example is C 1To C 4Alkyl, especially methyl or ethyl.Alternative scheme, X 2, X 3, Y 2And Y 3In at least one and preferably all are aryl and/or heterocyclic radical, such as pyridyl, pyrimidyl or contain the pyridine or the pyrimidine of group.
In preferred embodiment, X 1And Y 1Be respectively group CX 2X 3And CY 1Y 2, and dotted line represents not exist key.Therefore, preferred compound is the compound with following sub-molecular formula (IA):
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, X 2, X 3, Y 2And Y 3As defined above.One or more such parent materials can condense together.When using more than one parent material, will produce multipolymer.
When the dotted line key in the group molecular formula (I) exists, resulting polymkeric substance will comprise polyacetylene chain.This will produce the conjugated system that may have associated conductivity.
Compatibly, parent material is with the parent material of cyclopolymerization under the sort of condition used in polymkeric substance produces.This can comprise radiation, use such as the UV radiating, wherein must be under the situation that light trigger exists, the application (it can be the IR forms of radiation) of heat, wherein must be under the situation that initiator exists, the application of initiator such as the chemical initiator by other kind is perhaps by using the initiation of electron beam.Here used statement " chemical initiator " refer to can initiated polymerization compound, such as radical initiator and ionic initiator, positively charged ion or the anionic initiator understood such as this area.
Preferably, parent material under ultraviolet radiation or the thermal-radiating influence or both the influence under polymerization.Cyclopolymerization can spontaneous generation or is taken place under the situation that the initiator that is fit to exists.The example of the initiator that is fit to comprises 2,2, and-Diisopropyl azodicarboxylate (AIBN), aromatic ketone be such as benzophenone, particularly methyl phenyl ketone; Chloroacetophenone is such as two or three-chloro-acetophenone; The dialkoxy methyl phenyl ketone is such as dimethoxy-acetophenone (selling with trade(brand)name " Irgacure651 "), dialkyl group hydroxyacetophenonum, such as dimethyl hydroxyacetophenonum (selling with trade(brand)name " Darocure 1173 "); The dialkyl group hydroxyacetophenonum alkyl oxide that replaces, such as the compound of following molecular formula:
Figure A20068003574300102
R wherein yBe alkyl, particularly 2,2-methylethyl, R xBe hydroxyl or halogen such as chlorine, R pAnd R qBe independently selected from alkyl or halogen such as chlorine (example is sold with trade(brand)name " Darocure 1116 " and " TrigonalP1 "); 1-benzoyl hexalin 2 (selling) with trade(brand)name " Irgacure 184 "; Bitter almond oil camphor or derivative such as benzoin acetate, benzoin alkylether, particularly bitter almond oil camphor butyl ether, dialkoxy bitter almond oil camphor are such as dimethoxy bitter almond oil camphor or phenylbenzyl ketone; Dibenzyl ketone; Acyl group oxime ester is such as the methyl ester or the ethyl ester (selling with trade(brand)name " Quantaqure PDO ") of acyl group oxime; Acylphosphine oxides, acyl phosphonate, such as the dialkyl group acyl phosphonate, for example, the ketone sulfide that molecular formula is following:
Figure A20068003574300111
R wherein zBe alkyl, Ar is an aryl; Dibenzoyl disulphide such as, 4,4 '-dialkyl benzene formyl disulphide; The phenylbenzene dithiocarbonates; Benzophenone; 4,4 '-two (N, N-dialkyl amido) benzophenone; Fluorenone; Thioxanthone; Benzil; The perhaps compound of following molecular formula:
Figure A20068003574300112
Wherein Ar is an aryl, such as phenyl, and R zBe alkyl such as, methyl (being sold) with trade(brand)name " Speedcure BMDS ".
Terminology used here " alkyl " refers to the straight or branched alkyl, compatibly contains maximum 20, preferably maximum 6 carbon atoms.Term " thiazolinyl " and " alkynyl " refer to unsaturated straight or branched, and it for example comprises, from 2 to 20 carbon atoms, for example from 2 to 6 carbon atoms.Described chain can comprise one or more pairs of keys respectively to triple bond.In addition, term " aryl " refers to aromatic base such as, phenyl or naphthyl.
