CA2108552A1 - Method of processing neutral polyanilines in solvent and solvent mixtures - Google Patents
Method of processing neutral polyanilines in solvent and solvent mixturesInfo
- Publication number
- CA2108552A1 CA2108552A1 CA002108552A CA2108552A CA2108552A1 CA 2108552 A1 CA2108552 A1 CA 2108552A1 CA 002108552 A CA002108552 A CA 002108552A CA 2108552 A CA2108552 A CA 2108552A CA 2108552 A1 CA2108552 A1 CA 2108552A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- solvent
- polyaniline
- equal
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002904 solvent Substances 0.000 title claims abstract description 87
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title description 20
- 230000007935 neutral effect Effects 0.000 title description 8
- 239000011877 solvent mixture Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 28
- -1 alkylsufinyl Chemical group 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000004327 boric acid Chemical group 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 125000001769 aryl amino group Chemical group 0.000 claims description 12
- 125000004986 diarylamino group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000003282 alkyl amino group Chemical group 0.000 claims description 11
- 150000007942 carboxylates Chemical group 0.000 claims description 11
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 11
- 125000001475 halogen functional group Chemical group 0.000 claims description 11
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- 125000004947 alkyl aryl amino group Chemical group 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Chemical group 0.000 claims description 10
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 8
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical group OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical group [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Chemical group 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- UWYZHKAOTLEWKK-UHFFFAOYSA-N 1,2,3,4-tetrahydroisoquinoline Chemical compound C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000005135 aryl sulfinyl group Chemical group 0.000 claims description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 3
- 125000001589 carboacyl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 claims description 2
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 2
- YQDGQEKUTLYWJU-UHFFFAOYSA-N 5,6,7,8-tetrahydroquinoline Chemical compound C1=CC=C2CCCCC2=N1 YQDGQEKUTLYWJU-UHFFFAOYSA-N 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 150000001343 alkyl silanes Chemical class 0.000 claims description 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000004419 alkynylene group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical group 0.000 claims 2
- ANDLRLQIXLXLNZ-UHFFFAOYSA-N 3-(2-methyl-2h-pyridin-1-yl)propan-1-amine Chemical compound CC1C=CC=CN1CCCN ANDLRLQIXLXLNZ-UHFFFAOYSA-N 0.000 claims 1
- QQIZPZMCGUWNNO-UHFFFAOYSA-N OS(=O)[N+]([O-])=O Chemical group OS(=O)[N+]([O-])=O QQIZPZMCGUWNNO-UHFFFAOYSA-N 0.000 claims 1
- 125000005103 alkyl silyl group Chemical group 0.000 claims 1
- 125000005265 dialkylamine group Chemical group 0.000 claims 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims 1
- LBQAJLBSGOBDQF-UHFFFAOYSA-N nitro azanylidynemethanesulfonate Chemical group [O-][N+](=O)OS(=O)(=O)C#N LBQAJLBSGOBDQF-UHFFFAOYSA-N 0.000 claims 1
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 27
- 239000002585 base Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 15
- 239000002019 doping agent Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 230000003993 interaction Effects 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 8
- 235000010338 boric acid Nutrition 0.000 description 8
- 229960002645 boric acid Drugs 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methyl-1h-indole Chemical compound CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920000775 emeraldine polymer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KKGKDEZGXBKDRQ-UHFFFAOYSA-N ethanesulfonic acid;naphthalene-1,5-disulfonic acid Chemical compound CCS(O)(=O)=O.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O KKGKDEZGXBKDRQ-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229920000763 leucoemeraldine polymer Polymers 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 description 1
- SKECXRFZFFAANN-UHFFFAOYSA-N n,n-dimethylmethanethioamide Chemical compound CN(C)C=S SKECXRFZFFAANN-UHFFFAOYSA-N 0.000 description 1
- IYIAWAACGTUPCC-UHFFFAOYSA-N n-(diethylsulfamoyl)-n-ethylethanamine Chemical compound CCN(CC)S(=O)(=O)N(CC)CC IYIAWAACGTUPCC-UHFFFAOYSA-N 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 description 1
- ZPBSAMLXSQCSOX-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 ZPBSAMLXSQCSOX-UHFFFAOYSA-N 0.000 description 1
- FEWNRIKJXAQRJJ-UHFFFAOYSA-N naphthalene-1,3,7-trisulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC=C21 FEWNRIKJXAQRJJ-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- KQOATKAFTRNONV-UHFFFAOYSA-N oxolan-2-amine Chemical compound NC1CCCO1 KQOATKAFTRNONV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- LUDIBEMMLLZFBF-UHFFFAOYSA-N phenanthrene-2-sulfonic acid Chemical compound C1=CC=C2C3=CC=C(S(=O)(=O)O)C=C3C=CC2=C1 LUDIBEMMLLZFBF-UHFFFAOYSA-N 0.000 description 1
- DATCUBITXKHYTK-UHFFFAOYSA-N phenanthrene-3-sulfonic acid Chemical compound C1=CC=C2C3=CC(S(=O)(=O)O)=CC=C3C=CC2=C1 DATCUBITXKHYTK-UHFFFAOYSA-N 0.000 description 1
- LZSWYOHUWMZPOE-UHFFFAOYSA-N phenanthrene-9-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC3=CC=CC=C3C2=C1 LZSWYOHUWMZPOE-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- LWMPFIOTEAXAGV-UHFFFAOYSA-N piperidin-1-amine Chemical compound NN1CCCCC1 LWMPFIOTEAXAGV-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 150000004060 quinone imines Chemical group 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000008054 sulfonate salts Chemical group 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical group 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical class OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FCMRBZBGGXLKBC-UHFFFAOYSA-J tetrasodium 2-[[1,8-dioxido-3,6-disulfo-7-[(2-sulfonatophenyl)diazenyl]naphthalen-2-yl]diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccccc2S([O-])(=O)=O)c(cc2cc(c(N=Nc3ccccc3S([O-])(=O)=O)c(O)c12)S([O-])(=O)=O)S([O-])(=O)=O FCMRBZBGGXLKBC-UHFFFAOYSA-J 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
Abstract
This invention relates to a solution or plasticized composition comprising one or more polyanilines, and one or more solvents capable of dissolving said polyanilines.
Description
21~ 8 ~
~19q!HOD OF PROCB88ING Nl~UTRAI.
POLYANIL~:NE8 IN 80LVENq! AND I~OLVEN~I! MIXTIJREB
BACKGROUND OF THE INVENTION
l. Field of the Invention This invention relates to solutions of neutral substituted or unsubstituted polyanilines and to methods of forming such solutions. Another aspect of this invention relates to a method of using such solutions to form polymer articles, such as films, printings, coatings and parts.
~19q!HOD OF PROCB88ING Nl~UTRAI.
POLYANIL~:NE8 IN 80LVENq! AND I~OLVEN~I! MIXTIJREB
BACKGROUND OF THE INVENTION
l. Field of the Invention This invention relates to solutions of neutral substituted or unsubstituted polyanilines and to methods of forming such solutions. Another aspect of this invention relates to a method of using such solutions to form polymer articles, such as films, printings, coatings and parts.
2. Prior Art - There has recently been an increased interest in the electrochemistry and electrical phenomena of polymeric systems, such as polyaniline. See for example, U.S. Patent Nos. 3,963,498; 4,025,463;
4,855,361; 4,798,685; 4,806,271; 4,822,638; 4,851,487;
4,798,685 and PCT WO89/01694.
Several solvents for neutral (undoped) polyaniline are known. For example, F. Wudl et al., J. Am. Chem.
Soc. 109 3677(198); U.S. Patent No. 4,913,867; A.
MacDiarmid, et al. PolYm. PreDrints, 30, 147 (1989); X.
Tang et al. Makroml. Chem. RaDid Commun., 9, 829-834;
A.&. Green and A.E. Woodhead, J. Chem. Soc. , 2388(1940); M. Angelopoulos, et al. Mol. Crvst. Li~.
CrYst. Bulietin. p 240 (1988) and M. Inoue et al.
Svnth. Met. 30, 199(1989).
S~MMARY OF THE INVENTION
One aspect of this invention relates to a solution and to a plasticized composition comprising one or more substituted or unsubstituted polyanilines; and one or more solvents capable of dissolving said polyaniline to some extent, capable of plasticizing said polyaniline or a combination thereo~. As used herein "solution" is .
... ...
~ ' ~
-. .
. .
~ ~ rj 2 2 a real solution or an ultra-fine dispersion having an average particle si~e of less than about 100 nanometers, and, as used herein, a "plasticized composition" is a poly~er or a polymer blend which is softened by incorporation of a liquid or low melting temperature solid generally to a level of more than about 1% by weight and less than about 20%. As used herein "polyaniline" is a polymer which is synthesized for example by the head-to-tail linkage of substituted or unsubstituted anilines, and, which depending on oxidation state, consists of phenyl rings and amine linkages (-NH- or -NR- where R is a substituent other than hydrogen) with varying amounts of quinoid rings and imine (-N=) linkages. As used herein "neutral or undoped polyaniline" is characterized by an uncharged backbone and "polyaniline base" is a particular form of undoped polyaniline which contains at least one quinoid diimine linkage in the backbone.
Through use of the solution of this invention polyaniline can be conveniently processed into useful conductive articles of all shapes such as fibers, coatings, printings, films and the like using conventional solution or plasticized polymer techniques.
BRIEF DESCRIPTION OF THE INVENTION
The invention will be more fully understood and further advantages will become apparent when reference is made to the following detailed description of the invention and accompanying drawings in which:
Figure 1 shows a graph showing the Hansen solubility Parameters of solvents and co-solvents for polyaniline base.
Figure 2 is a graph showing the Hansen Solubility Parameters relative to polyaniline base for solvents W O 92/18572 PC~r/US92/03022 , ~1 ~3 ~ ~ 5 2 and non-solvents.
DETAILED DESCRIPTION OF THE INVENTION
One essential ingredient of the solutions or plasticized compositions of this invention is a substituted or unsubstituted polyaniline such. Any form of substituted and unsubstituted polyaniline can be conveniently used in the practice of this invention such as those are characterized by different ratios of phenylene amine and quinone imine backbone segments, as for example leucoemeraldine, protoemeraldine, emeraldine, nigraniline and pernigraniline.
Preferred polyanilines are of the type derived from the polymerization of unsubstituted and substituted anilines of the Formula I:
rl 1~ R,;,, (~
wherein: ( Rl) n is an integer from 0 to 5;
m is an integer from 0 to 5, with the proviso that the sum of n and m is equal to 5; and R1 is the same or different at each occurrence and is selected:from the group consisting of boric acid, phosphinic acid, phosphoric acid, sulfinate salt, amido, carboxylic acid, hydroxyamino, phosphonic acid, halo, hydroxy, cyano, sulfinic acid, carboxylate salt, borate salt, phosphate salt, sulfonate, phosphinate salt, phosphonate salt, amino, sulfonic acid, nitro, amino, cyano, sulfate salt, deuterium or substituted or unsubstituted arylsulfinyl, alkoxycarbonyl, arylsulfonyl, alkylamido, dialkylamido, arylamido, SUBSTITUTE SHEET
.
