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US5482655A
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Electrically conductive thermoplastic polymer formulations and the use thereof
Assignee: Japat AG
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Filing: 1993-06-11
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Granted: 1996-01-09
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Expires: 2013-06-11
Abstract
Abstract A formulation comprising a) at least one polythiophene in oxidised polycationic form and containing structural repeating units of formula I ##STR1## wherein R 1 and R 2 are each independently of the other linear or branched C 1 -C 18 alkyl or C 2 -C 18 alkoxyalkyl; or are C 3 -C 8 cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogen; or R 1 and R 2 , taken together, are linear C 1 -C 8 alkylene which is unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, C 3 -C 8 cycloalkyl, phenyl, benzyl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halophenyl, C 1 -C 4 alkylbenzyl, C 1 -C 4 alkoxybenzyl or halobenzyl; and b) at least one polyanion of a film-forming thermoplastic polymer containing sulfated alcohol groups ##STR2## and/or sulfonatoalkylated alcohol groups ##STR3## in structural repeating units, wherein the group --(C n H 2n )-- is linear or branched C 2 -C 12 alkylene which contains 2 to 5 carbon atoms in the carbon chain and is unsubstituted or substituted by C 1 -C 4 alkoxy. The formulation is an intrinsically electrically conductive themoformable material.
Inventors
- 👤 Thomas Vogel
- 👤 Jurgen Finter
- 👤 Hartmut Bleier
- 👤 Patrice Bujard
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 18:00
CPC Classifications
C; C08; C08L; C08L41/00; C08G; C08G61/00; C08G61/12; C08G61/122; C08G61/123; C08G61/126; C08L65/00; H; H01; H01B; H01B1/00; H01B1/06; H01B1/12; H01B1/124; H01B1/127; H01G; H01G11/00; H01G11/22; H01G11/30; H01G11/48; H01G11/54; H01G11/56; C08G2261/00; C08G2261/10; C08G2261/14; C08G2261/142; C08G2261/1424; C08G2261/30; C08G2261/32; C08G2261/322; C08G2261/3223; Y; Y02; Y02E; Y02E60/00; Y02E60/13
Claims Analysis
Total Claims: 62
Claim 1
Independent Claim
147 words
A formulation comprising a) at least one polythiophene in oxidised polycationic form and containing structural repeating units of formula I ##STR48## R 1 and R 2 , taken together, are linear C 1 -C 6 alkylene which is unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, C 3 -C 8 cycloalkyl, phenyl, benzyl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halophenyl, C 1 -C 4 alkylbenzyl, C 1 -C 4 alkoxybenzyl or halobenzyl; and b) at least one polyanion of a film-forming thermoplastic polymer containing sulfated alcohol groups ##STR49## and/or sulfonatoalkylated alcohol groups ##STR50## in structural repeating units, wherein the group --(C n H 2n )-- is linear or branched C 2 -C 12 alkylene which contains 2 to 5 carbon atoms in the carbon chain and is unsubstituted or substituted by C 1 -C 4 alkoxy.
Claim 2
Dependent Claim
147 words
A formulation comprising a) at least one polythiophene in oxidised polycationic form and containing structural repeating units of formula I ##STR48## R 1 and R 2 , taken together, are linear C 1 -C 6 alkylene which is unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, C 3 -C 8 cycloalkyl, phenyl, benzyl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halophenyl, C 1 -C 4 alkylbenzyl, C 1 -C 4 alkoxybenzyl or halobenzyl; and b) at least one polyanion of a film-forming thermoplastic polymer containing sulfated alcohol groups ##STR49## and/or sulfonatoalkylated alcohol groups ##STR50## in structural repeating units, wherein the group --(C n H 2n )-- is linear or branched C 2 -C 12 alkylene which contains 2 to 5 carbon atoms in the carbon chain and is unsubstituted or substituted by C 1 -C 4 alkoxy.
Claim 3
Dependent Claim
21 words
A formulation according to claim 1, wherein R 1 and R 2 together as alkylene are C 1 -C 4 alkylene.
Claim 4
Dependent Claim
18 words
A formulation according to claim 2, wherein R 1 and R 2 are C 1 -C 2 alkylene.