Term " alkyl " refers to comprise any structure of carbon and hydrogen atom.For example, these can be alkyl, thiazolinyl, alkynyl, aryl such as, phenyl or naphthyl, aralkyl, cycloalkyl, cycloalkenyl group or cycloalkynyl radical.Compatibly, they will contain maximum 20, preferably maximum 10 carbon atoms.Term " heterocyclic radical " comprises the ring of aromatic series or non-aromatic, for example contains 4 to 20, from 5 to 10 annular atomses compatibly, at least one of annular atoms be heteroatoms such as, oxygen, sulphur or nitrogen.The example of this group comprises: furyl, thienyl, pyrryl, pyrrolidyl, imidazolyl, triazolyl, thiazolyl, tetrazyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl, benzothiazolyl, benzoxazolyl, benzothienyl or benzofuryl.
Term " functional group " refers to reactive group, such as halogen, cyano group, nitro, oxo, C (O) nR a, OR a, S (O) tR a, NR bR c, OC (O) NR bR c, C (O) NR bR c, OC (O) NR bR c,-NR 7C (O) nR 6,-NR aCONR bR c,-C=NOR a,-N=CR bR c, S (O) tNR bR c, C (S) nR a, C (S) OR a, C (S) NR bR cOr-NR bS (O) tR a, R wherein a, R bAnd R cThe alkyl that is independently selected from hydrogen or replaces alternatively, perhaps R bAnd R cForm the ring that replaces alternatively together, this ring further contains heteroatoms such as S (O) alternatively s, oxygen and nitrogen, n is integer 1 or 2, t is 0 or integer 1-3.Especially, functional group is such as following group: halogen, cyano group, nitro, oxo, C (O) nR a, OR a, S (O) tR a, NR bR c, OC (O) NR bR c, C (O) NR bR c, OC (O) NR bR c,-NR 7C (O) nR 6,-NR aCONR bR c,-NR aCSNR bR c, C=NOR a,-N=CR bR c, S (O) tNR bR c, or-NR bS (O) tR a, R wherein a, R bAnd R c, n and t as defined above.
Terminology used here " heteroatoms " refer to non-carbon atom such as, oxygen, nitrogen or sulphur atom.When having nitrogen-atoms, they normally exist as the part of ammonia residue, so that they will be by for example, hydrogen or alkyl replaces.
Term " acid amides " is generally understood as and refers to component minor C (O) NR aR b, R wherein aAnd R bBe hydrogen or the alkyl that replaces alternatively.Similarly, term " sulphonamide " will refer to a component minor S (O) 2NR aR b
Employed any electron-withdrawing group or the character that invests the group of amine moiety will depend on its position with respect to the two keys of its required activatory under any particular case, and the character of any other functional group in the compound.Term " electron-withdrawing group " comprises replacing group such as halo in its scope, for example fluoro, chloro and bromo.
R wherein 11Be electron-withdrawing group, it is an acyl group compatibly, such as ethanoyl, nitrile or nitro.
Preferably, X 1, X 2, Y 1And Y 2All be hydrogen.
The radicals R that is fit to aComprise hydrogen or methyl, particularly hydrogen.
One group of preferred polymkeric substance has following array structure:
Figure A20068003574300121
Wherein A is key or CH 2, R 2, R 3, R 4, R 5And R 1Be to define if any pass above-mentioned sub-molecular formula (I) or (II), y is the integer greater than 1, is preferably more than 5 integer.The present invention comprises oligomer in its scope, wherein example y is normally between 2 and 15, preferably between 5 and 12.High-molecular weight polymer also within the scope of the invention, wherein example y can surpass 100.
Z M-Can be halide-ions, boride ion, fluoroform sulphonate, PF 6 -, HSO 4 -, H 2PO 4 -, BF 4 -, NO 3 -Or carboxylicesters, preferably have carboxylicesters, most preferably octanoate or per-fluoro octanoate greater than 5 carbon atom alkyls or perfluorinated alkyl.It also can be other negatively charged ion with alkyl or substituted hydrocarbon radical part.Negatively charged ion with branched hydrocarbyl part can destroy crystalline and form, and therefore increases amorphism.