:
.
.:
.
'~ X ~ S '~ ' diarylamido, alkylarylamido, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylamino, dialkylamino, alkylarylamino, arylamino, diarylamino, aryl, alkynyl, alkylsulfinyl, aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, alkoxyaryl, alkylsulfonyl, arylthio, alkylsulfonylalkyl, or alkylsilane or any two R2 groups together or any R1 group together with any R2 group may form a substituted or unsubstituted alkylene, alkynylene, or alkenylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroaromatic, heteroalicyclic or alicyclic ring, which ring may ôptionally include one or more divalent nitrogen, sulfur, sulfinyl, ester, carbonyl, sulfonyl or oxygen atoms, wherein permissible substituents are one or more amino, alkylamino, dialkylamino, amido, alkylamido, dialkylamido, arylamido, diarylamido, alkylarylamido, arylamino, sulfinic acid, diarylamino, alkylarylamino, phosphonic acid, sulfonic acid, phosphoric acid, boric acid, carboxylate salt, borate salt, sulfonate salt, phosphinate salt, phosphonate salt, hydroxylamino, quaternary ammonium salt, phosphate salt, sulfinate salt, phosphinic acid, sulfate salt, carboxylic acid, halo, nitro, cyano or epoxy moieties; Rl or R2 is an aliphatic moiety having repeat units of the formula:
( OCH2CH2) qOCH3, ( OCH2CH ( CH3 ) ) qOCH3 30(CH2)qCF3~ (CFz)qCF3 or (CH2)gCH3 wherein q is a positive whole number; and R2 is the same or different at each occurrence and is R1 substituents or hydrogen.
35Illustrative of the polyanilines useful in the : ; :
WO92/1~72 PCT/US92/03022 ~5~3 5 'J 2 practice of this invention are those of the Formula II:
S ~
(~)~
wherein:
R1 and R2 are as describe above;
n and m are the same or different at each occurrence and are integers from 0 to 4, with the proviso that the sum of n and m is 4; and y and x are the same or different at each occurrence and are integers equal to or greater than 0, with the proviso that the sum of x and y is greater than 0, preferably x is an integer equal to or greater than about l and/or the ratio of x to y is greater than or equal to about 0.5; and z is an integer equal to or greater than l.
Preferred for use in the practice of this invention are polyanilines of the above Formula II in which:
n is an integer from 0 to about 2;
m is an integer from 2 to 4, with the proviso that the sum of n and m is equal to 4;
R1 is aryl, alkyl or alkoxy having from l to about 30 carbon atoms, cyano, halo, sulfonic acid, carboxylic acid, boric acid, borate, phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid, phosphinate, sulfinic acid, sulfinate, carboxylate, sulfonate, amino, alkylamino, dialkylamino, arylamino, hydroxy, diarylamino, alkylarylamino, or alkyl, aryl or alkoxy substituted with phosphonic acid, phosphate, SUBSTlTUTE SHEE ~
.
: - , . - ~
.
8 ~
phosphoric acid, borate, sulfonate, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate, hydroxy, alkoxy, phosphonate, boric acid, alkyl, phosphinic acid, phosphonate, phosphinate, carboxylic acid or sulfonic acid substituents;
R2 is the same or different at each occurrence and is a alkyl or hydrogen;
x is an integer equal to or greater than l;
y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about l; and z is an integer equal to or greater than about 5.
Particularly preferred for use in the practice of this invention are polyanilines of the above Formula II
in which:
n is an integer from 0 to l;
m is an integer from 3 to 4, with the proviso that the sum of n and m is egual to 4;
Rl is aryl, alkyl or alkoxy having from 1 to about 20 carbon atoms, sulfonic acid, halo, carboxylic acid, amino, carboxylate, alkylamino, phosphonate, dialkylamino, arylamino, phosphonic acid, boric acid, phosphate, phosphoric acid, borate, diarylamino, alkylyarylamino or alXyl or aryl substituted with carboxylic acid, phosphoric acid, boric acid, phosphate, phosphonic acid, borate, sulfonate, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate, halo, phosphonate, or sulfonic acid substituents;
Rz is the same or different at each occurrence and is a hydrogen;
x is àn integer equal to or greater than 2;
y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 2; and . . ~ , :
- . : . :,~
:
W092/l8572 PCT/US92/03022 2 ~ r ~ 2 z is an integer equal to or greater than about 5 Amongst the particularly preferred embodiments, most preferred for use in the practice of this invention are polyanilines of the above Formulas III or V in which:
n is an integer from 0 to 1;
m is an integer from 3 to 4, with the proviso that the sum of n and m is equal to 4;
Rl is aryl, alkyl or alkoxy from 1 to about 15 carbon atoms, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, halo, sulfonic acid, sulfonate, carboxylic acid, carboxylate, or alkyl or aryl substituted with one or more sulfonic acid, carboxylate, amino, alkylamino, dialkylamino, arylamino, diarylamino, halo, alkylarylamino, sulfate, sulfonic acid, or carboxylic acid substituents;
R2 is hydrogen;
x is an integer equal to or greater than 2;
y is equal to or greater than 1, with the proviso that the ratio of x to y is equal to or greater than about 2; and z is an integer equal to or greater than about 5.
In the most preferred embodiments of this invention, the polyaniline is derived from unsubstituted aniline, alkoxy, alkyl, or sulfonic acid substituted aniline or copolymers thereof.
In general, the number of aniline repeat units is not critical and may vary widely. The number of aniline repeat units is preferably at least about 10.
The upper limit can vary widely depending on the desired viscosity and molecular weight and the required degree of processibility i.e. melt processibility, solution processibility and the like. The number of aniline repeat units is pre~erably at least about 20, more preferably, at least about 30 and most preferably - :. . ~ . : ., , : , - :~ - ~
wos2/l8s72 PCT/US92/03022 2 ~ 8 is at least about 40.
Useful polyanilines can be prepared through use of chemical and electrochemical synthetic procedures. For example, one form of polyaniline can be prepared chemically by treating aniline with a suitable oxidizing agent such as a~monium persulfate (NH4) 2S20 in excess acid such as lM HCl or can be prepared electrochemically by the electrochemical oxidation of aniline in aqueous fluoroboric acid electrolyte on a platinum foil anode.
The second component of the solution or plasticized composition of this invention is an "effective solvent". As used herein, "an effective solvent" is a solvent which has a relative dielectric lS constant of equal to or greater than about 5 (preferably equal to or greater than about 6), and a dipole moment equal to or greater than about 3.5 x 10-3 Cm (preferably equal to or greater than about 5 x 10-3 Cm) other than dimethylformamide, N-methylpyrrolidone, pyridine, and dimethylsulfoxide which is capable of dissolving a polyaniline.
Preferred solvents have a relatively strong hydrogen bonding capability. The degree of hydrogen bonding capability can be assessed by a variety of techniques. One method which we find to be most predictive of suitable solvents for the present invention is that Craver, J. A~l. Polvm Sci. 14, 1755 (1970). This method is based upon the relative sound velocity (g~) in paper wetted by the solvent, where water is arbitrarily assigned a value of 100. By this measure, suitable solvents are those which have a hydrogen bonding capability greater than about 50, and more preferably greater than about 60.
Another useful measure o~ suitable solvents is the solubility parameter of the liquid, also referred to as ~ ' '''''-, - : . , '~:
. .. ~
, : ,~ : -, ' '.. ~. "~', .,' ' ~ :
W O 92/18572 P~r/US92/03022 2 i'~ i3 ~
, the Hildebrand Parameter (d). Preferred solvents havea Hildebrand Parameter which lies in the range of from about 17 to about 29, more preferably in the range of from about 18 to about 26, and most preferably in the range of from about 19 to about 25.
An even more useful measure of suitable solvents is based on dividing the Hildebrand Parameter of the liquid into separate contributions from dispersion (dt), from polar interactions (dp), and from hydrogen bonding interactions (dh) In this scheme (which is disclosed in HHandbook of Solubility Parameters and Other Cohesion Parameters", by Allan F.M. Barton (CRC
Press, 1983) pp 141-162, 94-110) the Hildebrand Parameter is related to the contribution from dispersion (dd), polar interactions (dp) and hydrogen bonding interaction (dh) ("Hansen Parameters") by the relation dZ=dd2+dpZ Idh2 -~ For example, in order to judge the suitability of a solvent for polyaniline, we have empirically determined solubility parametQrs-for the neutral base form of polyaniline which contains approximately a 50/50 ratio of amine to imine nitrogen linkages as follows:
d d = 17.4 MPa d p ~ 8.5 MPa d h 5 10.4 MPa d = 22.0 NPa If we define a quantity (r) as:
r= t4(17.4-dd)2 + (8.5-dp)2 + (10.4 -db)2]
where da~ dp and d~ are the Hansen ParaoQters for a ~ ' .
~.- : . .-~ . .
:~i - ;,,: ......... .
,.. : : : ;: ;: ~ . ~ .
W O 92~18S72 PC~r/US92/03022 prospective solvent for polyaniline base, then suitable solvents are those for which r is less than about 7 MPa , more preferably less than about 6 MPa , and most preferably less than about 5 MPa .
Solvents for use in the practice of this invention are volatile. As used herein, a "volatile" solvent is a liquid which has a boiling point of equal to or less than about 300C under use condition, preferably at atmospheric or autogenous pressure. The lower limit to the boiling point is not critical provided that the solvent is in the liquid state under use conditions.
In the preferred embodiments of the invention the boiling point of the solvent is less than about 2S0C.
Particularly preferred solvents have boiling points of less than about 200C. More preferred solvents have boiling points of less than about 150C and most preferred solvents have boiling points of from about 40C to about 100C.
Illustrative of useful solvents are alkyl alkanesulfonates such as methyl methanesulfonate;
nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile, and the like; aromatic solvents such as nitrobenzene, benzene! toluene and the like; carbonates such as propylene carbonate, dimethyl carbonate, and the like; nitroalkanes such as nitromethane, and the like; amides such as dimethylformamide, dimethyl thioformamide, N,N-dimethylacetamide, N-methylpyrrolidone, oxazolidone, 2-methyl-3-oxazolidone, 1,3-dimethyltetrahydro-2-pyrimidone; lactams such as capyrlactam, caprolactam and the like; organophosphorus compounds such as hexamethylphosphoramide, diethylphosphate, triethylphosphite, trimethyphosphate and the like; glycols such as tetraethylene glycol and the like; organosulfur compounds such as sulfolane, .., .
~ . , ''' ~. .', . '' .