Claim 5
Dependent Claim
22 words
A formulation according to claim 2, wherein R 1 and R 2 as alkylene are methylene, ethylene, propylene, butylene, pentylene and hexylene.
Claim 6
Dependent Claim
31 words
A formulation according to claim 1, wherein substituents of R 1 and R 2 as alkylene are C 1 -C 6 alkyl, C 1 -C 6 alkoxy, cyclohexyl, phenyl and benzyl.
Claim 7
Dependent Claim
40 words
A formulation according to claim 1, R 1 and R 2 together are C 1 -C 4 alkylene which is unsubstituted or substituted by 1 or 2 C 1 -C 6 alkyl groups or C 1 -C 6 alkoxy groups.
Claim 8
Dependent Claim
20 words
A formulation according to claim 6, R 1 and R 2 , taken together, are C 1 -C 2 alkylene.
Claim 9
Dependent Claim
35 words
A formulation according to claim 7, wherein R 1 and R 2 are C 1 -C 2 alkylene which is unsubstituted or substituted by C 1 -C 6 alkyl or C 1 -C 6 alkoxy.
Claim 10
Dependent Claim
41 words
A formulation according to claim 8, wherein R 1 and R 2 are a radical of formula --CHR a --CHR b --, wherein R a and R b are each independently of the other H or C 1 -C 6 alkyl.
Claim 11
Dependent Claim
19 words
A formulation according to claim 9, wherein the structural unit of formula I is a radical of formula ##STR51##
Claim 12
Dependent Claim
30 words
A formulation according to claim 1, which contains per structural unit of the polythiophene preferably 0.1 to 0.9 structural units containing sulfated alcohol groups ##STR52## and/or sulfonatoalkylated alcohol groups ##STR53##
Claim 13
Dependent Claim
13 words
A formulation according to claim 11, which contains 0.1 to 0.6 structural units.
Claim 14
Dependent Claim
33 words
A formulation according to claim 1, wherein the group --(C n H 2n )-- is linear or branched C 3 -C 8 alkylene containing 3 to 5 carbon atoms in the carbon chain.
Claim 15
Dependent Claim
21 words
A formulation according to claim 13, wherein the group --(C n H 2n )-- is linear C 3 -C 5 alkylene.
Claim 16
Dependent Claim
18 words
A formulation according to claim 14, wherein the group --(C n H 2n )-- is trimethylene or tetramethylene.
Claim 17
Dependent Claim
56 words
A formulation according to claim 1, wherein a salt form of the thermoplastic polymer containing sulfated alcohol groups in salt form ##STR54## and/or sulfonatoalkylated alcohol groups in salt form ##STR55## has a glass transition temperature of -100° to 350° C., measured by the DSC method, wherein M.sup.⊕ is an alkali metal cation or an ammonium cation.
Claim 18
Dependent Claim
21 words
A formulation according to claim 1, wherein the degree of polymerisation of the thermoplastic polymer is from 5 to 10 000.
Claim 19
Dependent Claim
19 words
A formulation according to claim 1, wherein the alcohol groups in the thermoplastic polymer are completely sulfated and/or sulfonatoalkylated.
Claim 20
Dependent Claim
54 words
A formulation according to claim 16, wherein the salt form of the thermoplastic polymer contains unsubstituted and substituted alcohol groups, wherein the substituted alcohol groups are sulfated alcohol groups ##STR56## and/or sulfonatoalkylated alcohol groups ##STR57## and wherein the ratio of unsubstituted to substituted alcohol groups in the themoplastic polymer is from 50:1 to 1:50.
Claim 21
Dependent Claim
43 words
A formulation according to claim 19, wherein the salt form of the thermoplastic polymer contains 5 to 100% molar of structural units of sulfated alcohol groups ##STR58## and/or sulfonatoalkylated alcohol groups ##STR59## the remaining structural units being corresponding hydroxylated or non-hydroxylated structural units.