In the group of sub-molecular formula (I), X 1And Y 1Can represent CX respectively 2X 3And CY 2Y 3, dotted line key does not exist and X 2, X 3, Y 2, Y 3All be hydrogen.
Parent material can be the compound of structural formula (III):
Figure A20068003574300131
X wherein 1, Y 1, R 2, R 3, R 4, R 5Define if any closing above-mentioned molecular formula (I) with dotted line key, r is 1 or above integer, R 6The alkyl, perhaloalkyl radical, siloxanes or the acid amides that are the bridging group of valency r, replace alternatively.
In the compound of molecular formula (III), r is 1, according to radicals R 6Character, compound polymerization easily is to form various polymer types.Comprised the examples of groups of usually finding in the polymer technology in the table 1 below.
Such monomer can be expressed as structure (IV):
Figure A20068003574300132
X wherein 2, X 3, Y 2, Y 3, R 1, R 2, R 3, R 4And R 5If any close above-mentioned molecular formula (I) define R 6' be alkyl, perhaloalkyl radical, siloxanes or the acid amides that replaces alternatively.
The present invention also goes for the polymkeric substance of other kind; For example, in the compound of molecular formula (III), r is greater than 1, and polymerization can produce polymer network.Special example is the compound of the molecular formula (III) of above-mentioned definition, wherein R 6Be bridging group, r is 2 or above integer, for example from 2 to 8 integer, preferably from 2 to 4 integer.It is particularly preferred that r equals 2 embodiment.
When these this compound polymerizations, just formed network, the characteristic of this network can be according to R 6Amount and employed polymerizing condition that the precise nature of group, chain terminator exist are selected.
R 1Can be alkyl, preferably have alkyl, most preferably methyl less than 3 carbon atoms.As alternative technical scheme, R 1Can be H.R 1The embodiment that is H can be used to provide proton conduction mechanism.
In preferred construction, R 6Or R 6' comprise the straight or branched alkyl, the straight or branched alkyl that replaces or insert with functional group alternatively.
R 6Or R 6' can be the alkyl that replaces alternatively, this alkyl has 4 or more a plurality of carbon atom.Although R 6Or R 6' can be branched-chain alkyl, preferably, R 6Or R 6' can be alkyl, most preferably straight chained alkyl.R 6Or R 6' can have 5 and 20 carbon atoms between the carbon atom, preferably, the carbon atom between 8 and 14 carbon atoms, most preferably 10 carbon atoms.
Especially preferred embodiment in, parent material is the compound of molecule formula V:
Figure A20068003574300141
Parent material can be the compound of molecular formula (VI):
Figure A20068003574300142
In molecule formula V and embodiment (VI), Z M-Can be PF 6 -, per-fluoro octanoate or fluoroform sulphonate.
R 6Or R 6' can comprise perhalogeno alkyl, preferably perfluoroalkyl.R 6Or R 6' can comprise perhaloalkyl radical, such as perfluoroalkyl, the perfluoroalkyl of 1 to 3 carbon atom for example is such as perhalogeno methyl, particularly perfluoro-methyl.
R 6Or R 6' can comprise sulfonation group and/or contain the group of imidazoles.
The example of the bridging group that is fit to is included in the bridging group of finding in polyethylene, polypropylene, the nylon, as listed in the table 1.Can in WO 00/06610, find the further example of bridging group.