WO92/18572 PCT/US92/0~22 methyl sulfolane, dimethylsulfite, dimethylsulfone, dimethylsulfoxide, glycolsulfite, tetraethylsulfamide and the like; aliphatic and aromatic diamines and amines such as 2-picoline, 1-aminopiperidine, pyrrolidine, piperidine, morpholine, ethylamine, benzylamine, butylamine, ethylenediamine, piperazine, pyridine, indoline, toluidine, quinoline, aniline, ethylenediamine, N,N-dimethylethylenediamine, tetrahydrofurylamine, N,N-dimethylethylenediamine, 2-methoxyethylamine, 3-methoxypropylamine 1,2,3,4-tetrahydroisoquinoline,tributylamine, dimethylamine, diet~ylamine, dipropylamine, dibutylamine, allylmethylamine, amylamine, isopropylamine, cyclohexylamine, phenylethylamine, 2-methylbenzylamine, 2-(ethylamino)ethanol, isobutylamine, tert-butylamine, 1-(3-aminopropyl)-2-pipecoline, 2,3-cyclohexenopyridine, 2-(methylamino)pyridine, 6-methylindole and the like, and other organonitrogen compounds such as dime~hylhydrazine, tetramethylurea, 1,3-dimethyl-3-imidazolidinone, 4,4-dimethyl-2-imidazoline, 3,5-dimethylisoazole.
Ethers such as tetrahydrofuran, 1,3-dioxane, dimethoxyethane and 1,3-dioxolane are also useful solvents.
Nixtures of such organic solvents can also be used as for example mixtures of 2-ethylaminoethanol and tetrahydrofuran, 2-(ethylamino)ethanol and 1,4-dioxane, tributylamine and N-methylpyrolidone, and the like.
: 30 When employing mixtures of organic solvents or an excess of the Lewis base, an average set of Hansen - Parameters can be calculated using the technigues of matrix algebra. Suitable solvent mixtures are then preferably those whose average values of dd, ~, and dh lead to a value of r which is less than about 7 MPa .
., ,. . . - ~ . ~ .
" : ; .,, ~ ~ :
~ , .: . ~, ...
,:
:. , :: .. ..
~ 12 In addition to the essential polyaniline, and solvent, the solutions and plasticized composition of this invention can include other optional ingredients which either dissolve or do not dissolve in the solution and plasticized composition. The nature of such optional ingredients can vary widely, and include those materials which are known to those of skill in the art for inclusion in polymer articles and include other conventional polymers as for example, polyacrylonitrile, polyvinyl chloride, polyvinylidine fluoride, polyvinylidine chloride, polyvinyl alcohol, poly(phenylene oxide), poly(styrene), poly(l,4-cyclohexylidene dimethylene terephthalate), poly(phenylene sulfide), poly(ethylene terephthalate), poly(4-aminobutyric acid), poly(hexamethylene adipamide), poly(p-phenylene terephthalamide), poly[methane bis(4-phenyl)carbonate], polypropylene, polyethylene, and the like other conductive polymers, such as conjugated bac~bone polymers as for example poly(phenylene sulfide), polyacetylene, polyphenylene, polythiophene and the like; and other materials such as qraphite; carbon blacks; metal conductors; reinforcing fibers and inert fillers (such as clays and glass) and the like.
The proportion of polymer and solvent in the solution or plasticized composition of this invention containing the substituted or unsubstituted polyaniline homopolymer or copolymer, is not critical and can vary widely, such that the composition varies from a solution to a plasticized composition. However, the following guidelines are believed important for achieving solutions and plasticized compositions particularly useful in the present invention. In general, the minimum amount of solvent as a proportion of the amount of solution is not believed to be .. :: ,: . , : , . . .: ., : ... . , . :: :
; ;: .
... : : .. , , ., .. :
, , .
, ~ ' : .; .:. :
. . .
WO92/18572 P~/US92/03022 ~, 6J ~3 U r",1 ~"
critical, since any amount as a liquid will form at least a viscous gel or a plasticized composition with the polymer. These viscous gel embodiments of the invention are particularly useful for silk screening conductive circuitry and for applying thick film coatings on substrates. For other applications, it may be preferred, however, to use sufficient liquid solvent to lower the viscosity of the gel, composition or solution to a point where it flows at least sufficiently to conform to a container shape or mold in a reasonably short period of time, e.g., in 30 minutes or less. The maximum amount of solvant is again not critical, but it is recognized that additional solvent will lower viscosity and thereby effect processibility.
Excess solvent will also lenghten drying ti~e.
Preferably, the solvent is present in sufficient amounts to lower the viscosity of the solution to less than about 10,000 centipoise or preferably to from about 1 to about 1000 centipoise.
The method of forming the solutions or plasticized compositions of this invention is not critical and can vary widely. For example, one preferred method of forming the present composition or solution containing the substituted or unsubstituted polyaniline is to add the polyaniline in powderéd form to a suitable solvent - such as pyrrolidine, morpholine and the like in a mixing vessel using conventional mixing means as for example shaking, ultrasonics, stirring and the like.
In use, the solution or plasticized composition can be placed in the desired configuration. As the solvent is removed, the polyaniline solidifies forming solid polyaniline in the desired configuration.
Various methods are contemplated for using the solution of the present invention. The solvent can be removed from the solution through use of any ' - . ', ..
W O 92t18572 PC~r/US92tO3022 1~ ;3 r ~, 2 ` ~
conventional solvent removal method but is removed preferably by evaporation to form a solid polyaniline.
Alternatively, the solvent can be removed by extraction with an extractant in which the solvent is substantially more soluble than the doped polymer.
As will be appreciated by those skilled in polymer processing, the ability to form polymer articles by removing a solvent from a solution or plasticized composition enables one to prepare articles of a wide variety of shapes and sizes. Thus, for exa~ple, by removing volatiles from the present solution or plasticized composition spread on a surface, films of any desired thickness can be prepared. Even extremely thin films can be prepared which are substantially transparent. By extruding the solution or plasticized composition through a die, fibers or films can be made.
Similarly, by removing volatiles from the solution or plasticized composition in a mold of various shapes, shaped articles conforming in shape to the mold can be prepared. It will be appreciated that some shrinkage might occur between the solution or plasticized composition in its last flowable state to the final article, but such shrinkage is conventionally accounted for in moIding polymers from solution. It is also contemplated that, once a solution or plasticized composition is formed, a partial or substantial removal of solvent will occur prior to placing the solution or plasticized composition on a surface or in a mold, with the final removal of solvent occurring on the surface or in the mold. It is contemplated that, if additional soluble components are introduced into the solution, they will, unless also volatile, be present in the formed article . If the additional component is a non-volatile liquid, then the removal of volatile components may leave a new liquid or plasticized form .
, .~ ~ ' .: ;,. - .
WO92/1857~ PCT/US92/03022 t ~ t , ~
of undoped neutral polymer. If the additional components are volatile, then foamed or expanded cellular forms of the polymer may be formed.
In the event that the fourth or additional non-soluble components are present (or suspended) in the solution, the doped polymer will form around, or be filled with, the insoluble material. If, for example, the additional components are glass fibers, depending on the relative amounts of fibers and doped polymer, the removal of the solvent will cause either the polymer to be fiber-filled, or the fibers to be polymer coated or impregnated, or some intermediate composite of fibers and doped polymer to be formed. In the case of systems wherein the amount of non-soluble component greatly exceeds the doped po~ymer remaining, individual particles or shapes of non-soluble components coated or impregnated with doped polymer will be formed.
The neutral polyaniline forming the article produced from the solution of this invention can be rendered conductive by doping. Dopants for use in the practice of this invention can vary widely and can be such materials which are known in the art for use in doping conjugated homopolymers or polymers to form conductive or semi-conductive polymers, as for example, those described in detail in U.S. Patent Nos. 4,442,187 and 4,321,114, and PCT WO 90/10297 and PCT WO 89/1694, which are hereby incorporated by reference.
Illustrative of useful dopant species are oxidizing dopants such as AsFs, MoOCl~, MoCl5, PCl5, POCl3, PCl3, AlCl3, NO~ and NO2~ salts (such as NOBF~, NOPF6, NOSbF6, NOAsF6, NOCH3CO2, NO2BF~, NO2PF6, NO2AsF6, NO2SbF6, and NO2(CF3SO2), HClO~, HNO3, H2SO~, benzoylperoxide, S03 , Br2, (FSO3) 2 ~ ZnCl2~ FSO3H, and Fe(III) salts (such as Fe(BF~) 3, FeBr3, Fe( CH3S03) 3, Fe(ClO~)3, FeCl3, Fe(OTs)3, and Fe(CF3SO3)3 which give rise to doped polymers , . .
`; ;~
:
WO92/18572 PCT/US92/0~22 ,, 5h~ 16 containing dopant ions such as NO3-, C~3SO3-, AlCl~-,BF4-, ZnCl~~, PCl~-, PF6-, AsF6-, SbF6-, CF3SO3-, ClO~-, OTs~, SO3 2, C6H5CO2-, CH3SO3-, FSO3-, and FeCl~~, and Cu(II) salts such as CuCl2 which may give dopant anions such as Cl- or CuCl3-.
Illustrative of other dopants are protonic acid dopants. Such dopants include inorganic acids, such as hydrofluoric acid, hydriodic acid, inorganic phosphorus acids such as phosphoric acid and the like, nitric acid, boric acid, inorganic sulfur acids such as sulfuric acid and the like. Such dopants also include organic a~ids such as 1-anthracene sulfonic acid, oxalic acid, 9-anthracene sulfonic acid, tartaric acid, 2-phenanthrene sulfonic acid, malonic acid, 3-phenanthrene sulfonic acid, succinic acid, 9-phenanthrene sulfonic acid, glutaric acid, adipic acid, trifluoromethane sulfonic acid, pimelic acid, perflourooctyl sulfonic acid, azelaic acid, perfluorooctyl carboxylic acid, sebacic acid, octyl sulfonic acid, phthalic acid, dodecyl sul~onic acid, isophthalic, cetyl sulfonic acid, terephthalic, toluene sulfonic acid, methyl phosphinic acid, dimethyl phosphinic acid, phenyl phosphonic acid, dodecylbenzene sulfonic acid, naphthalene sulfonic ~: 25 acid, benzene disulfonic acid, benzene sulfonic acid, 1,3-benzene disulfonic acid, 2,5-dihydroxy-ll4-benzene disulfonic acid, camphor sulfinic acid, naphthalene trisulfonic acid, ethylbenzene sulfonic acid, ethane sulfonic acid 1,5-naphthalene disulfonic acid, nickel phthalocyanine tetrasulfonic acid, phenyl phosphonic acid, diphenyl phosphinic acid, phenyl phosphinic acid, ortho boric acid, 3-sulfopropyl acrylate, meta boric acid, 3-sulfopropyl methacrylate, sulfamic acid, 5-sulfosalicyclic acid, trion (4,5-dihydroxy-1, 3-benzene disulfonic acid), vinyl sulfonic acid, ~, - : ~' `' . `", ', W O 92~18572 P~r/US92/03022 .