Claim 22
Dependent Claim
69 words
A formulation according to claim 1, wherein the sulfated and/or sulfonatoalkylated alcohol groups are present as secondary groups ##STR60## or as tertiary groups ##STR61## in the polymer backbone; or in side groups of the polymer as terminal primary groups --CH 2 --O--SO 3 .sup.⊖ or --CH 2 --O--(C n H 2n )SO 3 .sup.⊖, or as secondary groups ##STR62## or as tertiary groups ##STR63## positioned centrally in the chain.
Claim 23
Dependent Claim
110 words
A formulation according to claim 1, wherein the thermoplastic polymers are derived from polymers or mixtures thereof which contain different hydroxyl groups, selected from the group consisting of polyesters, polyester amides, polycarbonates and polyimides obtained from hydroxyl-group containing monomers; saponified polymers of vinyl esters or ethers; hydroxylated polydiolefins as well as their copolymers with olefinic monomers; polyacrylates or polymethacrylates containing hydroxyalkyl radicals in the ester moiety; polysiloxanes containing hydroxyalkyl groups; reduced polyketones or copolymers thereof; polyethers of glycidyl compounds and diols; polyvinyl phenols or copolymers of vinyl phenols and olefinic comonomers; as well as copolymers of vinyl alcohol, or hydroxylalkyl-containing acrylates or methacrylates, or hydroxylated diolefins with ethylenically unsaturated comonomers.
Claim 24
Dependent Claim
96 words
A formulation according to claim 22, wherein the sulfated and/or sulfonatoalkylated thermoplastic polymers are derived from polymers selected from the group consisting of polyadducts of glycidyl compounds containing on average more than one epoxy group with a diol; homopolymers and copolymers of hydroxyalkyl acrylates and methacrylates; homopolymers and copolymers of butadiene, isoprene and chloroprene in which the double bonds are hydroxylated; polyimides of hydrogenated ketotetracarboxylic acids, especially benzophenonetetracarboxylic acids; hydroxyalkyl polysiloxanes; and polyesters, polyamides, polyurethanes and polyimides from C 4 -C 12 alkenylenediols or C 4 -C 12 alkenylenediamines in which the double bond is hydroxylated.
Claim 25
Dependent Claim
15 words
A formulation according to claim 22, wherein the thermoplastic polymer is either sulfated or sulfonatoalkylated.
Claim 26
Dependent Claim
57 words
A formulation according to claim 1, wherein the thermoplastic polymer is an at least partially sulfated and/or sulfonatoalkylated polyadduct of a) a glycidyl compound containing on average more than epoxy group and b) a diol that contains ##STR64## groups in the polymer chain, wherein the group --C n H 2n -- is as defined in claim 1.
Claim 27
Dependent Claim
102 words
A formulation according to claim 25, wherein the polyadduct contains a) 100 to 5% molar of identical or different structural units of formula II and/or IIa ##STR65## and b) 95 to 0% molar of identical or different structural units of formula III ##STR66## based on the polyadduct, wherein R 3 and R 4 are each independently of the other the radical of a diol containing aliphatic or aromatic diol groups and lacking two hydroxyl groups, and R' is H, C 1 -C 20 alkyl, C 1 -C 20 acyl or aminocarbonyl which is N-substituted by a C 1 -C 20 hydrocarbon radical.
Claim 28
Dependent Claim
13 words
A formulation according to claim 26, wherein R' in formula (III) is H.
Claim 29
Dependent Claim
15 words
A formulation according to claim 26, wherein R 3 and R 4 are identical radicals.
Claim 30
Dependent Claim
46 words
A formulation according to claim 26, wherein R 3 and R 4 defined as a radical containing aliphatic diol groups is linear or branched C 2 -C 2 alkylene, C 3 -C 8 cycloalkylene, C 1 -C 4 alkyl-C 5 -C 8 cycloalkylene, cyclohexylmethylene or cyclohexyldimethylene.
Claim 31
Dependent Claim
102 words
A formulation according to claim 26, wherein R 3 and R 4 are each independently of the other a radical of formula IV ##STR67## wherein X is a direct bond, C 1 -C 4 alkylene, C 2 -C 12 alkylidene, C 5 -C 8 cycloalkylidene, --O--, --S--, --SO--, --SO 2 --, --CO--, --CO 2 --, --N(C 1 -C 4 alkyl) or --Si(CH 3 ) 2 , R 5 and R 6 are each independently of the other H, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, and x is 1 or 2 and y is 0 or 1.