Table 1
Polymer type The repeating unit of bridging group
Polyethylene ?CH 2
Polystyrene ?CH 2CH(C 6H 5), wherein benzyl ring is to be substituted alternatively
Polyisobutene ?CH 2CH(CH(CH 3) 2)
Polyisoprene ?CH 2CH(CH 3)
Tetrafluoroethylene ?CH 2(CF 2) xCH 2
Poly(vinylidene fluoride) ?CH 2(CF 2CH 2) x
Polyethylene oxide ?(OCH 2CH(CH 3)) xO
Nylon ?CH 2(NHCOCH 2) xCH 2
Peptide ?CH 2(NHCOCH R) xCH 2
Polyurethanes ?-NH-CO-O-
Polyester R of-RC (O) OR '-wherein and R ' are organic groups, such as alkyl
Polysiloxane-based For example ,-SiO 2-，-R 2SiO-or
?-R 2Si 2O 3-, wherein R is an organic group, such as alkyl
Polyacrylate(s) ?-CH 2C(COOH)H-
Polyureas ?-NHCONH-
The polythiourea class ?-NH-C(S)-NH-
The present invention includes the possibility that produces multipolymer, wherein another kind of monomeric compound, the monomeric compound that does not for example have molecular formula (I) mixes before polymerization with the compound of molecular formula (I).This monomer is known in the art.Additionally or alternately, can in having the composite structure of one or more other materials, provide solid ion conductive polymer, to produce the machinery and/or the electrochemical properties of expectation.Solid ion conductive polymer can with one or more inorganic materials such as SiO 2, tungsten compound and glass fibre unite use.
At R 12Be not
Figure A20068003574300161
Embodiment in, monomer preferably has following molecular formula:
Figure A20068003574300162
R wherein 6As defined above, and can be as the defined radicals R in front 6'
Solid ion conductive polymer can be a free-standing, such as form membrane, perhaps can unite use with substrate.Therefore, according to a second aspect of the invention, the invention provides substrate and be positioned at the solid ion conductive polymer of the first aspect present invention on itself or its.
Substrate can be a solid substrate, or wherein has the structure of hole, such as silk screen, knitmesh or porous substrate.Silk screen or web structure can be used to add strength polymer.Can use nylon wire or web structure.
In structure is in the porous embodiment, and solid ion conductive polymer can be arranged in the hole of substrate.In this structure, softening agent not too is easy to wash off from polymkeric substance.Be impregnated in the base bore by the monomer that will be fit to, and in-situ polymerization, this structure can be produced.When polymerization took place, softening agent can exist with monomer.
Preferably, substrate is pottery or zeolite.Can provide tough electro-conductive material in this way, this electro-conductive material can at high temperature be worked, and does not need to conduct the existence of water.
This structure can be the form of ion-conducting membrane.This conducting film has a large amount of application, such as fuel cell.
According to a third aspect of the invention we, the invention provides the method that produces solid ion conductive polymer with quaternary amine repeating unit, the method comprising the steps of: the polymerization quaternary amine, softening agent is provided in polymkeric substance, it is non-crystalline that the amount that this softening agent exists is enough to make polymkeric substance to become, and therefore increases specific conductivity.
Advantageously, before polymerization procedure, quaternary amine can be sprayed on the target structure.This is a kind of extremely effective and practical method of using conductive coating.
Wherein must under the situation that initiator exists, can realize polymerization procedure by application of radiation.Preferably, realize polymerization by application of ultraviolet radiation.
Alternately, wherein must under the situation that initiator exists, can realize polymerization procedure by application of heat.
In one embodiment, before polymerization procedure, softening agent mixes with parent material.
Alternately, can behind the polymerization procedure or during add softening agent to polymkeric substance.
International publication application WO00/06610, WO00/06533, WO00/06658, WO01/40814 and WO01/74919 disclose the preparation of monomer and dialkylene type polymer.International publication application WO01/74919 also discloses monomer and the preparation of the polymkeric substance that formed by the quaternary amines with mono-vinyl type group.
According to a forth aspect of the invention, this aspect provides a kind of method that produces structure, the method comprising the steps of: the porous substrate is provided, introduce quaternary amine and softening agent in the based hole, and the polymerization parent material is to produce solid ion conductive polymer, it is non-crystalline that the amount that this softening agent exists is enough to make polymkeric substance to become, and therefore increases specific conductivity.
According to a fifth aspect of the invention, the invention provides a kind of fuel cell, this fuel cell comprises as the described solid ion conductive polymer of first aspect present invention.Fuel cell can comprise as the described ion-conducting membrane of second aspect present invention, preferably proton conductive membrane.