r t arsenic acid, arsenous acid, arsinic acid, arsonic acid, sulfanilic acid, 4-sulfophthalic acid, sulfoacetic acid, methyl phosphinic acid, phenylphosphonic acid, methyl phosphonic acid, methyl orange, sulfonated polystyrene, hydroboxofluoric acid, orthophosphoric acid, pyroboric acid, sulfonated poly(2-vinyl naphthalene), naphthol yellow, naphthol blue black, 1,2-naphthoquinone-4-sulfonic acid, naphthylazoxine S, l-octane sulfonic acid, pyrophosphoric acid, metaphosphoric acid, orthophosphorous acid, t-hutyl phosphonic acid, ethyl phosphonic acid, butyl phosphonic acid, 1,2-benzene disulfonic acid, 4-octylbenzene sulfonic acid, 2-mesitylene sulfonic acid, 2,6-naphthalene disulfonic acid, 2-naphthalene sulfonic acid, 1,3,6-naphthalene trisulfonic acid, 1,3,7-naphthalene trisulfonic acid, sulfonazo III acid, biphenyl disulfonic acid, biphenyl sulfonic acid, 1,8-dihydroxynaphthalene-3-6-disulfonic acid, 3,6-dihydroxynaphthalene-2,7-disulfonic acid, 4,5-dihydroxynaphthalene-2,7-disulfonic acid, 6,7-dihydroxy-2-naphthalene sulfonic acid, l-naphthalene phosphoric acid, l-naphthalene sulfonic acid, 1-naphthalene-5,~-dinitro-8-hydroxy, 1-naphthalene-4-hydroxy sulfonic acid, 4-bromo benzene sulfonic acid, 4-hydroxy-5-isopropyl-2-methyl benzene sulfonic acid, 3,4-diamino benzene sulfonic acid benzenephosphoric acid, 1,3,5-benzene trisulfonic acid, 2-methyl-5-isopropyl benzene sulfonic acid, 3,4-dinitro benzene sulfonic acid, 2-methoxy benzene sulfonic acid, 1-naphthalene-5-hydroxy suIfonic acid, l-naphthalene-7-hydroxy sulfonic acid, l-naphthalene-3-hydroxy sulfonic acid, 2-napthalene-1-hydroxy sulfonic acid, 4-phenylamino benzene sulfonic acid, 2,6-naphthalene disulfonic acid, 1,5-naphthalQne disulfonic acid, dinonylnaphthalene . - . : .
. . .
. .: , :. . :
..~
WO9~/18572 PCT/US92/03022 .;
~io~5 3Z 18 sulfonic acid, phenylboronic acid, 1,2-benzene boronic acid sulfonic acid, and 1,3-naphthalene-7-hydroxy disulfonic acid.
The amount of dopant included in the complex is 5 not critical and may vary widely. In general, sufficient dopant is included in the complex such that an amount of dopant is released from the complex on removal of the Lewis based and/or solvent from the complex and/or from the solution and/or composition 10 such that the polyaniline is doped the desired extent, usually an amount such that the polyaniline is doped to a conductivity of at least about 10-1 ohm~1cm~1. The upper level o~ conductivity is not critical and will usually depend on the type of aniline polymer employed.
15 In general, the highest level of conductivity obtained is provided without unduly adversely affecting the environmental stability of the polymer. Preferably the amount of dopant employed is sufficient to provide a conductivity of at least about 1O~5Ohm~1cm~l, more 20 preferably of from about lO~~ohm~~cm~1 to about 10+2ohm~lcm~~ and most preferably about lO~lohm~lcm~l to about 10~2ohm~lcm~1.
Examples of articles formed from non-soluble components and the present polymer solutions include 25 conductive polymer coated-housings for sensitive electronic equipment (microprocessors), infrared and microwave absorbing shields, flexible electrically conducting connectors, conductive bearings, motor or generator brushes and semiconducting junctions t 30 photoconductors, conductive traces or ground planes for electronic devices, antistatic materials for packaging electronic components, carpet fibers, tiles, or coatings for floors in computer rooms and antistatic spray finishers for plastics, and thin, optically 35 transparent antistatic finishes for C~T screens, . . .... .
~, . ~ .
..
, ., - `
~ ;,3 ~J
aircraft, auto windows and the like.
The following specific examples are present to illustrate the invention and are not to be construed as limitations thereon.
To a solution containing 1770ml of H~0, 50g of aniline (0.54 mole) and 172g p-toluene sulfonic acid (0.90 mole) was added, dropwise at 15C, a solution of ammonium persulfate (153.4g in 336.5 ml X20) over a period of 40 minutes. Then the reaction was allowed to continue at 15C for a 0.5 hours.
The resultant solid precipitate was collected and washed with 6 L of an aqueous toluene sulfonic acid solution (10 wt%) and then by 3 L of methanol. The resultant blue-black solid was dried in air for 25 hrs and dried at 130C for 3 hrs. under dynamic vacuum to give poly(anilinium tosylate) as a green powder. The conductivity of the dried and pressed pellet formed from thi8 material was 1 Scm~1 as measured by the co-linear four-probe method. The conductivity of the moisture-saturated pellet was 20 Scm~l The yield was 78g. The intrinsic viscosity (in H2SO~, at 25C) was 0.66 dl/g. Elemental analysis of the dried green powder gave:
C:64.37(Wt%)H:4.86% N:8.59%
S:8.40%0:13.51%
Moisture: less than 0.8 wt%
~L
Poly(anilinium tosylate) tl3g) obtained from Example 1 was suspended in water at room temperature and nuetralized with excess sodium carbonate (Na2CO3). The suspension was then filtered ` . ~ ' t .
WO92~18572 PCT/US92/03022 .
,~ ~ Q g v ~ 2 and the cake was dried to yield a blue-black powder of polyaniline base.
Calculations were carried out to suggest suitable solvents for use with unsubstituted undoped polyaniline using group additive contributions for determining individual components of the Hildebrand Parameter ~d). In the representations of Hansen, the following nomenclature is used A) Nomenclature ~1) d is the Hildebrand Parameter (units: MPa) and is related to the Hansen Parameters (dt, dp, dh) as follows:
d2=dt2=dd2+dp2+dh2 (2) dd is the contribution from dispersion interactions.
(3) dp is the contribution from polar interactions.
(4) dh is the contribution from hydrogen bonding interactions.
These components of d can be estimated from tabulated group molar attraction contributions from dispersion interactions (Fd), polar interactions (Fp) and from the cohesive hydrogen bonding energy (Uh). This analysis led to the estimate for the solubility parameter of the undoped (base) form of polyaniline given below:
: ~ , ,' ~ . ' :
, . : ' , . ''' ` , ,:, : , ,:
dd = 18.5 MPa dp = 4.1 MPa dh = 7.4 MPa d = (dd2 + dp2 + dh2) = 20.3 MPa Estimate of the Hildebrand Parameter based on group contributions to the heat of vaporization gave d = 23.8 MPa . Solvents which dissolve or swell undoped polyaniline will be those whose own solubility parameters are close to those of the polymer. Polar solvents with relatively strong hydrogen bonding are generally good solvents.
15 A series of potential solvents with significant polar and hydrogen bonding contributions were tested with undoped polyaniline base which had been synthesized as in Example 2. Solvents which were demonstrated to dissolve undoped polyaniline are shown in Table 1 below and in Figure 1.
:
WO~Z/~857Z PCT/US92/03022 3ia ~ 22 $ABLE 1 Observed Solvents For Unsubstituted Undoped Polyaniline Base S
Biquid BP(C) gw e m d Morpholine 129200.0 7.3 5.0 22.1 Piperidine 106 89.0 5.8 4.0 19.3 Pyridine 115 80.0 12.3 7.3 21.7 10 Pyrrolidine 88 - - 5.3 N-methyl pyrrolidone 204 - 32.0 - 23.7 Dimethylsulfoxide189 79.0 46.5 13.3 26.4 Dimethylformamide158 68.0 37.0 11.2 24.1 Dimethylhydrazine 63 - - - 19.8 15 Propylamine 48.5 - 5.3 4.7 19.7 Butylamine 78 - 5.3 4.7 18.6 Picoline 129 - 9.8 6.3 20.9 Aniline 182 94.0 6.9 5.0 22.6 Quinoline 114 - 9.0 7.6 22.0 20 2-Pyrrolidone 245 - - 7.7 28.4 Dimethylacetamide165 87.0 38.0 12.7 22.7 Tetramethylurea 177 - 23.1 13.0 21.7 Ethylene Diamine 117 - 12.9 6.6 25.3 Hexamethyl Phosphoramide235 - 30.0 17.6 23.2 m-Cresol 203 - 11.8 - 22.7 Benzyl alcohol 206 - 13.0 5.5 23.5 8enzylamine 185 - - - -2-~ethoxyethylamine 90 "-" means that the data is not available.
The parameters listed in Table 1 are as follows: "B.P.~ is the boiling point in C; "gw" is the relative sound velocity in paper wetted by the - ' ',' - ; '.~
.~
W092/18572 2 i ~ 3 ~ PCT/US92/0~22 solvent (water = 100) which is a measure of hydrogen bonding capability; "e" is the dielectric constant relative to the permittivity of free space teO = 8.854 x 10-12 F/m); "m" is the dipole moment in 10-30 Cm, and "d" is the Hildebrand (solubility) parameter in MPa It was noted that in cases where it was known, the hydrogen bonding parameter, g~, was equal to or greater than 68, and the dipole moment was equal to or greater than 4.7 x 10-3 Cm. The data were used to establish an empirical measure of the solubility parameters which characterize the interactions of undoped polyaniline according to a method developed by Hansen. Values of the Hansen parameters for the solvents used were taken from "Handbook of Solubility Parameters and other Cohesive Parameters" by A.F.M. Barton (CRC Press, 1983). When multiple literature sources were found with widely differing Hansen parameter values, those sets of values were taken which were the closest to those theoretically predicted by group additive techniques for the given solvent.
B) Hansen's Method for Solubilit~ Parameter:
(l) In this method, the polymer is characterized as having a "solubility sphere" in a three dimensional space defined by the coordinates da~ dp, dh. The center point of the solubility sphere is (2d'd,d'p,d'h) and the radius of the sphere is R.
(2) An interaction distance for a given solvent is defined as:
r=t4(dd-d~d)2 + (dp-d'p)2 + (dh-d",)2]
(3) The polymer should be soluble in a given solvent .
... . I
; ~ , :
,. : : , .
,: ,. , ,~ .
WO92/18572 P~T/US9Z/03022 -, r' ~ ~
when r~R.
C! Hansen Method with Polvaniline and Various Solvents (1) The following values of the Hansen Parameters (all in units of MPa~ were determined for polyaniline by sampling Hansen Space (i.e., the range of possible values for dd, dp and dh) with the series of solvents in Table 1.
(i) d'd=17.4 (ii) d,p=8.5 (iii) dh=10.4 (iv) R=6 (v) d=22.0 The following Table 2 sets forth the Hansen Parameters of various liquids which have been shown to be solvents for unsubstituted and undoped polyaniline base.