Claim 32
Dependent Claim
25 words
A formulation according to claim 30, wherein X is a direct bond, methylene, ethylene, C 2 -C 6 alkylidene, cyclohexylidene or cyclopentylidene, --O-- or --S--.
Claim 33
Dependent Claim
20 words
A formulation according to claim 30, wherein R 5 and R 6 are H or methyl and y is 1.
Claim 34
Dependent Claim
16 words
A formulation according to claim 26, wherein R 3 and R 4 are the radical ##STR68##
Claim 35
Dependent Claim
30 words
A formulation according to claim 1, wherein the thermoplastic polymer is an at least partially sulfated and/or sulfonatoalkylated polyvinyl alcohol or sulfated and/or sulfonatoalkylated polyvinyl alcohol copolymer containing ##STR69## groups.
Claim 36
Dependent Claim
18 words
A formulation according to claim 34, wherein the thermoplastic polymer is a sulfated and/or sulfonatoalkylated polyvinyl alcohol copolymer.
Claim 37
Dependent Claim
155 words
A formulation according to claim 35, wherein the polyvinyl alcohol copolymer contains a) 90 to 5% molar of structural units of formula V and/or Va ##STR70## and b) 95 to 10% molar of identical or different structural units of formula VI ##STR71## wherein R 7 is H, C 1 -C 6 alkyl, --COOR 10 or --COO.sup.⊖, R 8 is H, F, Cl, CN or C 1 -C 6 alkyl, and R 9 is H, OH, --R"OH, F, Cl, CN, R 10 --O--, C 1 -C 12 alkyl, --COO.sup.⊖, --COOR 10 , --OCO--R 10 , methylphenyl or phenyl, where R 10 is C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl, (C 1 -C 12 alkyl)-C 5 -C 7 cycloalkyl, phenyl, (C 1 -C 12 alkyl)phenyl, benzyl or (C 1 -C 12 alkyl)benzyl, and R" is linear or branched C 2 -C 18 alkylene, poly(C 2 -C 6 oxaalkylene) containing 2 to 6 oxaalkylene units.
Claim 38
Dependent Claim
31 words
A formulation according to claim 36, wherein the copolymer contains 60 to 10% molar of structural units of formula IV, and 40 to 90% molar of structural units of formula V.
Claim 39
Dependent Claim
37 words
A formulation according to claim 36, wherein R" as alkylene contains 2 to 12 carbon atoms, and R" defined as poly(oxaalkylene) contains 2 to 4 oxaalkylene units containing 2 to 4 carbon atoms in the alkylene moiety.
Claim 40
Dependent Claim
51 words
A formulation according to claim 36, wherein R 7 is H, R 8 is H, F, Cl, methyl or ethyl, and R 9 is H, OH, F, Cl, CN, C 1 -C 4 alkyl, C 1 -C 6 alkoxy, --COO--C 1 -C 6 alkyl, --OOC--C 1 -C 6 alkyl or phenyl.
Claim 41
Dependent Claim
34 words
A formulation according to claim 39, wherein in formula (VI) R 7 is H, R 8 is H or methyl, and R 9 is H, OH, CN, methyl, OCH 3 or --COOCH 3 .
Claim 42
Dependent Claim
54 words
A formulation according to claim 36, which contains 20 to 60% molar of structural units of formula V, 50 to 40% molar of structural units of formula --CH 2 --CH 2 -- and 0 to 50% molar of structural units of formula --CH 2 --CH(OH)--, the sum of the molar percentages being 100 percent.
Claim 43
Dependent Claim
24 words
A formulation according to claim 1, wherein the thermoplastic polymer is a sulfated and/or sulfonatoalkylated polymer of a partially hydroxylated polybutadiene, chloroprene or polyisoprene.
Claim 44
Dependent Claim
68 words
A formulation according to claim 42, wherein the thermoplastic polymer contains 5 to 100% molar of structural units of formulae VII and/or VIIa ##STR72## and 0 to 95% molar of structural units of formulae VIII and/or VIIIa, ##STR73## wherein R 11 and R 12 are each independently of the other H, OH or Cl, and the group --C n H 2n -- is as defined in claim 1.