Although the present invention described above, the present invention prolong and above-mentioned or describe below or claim in any creationary combination or the recombinant of feature.
Embodiment 1
Target molecule formula 1 is as follows.
Figure A20068003574300171
With the dry arm on the condenser, refluxed overnight 1 in dehydrated alcohol, 10-dibromo-decane (28.3g), diallyl amine (15.4g) and K 2CO 3Mixture (58.0g).Use TLC to check reaction process.By filtering, from solvent removal solid K Br and excessive K 2CO 3Remove ethanol and any residual diallyl amine together by rotary evaporation.Any solid K Br that this point occurs in synthetic can be dissolved in the methylene dichloride (DCM), and is filtered.Use dried silica gel to obtain monomer by anhydrous methylene chloride (DCM) flushing.Monomer solution in methyl alcohol or anhydrous methylene chloride (DCM) adds 6M hydrogen perfluor acid (HPF 6) aqueous solution, reach about 5-6 up to mixture pH.The evaporation of permission water, remaining quaternary amine.
Embodiment 2
In embodiment 1, add Irgacure 184 light triggers of propylene carbonate and 3%wt in the prepared quaternary amine 1,, and use the whili mixing tank to mix by slow heating (at about ℃) dissolving.In different experiments, add the propylene carbonate of various amounts, but find that the mixture with 25% and 60% weight propylene carbonate provides best result.
By being exposed to UV radiation curing mixture.Expose number of times and depend on UV source of radiation and exposure condition: in this case, exposure comprises 2 scanning, and each about 1 second, 600W/cm Ga mixed the UV source of mercury.Find that the polymkeric substance that forms thus conducts electricity.
Embodiment 3
In zeolite, add the mixture of quaternary amine 1, light trigger and the propylene carbonate of preparation among the embodiment 2, and by being exposed to UV radiation polymerization in position.Zeolite has shown specific conductivity.
Embodiment 4
Prepared the analogue of target molecule 1, wherein negatively charged ion is a per-fluoro octanoate.Use the method described in the embodiment 1 to prepare analogue, difference is to use moisture Perfluorocaprylic Acid to replace the acid of hydrogen perfluor.Use embodiment 2 described methodology polymerization analogues, and the polymkeric substance of gained has shown the specific conductivity higher a little than the polymkeric substance of embodiment 2.
Embodiment 5
Prepared the analogue of target molecule 1, wherein negatively charged ion is a fluoroform sulphonate.Use the method described in the embodiment 1 to prepare analogue, difference is to use trifluoromethanesulfonic acid (CF 3SO 3H) replaced the acid of hydrogen perfluor.Use embodiment 2 described methodology polymerization analogues, and the polymkeric substance of gained has shown the specific conductivity higher a little than the polymkeric substance of embodiment 2.
Bromoalkane, diallyl amine and K 2CO 3Response strategy be general response strategy, can be used to prepare monomer, this monomer is used for polymerization and purposes of the present invention subsequently.Two replacement bromoalkanes (especially bromine replaces each end that is positioned at alkyl chain) are used to produce the monomer with two dienyl end groups.Mono-substituted bromoalkane is used to produce the monomer with mono alkenyl end group.

Claims (40)

1. solid ion conductive polymer, it has quaternary amine repeating unit and comprises softening agent, and it is non-crystalline that the amount of described softening agent is enough to make polymkeric substance to become, and therefore increases specific conductivity.
2. solid ion conductive polymer as claimed in claim 1, wherein said softening agent exists as the additive of polymkeric substance.
3. solid ion conductive polymer as claimed in claim 2, wherein said softening agent is a propylene carbonate.
4. solid ion conductive polymer as claimed in claim 1, wherein said polymkeric substance is a self-plasticization.
5. solid ion conductive polymer as claimed in claim 4, wherein said polymkeric substance comprises negatively charged ion, and described negatively charged ion is as the counter ion of quaternary amine, and described negatively charged ion itself is as softening agent.
6. solid ion conductive polymer as claimed in claim 4, wherein said quaternary amine itself is as the self-plasticization agent.