WO~2/18572 PCT/US92/03022 ~ ~ sJ v ~ ` 2 Table 2 Hansen Parameters of Solvents For Unsubstituted Undo~ed Polvaniline Base Liguid d~ d~ d~_ r Morpholine 16.0 11.410.1 4.0 Piperidine 16.2 8.7 5.8 5.2 Pyridine 17.6 10.1 7.7 3.2 Dimethylsulfoxide 1~.416.4 10.2 8.2 N-methylpyrrolidone 16.510.4 13.5 4.1 Dimethylformamide 17.413.7 11.3 5.3 Dimethylhydrazine lS.3 5.9 11.0 5.0 Propylamine 17.0 4.9 8.6 4.1 Butylamine 16.2 4.9 8.0 4.9 Picoline 18.2 7.8 6.8 4.0 Aniline 19.4 5.110.0 5.3 Quinoline 19.4 7.0 7.6 5.1 2-Pyrrolidone 19.4 17.411.3 9.8 Dimethylacetamide 16.811.5 10.2 3.2 Tetramethylurea16.8 8.211.1 1.4 Ethylene Diamine 16.6 8.8 17.0 6.8 ~examethyl Phosphoramide 18.3 8.6 11.3 2.0 m-Cresol 18.7 4.813.5 5.5 Benzylalcohol 18.5 4.913.9 5.5 The average values of the Parameters, dd, dp and dh, in Table 2 determine the approximate center of the solubility sphere (2d d, dp, d b) and the span of r values determine the approximate radius.
(2) Examples:
(i) Methano~:
,.: ' .
:,, ~ ; ' WO92/lB572 PCT/VS92/03022 3 r~; ~3~
~6 dd=ll.60, dp=13.0, dh=24.0 r=[4(16-17.4)2 + (13-8.5)2 + (24-10.4) 2] , 18.4 Since r>>R, methanol should be a nonsolvent which was observed.
(ii) Methvl Ethyl Ketone (MEK!:
dd=14 .1, dp=9.3, dh=9.5 t4(14.1 17.4) + (9.3-8 5) 2 + ( 9 5 1 0 A ) 2 Since r>R, methylethylketone should not be a solvent. It was found in accordance with the prediction that although methylethylXetone swells undoped polyaniline it does not dissolve it to a noticeable degree.
(il) Pi~eridine:
dd=16.2, dp=8.7, dh=9.5 r=~4(16.2-17.4)2 + (8.7-8.5)2 + (5.8-10.4)2] = 5.2 Since r<R, piperidine should be a solvent which was observed.
A number of prospective solvents were examined and found to be non-solvents for undoped polyaniline.
These non-solvents are summarized in the following Table 3 along with the predicted interaction distance ~r) of the Hansen Method.
: , ,.,. . ~
~' , . . .
, ~. .
2 ~
Non-Solvents of PolYaniline Tosvlate and Polyaniline Base Non-Solvents Non-Solvent _ _ ar _m~ d d~
Acetonitrile 11.2 24.4 15.3 Dipropylamine - - 16.3 14.0 Triethylamine - 2.2 15.3 14.6 Tributylamine - 2.3 lS.9 15.1 Diisopropylamine - - 15.2 13.8 Cyclohexanone38.0 9.3 20.2 17.7 Methylene Chloride - 5.0 20.2 13.4 Chloroform - 6.2 18.7 11.0 Methylethylketone 31.0 9.0 19.3 14.1 Tetrahydrofuran 32.0 5.4 18.5 13.3 1,4-Dioxane 46.0 0.0 19.8 18.3 1,3-Dioxolane - - 23.2 14.8 Diethyl Ether24.0 3.8 15.6 14.4 Methanol 72.0 5.7 29.7 11.6 Ethanol 38.0 5.6 26.1 12.6 Acetone 29.0 9.1 19.7 13.0 Water lO0.0 6.1 47.9 12.3 N-Ethylaniline - - 21.5 17.1 4-Butylaniline - - 20.4 16.9 Toluene 27.0 1.2 18.2 17.9 Hexane 24.0 0.3 14.9 14.9 Nitrobenzene - 14.1 22.5 17.6 Ethyl Acetate29.0 6.0 18.2 13.4 2-(Ethylamino)ethanol -1,3-Dioxane In the Table, "-" denotes that the data is not available.
. . ~ ' ~ .: ' ~ ' .
.. . .
,- ~ .
.
;~ 2 TABLE 3 ~cont'd) Non-Solvent d~_ dh r Acetonitrile18.0 6.1 11.2 Dipropylamine6.2 5.8 8.5 Triethylamine3.7 1.9 11.3 Tributylamine2.8 4.0 9.7 Diisopropylamine 6.2 2.0 11. 3 Cyclohexanone8.9 5.1 5.3 lo Methylene Chloride 11.7 9.6 ~.7 Chloroform 13.7 6.3 14.4 Methylethylketone 9.3 9.5 6.7 Tetrahydrofuran11.0 6.7 9.3 1,4-Dioxane 1.3 7.4 8.0 1,3-Dioxolane11.3 13.9 6.9 Diethyl Ether2.9 5.1 9.8 Methanol 13.0 24.0 18 . 4 Ethanol 11.2 20.0 13.8 Acetone 9.8 11.0 8.9 Water 31.3 34.2 34.5 N-ethylaniline10.5 7.7 3.4 4-butylaniline9.1 6.6 4.0 Toluene 1.1 2~1 11.2 Hexane 0.0 0.0 14O3 Nitrobenzene14.0 0.0 11.8 Ethyl Acetate8.6 8.9 8.1 1,3-Dioxane - - -~-(Ethylamino)ethanol -In the table, "-" denotes that the data is not available.
The Hansen Parameters of these non-solvents are graphically compared to those for the solvents of Example 4 in Figure 2. The majority of non-solvents in Table 3 have as expected,~ r>R (R_6 from Example 4);
however, there are also a few exceptions. Such exceptions are frequently seen and can stem from inaccurately known Hansen Parameters. Refexence to Table 1 reveals that solvents of polyaniline possess hydrogen bonding parameters , g~, in cases where they are known, that are greater than 68. The only non-solvents with g~ > 68 in Table 3 are methanol and water which both have r ~> R and are not expected to be solvents.
.: ` . .; ' ~ -;, `:
~ 3~ w Doped polyaniline tosylate was prepared as in Example l. Undoped polyaniline base was prepared as in Example 2. A few milligrams of these powdered polyanilines were added to 2 ml of the prospective solvents and solvent mixtures listed below in Table 4.
lO sOlubility of Polyaniline Base (PAni Base) and Polyaniline Tosylate (PAni tosylate) in Selected Solvents Solvent Solubility for Solubility for PAni Base PAni Tosvlate -l,3-Dioxane l,4-Dioxane 20 Tetrahydrofuran (THF) 2-Ethylaminoethanol (EAE) i s EAE/l,3-Dioxane ss EA~/l/4-Dioxane ss EAE/THF s . s In the Table, "i~ is insoluble; "s" is soluble;
and "ss" is slightly soluble.
The results obtained with 2-ethylaminoethanol in combination with selected ethers demonstrated that polyaniline base can be soluble in mixtures of solvents even when it in insoluble in the neat constituents.
: .
W092/~8572 PCT/US92/03022 ~ .., ,~
i~la^~2 Undoped polyaniline in its base form was dissolved in dimethylformamide (DMFI and filtered to give a deep blue solution. Likewise polyaniline base was dissolved in pyrrolidine to give a deep blue solution. Phenyl hydrazine was added to each solution in an amount sufficient to render the solutions very light yellow and pale brown, respectively, indicating thereby that the polyaniline base had been reduced in each case to its leuco form (poly(phenylene amine), Formula IV). No clouding or precipitate was observed after 48 hours of standing which demonstrated t~at the leuco form is also at least equivalently soluble in these solvents.
Several pieces of polyethylene terephthalate film (5 inches x 4 inches) were coated with a 1.5 wt%
solution of neutral polyaniline base in pyrrolidine by a transfer coating technigue. In this technique, polyaniline solution was homogeneously laid down on the plastic films by a metal screen roller which contained hundreds of regularly engraved cells per sguare inch.
~;~ The coated films were blue and nonconductive. After doping with an acid dopant solution, the films turned green and conductive.
When p-toluene sulfonic acid was used as the dopant, the surface resistances, measured by a disc probe (Xeithley 610S), of these films ranged from 106 to 107 ohm/sq. When dodecylbenzenesulfonic acid was used, the surface resistance ranged from 107 to lOa ohm/sq.
: -: .: :
, , , ~ . . . ..
. . : ;: ~ . : :
4,855,361; 4,798,685; 4,806,271; 4,822,638; 4,851,487;
4,798,685 and PCT WO89/01694.
Several solvents for neutral (undoped) polyaniline are known. For example, F. Wudl et al., J. Am. Chem.
Soc. 109 3677(198); U.S. Patent No. 4,913,867; A.
MacDiarmid, et al. PolYm. PreDrints, 30, 147 (1989); X.
Tang et al. Makroml. Chem. RaDid Commun., 9, 829-834;
A.&. Green and A.E. Woodhead, J. Chem. Soc. , 2388(1940); M. Angelopoulos, et al. Mol. Crvst. Li~.
CrYst. Bulietin. p 240 (1988) and M. Inoue et al.
Svnth. Met. 30, 199(1989).
S~MMARY OF THE INVENTION
One aspect of this invention relates to a solution and to a plasticized composition comprising one or more substituted or unsubstituted polyanilines; and one or more solvents capable of dissolving said polyaniline to some extent, capable of plasticizing said polyaniline or a combination thereo~. As used herein "solution" is .
... ...
~ ' ~
-. .
. .
~ ~ rj 2 2 a real solution or an ultra-fine dispersion having an average particle si~e of less than about 100 nanometers, and, as used herein, a "plasticized composition" is a poly~er or a polymer blend which is softened by incorporation of a liquid or low melting temperature solid generally to a level of more than about 1% by weight and less than about 20%. As used herein "polyaniline" is a polymer which is synthesized for example by the head-to-tail linkage of substituted or unsubstituted anilines, and, which depending on oxidation state, consists of phenyl rings and amine linkages (-NH- or -NR- where R is a substituent other than hydrogen) with varying amounts of quinoid rings and imine (-N=) linkages. As used herein "neutral or undoped polyaniline" is characterized by an uncharged backbone and "polyaniline base" is a particular form of undoped polyaniline which contains at least one quinoid diimine linkage in the backbone.
Through use of the solution of this invention polyaniline can be conveniently processed into useful conductive articles of all shapes such as fibers, coatings, printings, films and the like using conventional solution or plasticized polymer techniques.
BRIEF DESCRIPTION OF THE INVENTION
The invention will be more fully understood and further advantages will become apparent when reference is made to the following detailed description of the invention and accompanying drawings in which:
Figure 1 shows a graph showing the Hansen solubility Parameters of solvents and co-solvents for polyaniline base.
Figure 2 is a graph showing the Hansen Solubility Parameters relative to polyaniline base for solvents W O 92/18572 PC~r/US92/03022 , ~1 ~3 ~ ~ 5 2 and non-solvents.
DETAILED DESCRIPTION OF THE INVENTION
One essential ingredient of the solutions or plasticized compositions of this invention is a substituted or unsubstituted polyaniline such. Any form of substituted and unsubstituted polyaniline can be conveniently used in the practice of this invention such as those are characterized by different ratios of phenylene amine and quinone imine backbone segments, as for example leucoemeraldine, protoemeraldine, emeraldine, nigraniline and pernigraniline.