Claim 45
Dependent Claim
33 words
A formulation according to claim 43, which contains 10 to 100% molar of structural units of formulae VII and/or VIIa, and 90 to 0% molar of structural units of formulae VIII and/or VIIIa.
Claim 46
Dependent Claim
33 words
A formulation according to claim 44, which contains 20 to 60% molar of structural units of formulae VII and/or VIIa, and 80 to 40% molar of structural units of formulae VIII and/or VIIIa.
Claim 47
Dependent Claim
18 words
A formulation according to claim 43, wherein R 11 is Cl or H and R 12 is H.
Claim 48
Dependent Claim
104 words
A formulation according to claim 1, wherein the film-forming thermoplastic polymer contains a) 100 to 50% molar of identical or different structural units of formula II and/or IIa ##STR74## and b) 0 to 50% molar of identical or different structural units of formula III ##STR75## based on the polyadduct, wherein R 3 and R 4 are each independently of the other the radical of a diol lacking two hydroxyl groups and containing aliphatic or aromatic diol groups, and R' is H, C 1 -C 20 alkyl, C 1 -C 20 acyl or aminocarbonyl which is N-substituted by a C 1 -C 20 hydrocarbon radical.
Claim 49
Dependent Claim
33 words
A formulation according to claim 47, wherein the polymer contains 60 to 100% molar of structural units of formulae II and/or IIa, and 40 to 0% molar of structural units of formula III.
Claim 50
Dependent Claim
33 words
A formulation according to claim 48, wherein the polymer contains 60 to 90% molar of structural units of formulae II and/or IIa, and 40 to 10% molar of structural units of formula III.
Claim 51
Dependent Claim
10 words
A formulation according to claim 47, wherein R' is H.
Claim 52
Dependent Claim
56 words
A formulation according to claim 47, which contains a polythiophene in oxidised polycationic form and structural repeating units of formula I ##STR76## R 1 and R 2 , taken together, are methylene or the radical --CHR a --CHR b --, wherein R a and R b are each independently of the other H, methyl or ethyl.
Claim 53
Dependent Claim
19 words
A formulation according to claim 51, wherein R a and R b are each independently of the other H.
Claim 54
Dependent Claim
102 words
A formulation according to claim 47, wherein R 3 and R 4 are each independently of the other a radical of formula IV ##STR77## wherein X is a direct bond, C 1 -C 4 alkylene, C 2 -C 12 alkylidene, C 5 -C 8 cycloalkylidene, ----O--, --S--, --SO--, --SO 2 --, --CO--, --CO 2 --, --N(C 1 -C 4 alkyl) or --Si(CH 3 ) 2 , R 5 and R 6 are each independently of the other H, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, and x is 1 or 2, and y is 0 or 1.
Claim 55
Dependent Claim
25 words
A formulation according to claim 53, wherein X is a direct bond, methylene, ethylene, C 2 -C 6 alkylidene, cyclohexylidene or cyclopentylidene, --O-- or --S--.
Claim 56
Dependent Claim
20 words
A formulation according to claim 53, wherein R 5 and R 6 are H or methyl and y is 1.
Claim 57
Dependent Claim
16 words
A formulation according to claim 53, wherein R 3 and R 4 are the radical ##STR78##
Claim 58
Dependent Claim
19 words
A composition according to claim 51, wherein the structural units of the polythiophene correspond to radicals of formula ##STR79##
Claim 59
Dependent Claim
34 words
A formulation comprising a) a thermoplastic or thermosetting resin or a structurally crosslinked polymer in which is incorporated b) an electrically conductive, finely particulate filler obtained from a powder formulation according to claim 1.
Claim 60
Dependent Claim
22 words
A formulation according to claim 58, wherein the amount of component b) is 0.1 to 90% by weight, based on component a).
Claim 61
Dependent Claim
18 words
A formulation according to claim 59, wherein the amount of component b) is 5 to 80% by weight.
Claim 62
Dependent Claim
13 words
A moulding material consisting of a powder formulation as claimed in claim 1.
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