7. as the described solid ion conductive polymer of arbitrary claim in the claim 1 to 6, described polymkeric substance conducts electricity by anionic conduction.
8. as the described solid ion conductive polymer of arbitrary claim in the claim 1 to 6, described polymkeric substance conducts electricity by cation conductive.
9. solid ion conductive polymer as claimed in claim 8, described polymkeric substance conducts electricity by proton conduction.
10. the described solid ion conductive polymer of arbitrary as described above claim, wherein said polymkeric substance are to be formed by the polymerization of dialkylene quaternary amine.
Form 11. solid ion conductive polymer as claimed in claim 10, wherein said polymkeric substance are the polymerizations by parent material, described parent material comprises one group of sub-molecular formula (I)
Figure A20068003574300021
R wherein 2And R 3Be independently selected from (CR 7R 8) n, perhaps group CR 9R 10, CR 7R 8CR 9R 10Or CR 9R 10CR 7R 8, wherein n is 0,1 or 2, R 7And R 8Be independently selected from hydrogen, halogen or alkyl, and R 9Or R 10One of be hydrogen, another is an electron-withdrawing group, perhaps R 9And R 10Form electron-withdrawing group together, and
R 4And R 5Be independently selected from CH or CR 11, R wherein 11It is electron-withdrawing group;
Dotted line is represented the existence of key or is not had X 1Be group CX 2X 3, wherein the dotted line key that it connected does not exist and group CX 2, the dotted line key that wherein it connected exists, Y 1Be group CY 2Y 3, wherein the dotted line key that it connected does not exist and group CY 2, the dotted line key that wherein it connected exists, and X 2, X 3, Y 2And Y 3Be independently selected from hydrogen, fluorine or other substituting group;
R 1Be selected from hydrogen, halogen, nitro or alkyl, replaced by functional group alternatively or insert;
R 12Be selected from hydrogen, halogen, nitro, alkyl, replaced by functional group alternatively or insert, perhaps
Figure A20068003574300031
With
Z is the negatively charged ion of electric charge m.
Form 12. solid ion conductive polymer as claimed in claim 11, wherein said polymkeric substance are the polymerizations by parent material, described parent material comprises one group of sub-molecular formula (II)
Figure A20068003574300032
R wherein 2And R 3Be independently selected from (CR 7R 8) n, perhaps group CR 9R 10, CR 7R 8CR 9R 10Or CR 9R 10CR 7R 8, wherein n is 0,1 or 2, R 7And R 8Be independently selected from hydrogen, halogen or alkyl, and R 9Or R 10One of be hydrogen, another is an electron-withdrawing group, perhaps R 9And R 10Form electron-withdrawing group together, and
R 4And R 5Be independently selected from CH or CR 11, R wherein 11It is electron-withdrawing group;
Dotted line is represented the existence of key or is not had X 1Be group CX 2X 3, wherein the dotted line key that it connected does not exist and group CX 2, the dotted line key that wherein it connected exists, Y 1Be group CY 2Y 3, wherein the dotted line key that it connected does not exist and group CY 2, the dotted line key that wherein it connected exists, and X 2, X 3, Y 2And Y 3Be independently selected from hydrogen and fluorine;
And, R 1Be hydrogen or alkyl, Z is the negatively charged ion of electric charge m.
13. as claim 11 or 12 described solid ion conductive polymers, wherein polymkeric substance is to be formed by the parent material cyclopolymerization.
14. as the described solid ion conductive polymer of arbitrary claim, wherein Z in the claim 11 to 13 M-Be halide-ions, boride ion, fluoroform sulphonate, PF 6 -, HSO 4 -, H 2PO 4 -, BF 4 -, NO 3 -Or carboxylicesters, preferably have greater than the alkyl of 5 carbon atoms or the carboxylicesters of perfluorinated alkyl, most preferably octanoate or per-fluoro octanoate.
15. as the described solid ion conductive polymer of arbitrary claim in the claim 11 to 14, sub-molecular formula (I) or (II) group in, X 1And Y 1Represent CX respectively 2X 3And CY 2Y 3, dotted line key does not exist, and X 2, X 3, Y 2And Y 3All be hydrogen.