Preferred polyanilines are of the type derived from the polymerization of unsubstituted and substituted anilines of the Formula I:
rl 1~ R,;,, (~
wherein: ( Rl) n is an integer from 0 to 5;
m is an integer from 0 to 5, with the proviso that the sum of n and m is equal to 5; and R1 is the same or different at each occurrence and is selected:from the group consisting of boric acid, phosphinic acid, phosphoric acid, sulfinate salt, amido, carboxylic acid, hydroxyamino, phosphonic acid, halo, hydroxy, cyano, sulfinic acid, carboxylate salt, borate salt, phosphate salt, sulfonate, phosphinate salt, phosphonate salt, amino, sulfonic acid, nitro, amino, cyano, sulfate salt, deuterium or substituted or unsubstituted arylsulfinyl, alkoxycarbonyl, arylsulfonyl, alkylamido, dialkylamido, arylamido, SUBSTITUTE SHEET
.
:
.
.:
.
'~ X ~ S '~ ' diarylamido, alkylarylamido, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylamino, dialkylamino, alkylarylamino, arylamino, diarylamino, aryl, alkynyl, alkylsulfinyl, aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, alkoxyaryl, alkylsulfonyl, arylthio, alkylsulfonylalkyl, or alkylsilane or any two R2 groups together or any R1 group together with any R2 group may form a substituted or unsubstituted alkylene, alkynylene, or alkenylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroaromatic, heteroalicyclic or alicyclic ring, which ring may ôptionally include one or more divalent nitrogen, sulfur, sulfinyl, ester, carbonyl, sulfonyl or oxygen atoms, wherein permissible substituents are one or more amino, alkylamino, dialkylamino, amido, alkylamido, dialkylamido, arylamido, diarylamido, alkylarylamido, arylamino, sulfinic acid, diarylamino, alkylarylamino, phosphonic acid, sulfonic acid, phosphoric acid, boric acid, carboxylate salt, borate salt, sulfonate salt, phosphinate salt, phosphonate salt, hydroxylamino, quaternary ammonium salt, phosphate salt, sulfinate salt, phosphinic acid, sulfate salt, carboxylic acid, halo, nitro, cyano or epoxy moieties; Rl or R2 is an aliphatic moiety having repeat units of the formula:
( OCH2CH2) qOCH3, ( OCH2CH ( CH3 ) ) qOCH3 30(CH2)qCF3~ (CFz)qCF3 or (CH2)gCH3 wherein q is a positive whole number; and R2 is the same or different at each occurrence and is R1 substituents or hydrogen.
35Illustrative of the polyanilines useful in the : ; :
WO92/1~72 PCT/US92/03022 ~5~3 5 'J 2 practice of this invention are those of the Formula II:
S ~
(~)~
wherein:
R1 and R2 are as describe above;
n and m are the same or different at each occurrence and are integers from 0 to 4, with the proviso that the sum of n and m is 4; and y and x are the same or different at each occurrence and are integers equal to or greater than 0, with the proviso that the sum of x and y is greater than 0, preferably x is an integer equal to or greater than about l and/or the ratio of x to y is greater than or equal to about 0.5; and z is an integer equal to or greater than l.
Preferred for use in the practice of this invention are polyanilines of the above Formula II in which:
n is an integer from 0 to about 2;
m is an integer from 2 to 4, with the proviso that the sum of n and m is equal to 4;
R1 is aryl, alkyl or alkoxy having from l to about 30 carbon atoms, cyano, halo, sulfonic acid, carboxylic acid, boric acid, borate, phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid, phosphinate, sulfinic acid, sulfinate, carboxylate, sulfonate, amino, alkylamino, dialkylamino, arylamino, hydroxy, diarylamino, alkylarylamino, or alkyl, aryl or alkoxy substituted with phosphonic acid, phosphate, SUBSTlTUTE SHEE ~
.
: - , . - ~
.
8 ~
phosphoric acid, borate, sulfonate, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate, hydroxy, alkoxy, phosphonate, boric acid, alkyl, phosphinic acid, phosphonate, phosphinate, carboxylic acid or sulfonic acid substituents;
R2 is the same or different at each occurrence and is a alkyl or hydrogen;
x is an integer equal to or greater than l;
y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about l; and z is an integer equal to or greater than about 5.
Particularly preferred for use in the practice of this invention are polyanilines of the above Formula II
in which:
n is an integer from 0 to l;
m is an integer from 3 to 4, with the proviso that the sum of n and m is egual to 4;
Rl is aryl, alkyl or alkoxy having from 1 to about 20 carbon atoms, sulfonic acid, halo, carboxylic acid, amino, carboxylate, alkylamino, phosphonate, dialkylamino, arylamino, phosphonic acid, boric acid, phosphate, phosphoric acid, borate, diarylamino, alkylyarylamino or alXyl or aryl substituted with carboxylic acid, phosphoric acid, boric acid, phosphate, phosphonic acid, borate, sulfonate, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate, halo, phosphonate, or sulfonic acid substituents;
Rz is the same or different at each occurrence and is a hydrogen;
x is àn integer equal to or greater than 2;
y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 2; and . . ~ , :
- . : . :,~
:
W092/l8572 PCT/US92/03022 2 ~ r ~ 2 z is an integer equal to or greater than about 5 Amongst the particularly preferred embodiments, most preferred for use in the practice of this invention are polyanilines of the above Formulas III or V in which:
n is an integer from 0 to 1;
m is an integer from 3 to 4, with the proviso that the sum of n and m is equal to 4;
Rl is aryl, alkyl or alkoxy from 1 to about 15 carbon atoms, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, halo, sulfonic acid, sulfonate, carboxylic acid, carboxylate, or alkyl or aryl substituted with one or more sulfonic acid, carboxylate, amino, alkylamino, dialkylamino, arylamino, diarylamino, halo, alkylarylamino, sulfate, sulfonic acid, or carboxylic acid substituents;
R2 is hydrogen;
x is an integer equal to or greater than 2;
y is equal to or greater than 1, with the proviso that the ratio of x to y is equal to or greater than about 2; and z is an integer equal to or greater than about 5.
In the most preferred embodiments of this invention, the polyaniline is derived from unsubstituted aniline, alkoxy, alkyl, or sulfonic acid substituted aniline or copolymers thereof.
In general, the number of aniline repeat units is not critical and may vary widely. The number of aniline repeat units is preferably at least about 10.
The upper limit can vary widely depending on the desired viscosity and molecular weight and the required degree of processibility i.e. melt processibility, solution processibility and the like. The number of aniline repeat units is pre~erably at least about 20, more preferably, at least about 30 and most preferably - :. . ~ . : ., , : , - :~ - ~
wos2/l8s72 PCT/US92/03022 2 ~ 8 is at least about 40.
Useful polyanilines can be prepared through use of chemical and electrochemical synthetic procedures. For example, one form of polyaniline can be prepared chemically by treating aniline with a suitable oxidizing agent such as a~monium persulfate (NH4) 2S20 in excess acid such as lM HCl or can be prepared electrochemically by the electrochemical oxidation of aniline in aqueous fluoroboric acid electrolyte on a platinum foil anode.
The second component of the solution or plasticized composition of this invention is an "effective solvent". As used herein, "an effective solvent" is a solvent which has a relative dielectric lS constant of equal to or greater than about 5 (preferably equal to or greater than about 6), and a dipole moment equal to or greater than about 3.5 x 10-3 Cm (preferably equal to or greater than about 5 x 10-3 Cm) other than dimethylformamide, N-methylpyrrolidone, pyridine, and dimethylsulfoxide which is capable of dissolving a polyaniline.
Preferred solvents have a relatively strong hydrogen bonding capability. The degree of hydrogen bonding capability can be assessed by a variety of techniques. One method which we find to be most predictive of suitable solvents for the present invention is that Craver, J. A~l. Polvm Sci. 14, 1755 (1970). This method is based upon the relative sound velocity (g~) in paper wetted by the solvent, where water is arbitrarily assigned a value of 100. By this measure, suitable solvents are those which have a hydrogen bonding capability greater than about 50, and more preferably greater than about 60.
Another useful measure o~ suitable solvents is the solubility parameter of the liquid, also referred to as ~ ' '''''-, - : . , '~:
. .. ~
, : ,~ : -, ' '.. ~. "~', .,' ' ~ :
W O 92/18572 P~r/US92/03022 2 i'~ i3 ~
, the Hildebrand Parameter (d). Preferred solvents havea Hildebrand Parameter which lies in the range of from about 17 to about 29, more preferably in the range of from about 18 to about 26, and most preferably in the range of from about 19 to about 25.
An even more useful measure of suitable solvents is based on dividing the Hildebrand Parameter of the liquid into separate contributions from dispersion (dt), from polar interactions (dp), and from hydrogen bonding interactions (dh) In this scheme (which is disclosed in HHandbook of Solubility Parameters and Other Cohesion Parameters", by Allan F.M. Barton (CRC
Press, 1983) pp 141-162, 94-110) the Hildebrand Parameter is related to the contribution from dispersion (dd), polar interactions (dp) and hydrogen bonding interaction (dh) ("Hansen Parameters") by the relation dZ=dd2+dpZ Idh2 -~ For example, in order to judge the suitability of a solvent for polyaniline, we have empirically determined solubility parametQrs-for the neutral base form of polyaniline which contains approximately a 50/50 ratio of amine to imine nitrogen linkages as follows:
d d = 17.4 MPa d p ~ 8.5 MPa d h 5 10.4 MPa d = 22.0 NPa If we define a quantity (r) as:
r= t4(17.4-dd)2 + (8.5-dp)2 + (10.4 -db)2]
where da~ dp and d~ are the Hansen ParaoQters for a ~ ' .
~.- : . .-~ . .
:~i - ;,,: ......... .
,.. : : : ;: ;: ~ . ~ .
W O 92~18S72 PC~r/US92/03022 prospective solvent for polyaniline base, then suitable solvents are those for which r is less than about 7 MPa , more preferably less than about 6 MPa , and most preferably less than about 5 MPa .
Solvents for use in the practice of this invention are volatile. As used herein, a "volatile" solvent is a liquid which has a boiling point of equal to or less than about 300C under use condition, preferably at atmospheric or autogenous pressure. The lower limit to the boiling point is not critical provided that the solvent is in the liquid state under use conditions.
In the preferred embodiments of the invention the boiling point of the solvent is less than about 2S0C.
Particularly preferred solvents have boiling points of less than about 200C. More preferred solvents have boiling points of less than about 150C and most preferred solvents have boiling points of from about 40C to about 100C.