16. as the described solid ion conductive polymer of arbitrary claim in the claim 11 to 15, wherein parent material is the compound of structural formula (III)
Figure A20068003574300041
X wherein 1, Y 1, R 2, R 3, R 4, R 5With dotted line key as defined in claim 11, r is 1 or above integer, R 6The alkyl, perhaloalkyl radical, siloxanes or the acid amides that are the bridging group of valency r, replace alternatively.
17. solid ion conductive polymer as claimed in claim 16, wherein parent material comprises the compound of molecular formula (IV)
X wherein 2, X 3, Y 2, Y 3, R 2, R 3, R 4And R 5As defined in claim 11, R 6' be alkyl, perhaloalkyl radical, siloxanes or the acid amides that replaces alternatively.
18. as claim 16 or 17 described solid ion conductive polymers, wherein r equals 2.
19. as the described solid ion conductive polymer of arbitrary claim, wherein R in the claim 16 to 18 6Or R 6' comprise the straight or branched alkyl, the straight or branched alkyl that replaces or insert with functional group alternatively.
20. as the described solid ion conductive polymer of arbitrary claim, wherein R in the claim 16 to 19 6Or R 6' be the alkyl that replaces alternatively, this alkyl has 4 or more a plurality of carbon atom.
21. solid ion conductive polymer as claimed in claim 20, wherein R 6Or R 6' be alkyl, straight chained alkyl preferably.
22. solid ion conductive polymer as claimed in claim 21, wherein R 6Or R 6' have 5 and 20 carbon atoms between the carbon atom, preferably, the carbon atom between 8 and 14 carbon atoms, most preferably 10 carbon atoms.
23. solid ion conductive polymer as claimed in claim 22, wherein parent material is the compound of molecule formula V
Figure A20068003574300051
24. as the described solid ion conductive polymer of arbitrary claim, wherein R in the claim 11 to 22 1Be alkyl, preferably have the alkyl that is less than 3 carbon atoms, most preferably methyl.
25. a structure, it comprises substrate and is positioned at wherein or the described solid ion conductive polymer of aforementioned arbitrary claim on it.
26. structure as claimed in claim 25, wherein said substrate is a porous, and solid ion conductive polymer is arranged in the hole of described substrate.
27. structure as claimed in claim 26, wherein said substrate are potteries.
28. structure as claimed in claim 26, wherein said substrate is a zeolite.
29. the described structure of arbitrary claim is the ionic conduction form membrane in the claim 25 to 28.
30. a generation has the method for the solid ion conductive polymer of quaternary amine repeating unit, the method comprising the steps of: the polymerization quaternary amine, softening agent is provided in polymkeric substance, and it is non-crystalline that the amount that described softening agent exists is enough to make polymkeric substance to become, and therefore increases specific conductivity.
31. method as claimed in claim 30, wherein said quaternary amine is sprayed on the target structure before polymerization procedure.
32. as claim 30 or 31 described methods, wherein by must be under the situation that initiator exists, application of radiation realizes polymerization procedure.
33. method as claimed in claim 32 wherein realizes polymerization by application of ultraviolet radiation.
34. as claim 30 or 31 described methods, wherein by must be under the situation that initiator exists, application of heat realizes polymerization procedure.
35. as the described method of arbitrary claim in the claim 30 to 34, wherein before polymerization procedure, softening agent mixes with parent material.
36. as the described method of arbitrary claim in the claim 30 to 34, wherein after polymerization procedure or during, add softening agent to polymkeric substance.
37. method that produces structure, the method comprising the steps of: the porous substrate is provided, introduce quaternary amine and softening agent in the based hole, and the polymerization parent material is to produce solid ion conductive polymer, it is non-crystalline that the amount that this softening agent exists is enough to make polymkeric substance to become, and therefore increases specific conductivity.
38. a fuel cell, it comprises the described solid ion conductive polymer of arbitrary claim in the claim 1 to 24.
39. a fuel cell, it comprises ion-conducting membrane as claimed in claim 29.
40. a kind of as described herein basically polymkeric substance, structure, fuel cell or method.
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