Illustrative of useful solvents are alkyl alkanesulfonates such as methyl methanesulfonate;
nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile, and the like; aromatic solvents such as nitrobenzene, benzene! toluene and the like; carbonates such as propylene carbonate, dimethyl carbonate, and the like; nitroalkanes such as nitromethane, and the like; amides such as dimethylformamide, dimethyl thioformamide, N,N-dimethylacetamide, N-methylpyrrolidone, oxazolidone, 2-methyl-3-oxazolidone, 1,3-dimethyltetrahydro-2-pyrimidone; lactams such as capyrlactam, caprolactam and the like; organophosphorus compounds such as hexamethylphosphoramide, diethylphosphate, triethylphosphite, trimethyphosphate and the like; glycols such as tetraethylene glycol and the like; organosulfur compounds such as sulfolane, .., .
~ . , ''' ~. .', . '' .
WO92/18572 PCT/US92/0~22 methyl sulfolane, dimethylsulfite, dimethylsulfone, dimethylsulfoxide, glycolsulfite, tetraethylsulfamide and the like; aliphatic and aromatic diamines and amines such as 2-picoline, 1-aminopiperidine, pyrrolidine, piperidine, morpholine, ethylamine, benzylamine, butylamine, ethylenediamine, piperazine, pyridine, indoline, toluidine, quinoline, aniline, ethylenediamine, N,N-dimethylethylenediamine, tetrahydrofurylamine, N,N-dimethylethylenediamine, 2-methoxyethylamine, 3-methoxypropylamine 1,2,3,4-tetrahydroisoquinoline,tributylamine, dimethylamine, diet~ylamine, dipropylamine, dibutylamine, allylmethylamine, amylamine, isopropylamine, cyclohexylamine, phenylethylamine, 2-methylbenzylamine, 2-(ethylamino)ethanol, isobutylamine, tert-butylamine, 1-(3-aminopropyl)-2-pipecoline, 2,3-cyclohexenopyridine, 2-(methylamino)pyridine, 6-methylindole and the like, and other organonitrogen compounds such as dime~hylhydrazine, tetramethylurea, 1,3-dimethyl-3-imidazolidinone, 4,4-dimethyl-2-imidazoline, 3,5-dimethylisoazole.
Ethers such as tetrahydrofuran, 1,3-dioxane, dimethoxyethane and 1,3-dioxolane are also useful solvents.
Nixtures of such organic solvents can also be used as for example mixtures of 2-ethylaminoethanol and tetrahydrofuran, 2-(ethylamino)ethanol and 1,4-dioxane, tributylamine and N-methylpyrolidone, and the like.
: 30 When employing mixtures of organic solvents or an excess of the Lewis base, an average set of Hansen - Parameters can be calculated using the technigues of matrix algebra. Suitable solvent mixtures are then preferably those whose average values of dd, ~, and dh lead to a value of r which is less than about 7 MPa .
., ,. . . - ~ . ~ .
" : ; .,, ~ ~ :
~ , .: . ~, ...
,:
:. , :: .. ..
~ 12 In addition to the essential polyaniline, and solvent, the solutions and plasticized composition of this invention can include other optional ingredients which either dissolve or do not dissolve in the solution and plasticized composition. The nature of such optional ingredients can vary widely, and include those materials which are known to those of skill in the art for inclusion in polymer articles and include other conventional polymers as for example, polyacrylonitrile, polyvinyl chloride, polyvinylidine fluoride, polyvinylidine chloride, polyvinyl alcohol, poly(phenylene oxide), poly(styrene), poly(l,4-cyclohexylidene dimethylene terephthalate), poly(phenylene sulfide), poly(ethylene terephthalate), poly(4-aminobutyric acid), poly(hexamethylene adipamide), poly(p-phenylene terephthalamide), poly[methane bis(4-phenyl)carbonate], polypropylene, polyethylene, and the like other conductive polymers, such as conjugated bac~bone polymers as for example poly(phenylene sulfide), polyacetylene, polyphenylene, polythiophene and the like; and other materials such as qraphite; carbon blacks; metal conductors; reinforcing fibers and inert fillers (such as clays and glass) and the like.
The proportion of polymer and solvent in the solution or plasticized composition of this invention containing the substituted or unsubstituted polyaniline homopolymer or copolymer, is not critical and can vary widely, such that the composition varies from a solution to a plasticized composition. However, the following guidelines are believed important for achieving solutions and plasticized compositions particularly useful in the present invention. In general, the minimum amount of solvent as a proportion of the amount of solution is not believed to be .. :: ,: . , : , . . .: ., : ... . , . :: :
; ;: .
... : : .. , , ., .. :
, , .
, ~ ' : .; .:. :
. . .
WO92/18572 P~/US92/03022 ~, 6J ~3 U r",1 ~"
critical, since any amount as a liquid will form at least a viscous gel or a plasticized composition with the polymer. These viscous gel embodiments of the invention are particularly useful for silk screening conductive circuitry and for applying thick film coatings on substrates. For other applications, it may be preferred, however, to use sufficient liquid solvent to lower the viscosity of the gel, composition or solution to a point where it flows at least sufficiently to conform to a container shape or mold in a reasonably short period of time, e.g., in 30 minutes or less. The maximum amount of solvant is again not critical, but it is recognized that additional solvent will lower viscosity and thereby effect processibility.
Excess solvent will also lenghten drying ti~e.
Preferably, the solvent is present in sufficient amounts to lower the viscosity of the solution to less than about 10,000 centipoise or preferably to from about 1 to about 1000 centipoise.
The method of forming the solutions or plasticized compositions of this invention is not critical and can vary widely. For example, one preferred method of forming the present composition or solution containing the substituted or unsubstituted polyaniline is to add the polyaniline in powderéd form to a suitable solvent - such as pyrrolidine, morpholine and the like in a mixing vessel using conventional mixing means as for example shaking, ultrasonics, stirring and the like.
In use, the solution or plasticized composition can be placed in the desired configuration. As the solvent is removed, the polyaniline solidifies forming solid polyaniline in the desired configuration.
Various methods are contemplated for using the solution of the present invention. The solvent can be removed from the solution through use of any ' - . ', ..
W O 92t18572 PC~r/US92tO3022 1~ ;3 r ~, 2 ` ~
conventional solvent removal method but is removed preferably by evaporation to form a solid polyaniline.
Alternatively, the solvent can be removed by extraction with an extractant in which the solvent is substantially more soluble than the doped polymer.
As will be appreciated by those skilled in polymer processing, the ability to form polymer articles by removing a solvent from a solution or plasticized composition enables one to prepare articles of a wide variety of shapes and sizes. Thus, for exa~ple, by removing volatiles from the present solution or plasticized composition spread on a surface, films of any desired thickness can be prepared. Even extremely thin films can be prepared which are substantially transparent. By extruding the solution or plasticized composition through a die, fibers or films can be made.
Similarly, by removing volatiles from the solution or plasticized composition in a mold of various shapes, shaped articles conforming in shape to the mold can be prepared. It will be appreciated that some shrinkage might occur between the solution or plasticized composition in its last flowable state to the final article, but such shrinkage is conventionally accounted for in moIding polymers from solution. It is also contemplated that, once a solution or plasticized composition is formed, a partial or substantial removal of solvent will occur prior to placing the solution or plasticized composition on a surface or in a mold, with the final removal of solvent occurring on the surface or in the mold. It is contemplated that, if additional soluble components are introduced into the solution, they will, unless also volatile, be present in the formed article . If the additional component is a non-volatile liquid, then the removal of volatile components may leave a new liquid or plasticized form .
, .~ ~ ' .: ;,. - .
WO92/1857~ PCT/US92/03022 t ~ t , ~
of undoped neutral polymer. If the additional components are volatile, then foamed or expanded cellular forms of the polymer may be formed.
In the event that the fourth or additional non-soluble components are present (or suspended) in the solution, the doped polymer will form around, or be filled with, the insoluble material. If, for example, the additional components are glass fibers, depending on the relative amounts of fibers and doped polymer, the removal of the solvent will cause either the polymer to be fiber-filled, or the fibers to be polymer coated or impregnated, or some intermediate composite of fibers and doped polymer to be formed. In the case of systems wherein the amount of non-soluble component greatly exceeds the doped po~ymer remaining, individual particles or shapes of non-soluble components coated or impregnated with doped polymer will be formed.
The neutral polyaniline forming the article produced from the solution of this invention can be rendered conductive by doping. Dopants for use in the practice of this invention can vary widely and can be such materials which are known in the art for use in doping conjugated homopolymers or polymers to form conductive or semi-conductive polymers, as for example, those described in detail in U.S. Patent Nos. 4,442,187 and 4,321,114, and PCT WO 90/10297 and PCT WO 89/1694, which are hereby incorporated by reference.
Illustrative of useful dopant species are oxidizing dopants such as AsFs, MoOCl~, MoCl5, PCl5, POCl3, PCl3, AlCl3, NO~ and NO2~ salts (such as NOBF~, NOPF6, NOSbF6, NOAsF6, NOCH3CO2, NO2BF~, NO2PF6, NO2AsF6, NO2SbF6, and NO2(CF3SO2), HClO~, HNO3, H2SO~, benzoylperoxide, S03 , Br2, (FSO3) 2 ~ ZnCl2~ FSO3H, and Fe(III) salts (such as Fe(BF~) 3, FeBr3, Fe( CH3S03) 3, Fe(ClO~)3, FeCl3, Fe(OTs)3, and Fe(CF3SO3)3 which give rise to doped polymers , . .
`; ;~
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WO92/18572 PCT/US92/0~22 ,, 5h~ 16 containing dopant ions such as NO3-, C~3SO3-, AlCl~-,BF4-, ZnCl~~, PCl~-, PF6-, AsF6-, SbF6-, CF3SO3-, ClO~-, OTs~, SO3 2, C6H5CO2-, CH3SO3-, FSO3-, and FeCl~~, and Cu(II) salts such as CuCl2 which may give dopant anions such as Cl- or CuCl3-.
Illustrative of other dopants are protonic acid dopants. Such dopants include inorganic acids, such as hydrofluoric acid, hydriodic acid, inorganic phosphorus acids such as phosphoric acid and the like, nitric acid, boric acid, inorganic sulfur acids such as sulfuric acid and the like. Such dopants also include organic a~ids such as 1-anthracene sulfonic acid, oxalic acid, 9-anthracene sulfonic acid, tartaric acid, 2-phenanthrene sulfonic acid, malonic acid, 3-phenanthrene sulfonic acid, succinic acid, 9-phenanthrene sulfonic acid, glutaric acid, adipic acid, trifluoromethane sulfonic acid, pimelic acid, perflourooctyl sulfonic acid, azelaic acid, perfluorooctyl carboxylic acid, sebacic acid, octyl sulfonic acid, phthalic acid, dodecyl sul~onic acid, isophthalic, cetyl sulfonic acid, terephthalic, toluene sulfonic acid, methyl phosphinic acid, dimethyl phosphinic acid, phenyl phosphonic acid, dodecylbenzene sulfonic acid, naphthalene sulfonic ~: 25 acid, benzene disulfonic acid, benzene sulfonic acid, 1,3-benzene disulfonic acid, 2,5-dihydroxy-ll4-benzene disulfonic acid, camphor sulfinic acid, naphthalene trisulfonic acid, ethylbenzene sulfonic acid, ethane sulfonic acid 1,5-naphthalene disulfonic acid, nickel phthalocyanine tetrasulfonic acid, phenyl phosphonic acid, diphenyl phosphinic acid, phenyl phosphinic acid, ortho boric acid, 3-sulfopropyl acrylate, meta boric acid, 3-sulfopropyl methacrylate, sulfamic acid, 5-sulfosalicyclic acid, trion (4,5-dihydroxy-1, 3-benzene disulfonic acid), vinyl sulfonic acid, ~, - : ~' `' . `", ', W O 92~18572 P~r/US92/03022 .
r t arsenic acid, arsenous acid, arsinic acid, arsonic acid, sulfanilic acid, 4-sulfophthalic acid, sulfoacetic acid, methyl phosphinic acid, phenylphosphonic acid, methyl phosphonic acid, methyl orange, sulfonated polystyrene, hydroboxofluoric acid, orthophosphoric acid, pyroboric acid, sulfonated poly(2-vinyl naphthalene), naphthol yellow, naphthol blue black, 1,2-naphthoquinone-4-sulfonic acid, naphthylazoxine S, l-octane sulfonic acid, pyrophosphoric acid, metaphosphoric acid, orthophosphorous acid, t-hutyl phosphonic acid, ethyl phosphonic acid, butyl phosphonic acid, 1,2-benzene disulfonic acid, 4-octylbenzene sulfonic acid, 2-mesitylene sulfonic acid, 2,6-naphthalene disulfonic acid, 2-naphthalene sulfonic acid, 1,3,6-naphthalene trisulfonic acid, 1,3,7-naphthalene trisulfonic acid, sulfonazo III acid, biphenyl disulfonic acid, biphenyl sulfonic acid, 1,8-dihydroxynaphthalene-3-6-disulfonic acid, 3,6-dihydroxynaphthalene-2,7-disulfonic acid, 4,5-dihydroxynaphthalene-2,7-disulfonic acid, 6,7-dihydroxy-2-naphthalene sulfonic acid, l-naphthalene phosphoric acid, l-naphthalene sulfonic acid, 1-naphthalene-5,~-dinitro-8-hydroxy, 1-naphthalene-4-hydroxy sulfonic acid, 4-bromo benzene sulfonic acid, 4-hydroxy-5-isopropyl-2-methyl benzene sulfonic acid, 3,4-diamino benzene sulfonic acid benzenephosphoric acid, 1,3,5-benzene trisulfonic acid, 2-methyl-5-isopropyl benzene sulfonic acid, 3,4-dinitro benzene sulfonic acid, 2-methoxy benzene sulfonic acid, 1-naphthalene-5-hydroxy suIfonic acid, l-naphthalene-7-hydroxy sulfonic acid, l-naphthalene-3-hydroxy sulfonic acid, 2-napthalene-1-hydroxy sulfonic acid, 4-phenylamino benzene sulfonic acid, 2,6-naphthalene disulfonic acid, 1,5-naphthalQne disulfonic acid, dinonylnaphthalene . - . : .
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WO9~/18572 PCT/US92/03022 .;
~io~5 3Z 18 sulfonic acid, phenylboronic acid, 1,2-benzene boronic acid sulfonic acid, and 1,3-naphthalene-7-hydroxy disulfonic acid.
The amount of dopant included in the complex is 5 not critical and may vary widely. In general, sufficient dopant is included in the complex such that an amount of dopant is released from the complex on removal of the Lewis based and/or solvent from the complex and/or from the solution and/or composition 10 such that the polyaniline is doped the desired extent, usually an amount such that the polyaniline is doped to a conductivity of at least about 10-1 ohm~1cm~1. The upper level o~ conductivity is not critical and will usually depend on the type of aniline polymer employed.
15 In general, the highest level of conductivity obtained is provided without unduly adversely affecting the environmental stability of the polymer. Preferably the amount of dopant employed is sufficient to provide a conductivity of at least about 1O~5Ohm~1cm~l, more 20 preferably of from about lO~~ohm~~cm~1 to about 10+2ohm~lcm~~ and most preferably about lO~lohm~lcm~l to about 10~2ohm~lcm~1.
Examples of articles formed from non-soluble components and the present polymer solutions include 25 conductive polymer coated-housings for sensitive electronic equipment (microprocessors), infrared and microwave absorbing shields, flexible electrically conducting connectors, conductive bearings, motor or generator brushes and semiconducting junctions t 30 photoconductors, conductive traces or ground planes for electronic devices, antistatic materials for packaging electronic components, carpet fibers, tiles, or coatings for floors in computer rooms and antistatic spray finishers for plastics, and thin, optically 35 transparent antistatic finishes for C~T screens, . . .... .
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aircraft, auto windows and the like.
The following specific examples are present to illustrate the invention and are not to be construed as limitations thereon.
To a solution containing 1770ml of H~0, 50g of aniline (0.54 mole) and 172g p-toluene sulfonic acid (0.90 mole) was added, dropwise at 15C, a solution of ammonium persulfate (153.4g in 336.5 ml X20) over a period of 40 minutes. Then the reaction was allowed to continue at 15C for a 0.5 hours.
The resultant solid precipitate was collected and washed with 6 L of an aqueous toluene sulfonic acid solution (10 wt%) and then by 3 L of methanol. The resultant blue-black solid was dried in air for 25 hrs and dried at 130C for 3 hrs. under dynamic vacuum to give poly(anilinium tosylate) as a green powder. The conductivity of the dried and pressed pellet formed from thi8 material was 1 Scm~1 as measured by the co-linear four-probe method. The conductivity of the moisture-saturated pellet was 20 Scm~l The yield was 78g. The intrinsic viscosity (in H2SO~, at 25C) was 0.66 dl/g. Elemental analysis of the dried green powder gave:
C:64.37(Wt%)H:4.86% N:8.59%
S:8.40%0:13.51%
Moisture: less than 0.8 wt%
~L
Poly(anilinium tosylate) tl3g) obtained from Example 1 was suspended in water at room temperature and nuetralized with excess sodium carbonate (Na2CO3). The suspension was then filtered ` . ~ ' t .
WO92~18572 PCT/US92/03022 .
,~ ~ Q g v ~ 2 and the cake was dried to yield a blue-black powder of polyaniline base.
Calculations were carried out to suggest suitable solvents for use with unsubstituted undoped polyaniline using group additive contributions for determining individual components of the Hildebrand Parameter ~d). In the representations of Hansen, the following nomenclature is used A) Nomenclature ~1) d is the Hildebrand Parameter (units: MPa) and is related to the Hansen Parameters (dt, dp, dh) as follows:
d2=dt2=dd2+dp2+dh2 (2) dd is the contribution from dispersion interactions.
(3) dp is the contribution from polar interactions.
(4) dh is the contribution from hydrogen bonding interactions.
These components of d can be estimated from tabulated group molar attraction contributions from dispersion interactions (Fd), polar interactions (Fp) and from the cohesive hydrogen bonding energy (Uh). This analysis led to the estimate for the solubility parameter of the undoped (base) form of polyaniline given below:
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dd = 18.5 MPa dp = 4.1 MPa dh = 7.4 MPa d = (dd2 + dp2 + dh2) = 20.3 MPa Estimate of the Hildebrand Parameter based on group contributions to the heat of vaporization gave d = 23.8 MPa . Solvents which dissolve or swell undoped polyaniline will be those whose own solubility parameters are close to those of the polymer. Polar solvents with relatively strong hydrogen bonding are generally good solvents.
15 A series of potential solvents with significant polar and hydrogen bonding contributions were tested with undoped polyaniline base which had been synthesized as in Example 2. Solvents which were demonstrated to dissolve undoped polyaniline are shown in Table 1 below and in Figure 1.
:
WO~Z/~857Z PCT/US92/03022 3ia ~ 22 $ABLE 1 Observed Solvents For Unsubstituted Undoped Polyaniline Base S
Biquid BP(C) gw e m d Morpholine 129200.0 7.3 5.0 22.1 Piperidine 106 89.0 5.8 4.0 19.3 Pyridine 115 80.0 12.3 7.3 21.7 10 Pyrrolidine 88 - - 5.3 N-methyl pyrrolidone 204 - 32.0 - 23.7 Dimethylsulfoxide189 79.0 46.5 13.3 26.4 Dimethylformamide158 68.0 37.0 11.2 24.1 Dimethylhydrazine 63 - - - 19.8 15 Propylamine 48.5 - 5.3 4.7 19.7 Butylamine 78 - 5.3 4.7 18.6 Picoline 129 - 9.8 6.3 20.9 Aniline 182 94.0 6.9 5.0 22.6 Quinoline 114 - 9.0 7.6 22.0 20 2-Pyrrolidone 245 - - 7.7 28.4 Dimethylacetamide165 87.0 38.0 12.7 22.7 Tetramethylurea 177 - 23.1 13.0 21.7 Ethylene Diamine 117 - 12.9 6.6 25.3 Hexamethyl Phosphoramide235 - 30.0 17.6 23.2 m-Cresol 203 - 11.8 - 22.7 Benzyl alcohol 206 - 13.0 5.5 23.5 8enzylamine 185 - - - -2-~ethoxyethylamine 90 "-" means that the data is not available.
The parameters listed in Table 1 are as follows: "B.P.~ is the boiling point in C; "gw" is the relative sound velocity in paper wetted by the - ' ',' - ; '.~
.~
W092/18572 2 i ~ 3 ~ PCT/US92/0~22 solvent (water = 100) which is a measure of hydrogen bonding capability; "e" is the dielectric constant relative to the permittivity of free space teO = 8.854 x 10-12 F/m); "m" is the dipole moment in 10-30 Cm, and "d" is the Hildebrand (solubility) parameter in MPa It was noted that in cases where it was known, the hydrogen bonding parameter, g~, was equal to or greater than 68, and the dipole moment was equal to or greater than 4.7 x 10-3 Cm. The data were used to establish an empirical measure of the solubility parameters which characterize the interactions of undoped polyaniline according to a method developed by Hansen. Values of the Hansen parameters for the solvents used were taken from "Handbook of Solubility Parameters and other Cohesive Parameters" by A.F.M. Barton (CRC Press, 1983). When multiple literature sources were found with widely differing Hansen parameter values, those sets of values were taken which were the closest to those theoretically predicted by group additive techniques for the given solvent.
B) Hansen's Method for Solubilit~ Parameter:
(l) In this method, the polymer is characterized as having a "solubility sphere" in a three dimensional space defined by the coordinates da~ dp, dh. The center point of the solubility sphere is (2d'd,d'p,d'h) and the radius of the sphere is R.
(2) An interaction distance for a given solvent is defined as:
r=t4(dd-d~d)2 + (dp-d'p)2 + (dh-d",)2]
(3) The polymer should be soluble in a given solvent .
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WO92/18572 P~T/US9Z/03022 -, r' ~ ~
when r~R.
C! Hansen Method with Polvaniline and Various Solvents (1) The following values of the Hansen Parameters (all in units of MPa~ were determined for polyaniline by sampling Hansen Space (i.e., the range of possible values for dd, dp and dh) with the series of solvents in Table 1.
(i) d'd=17.4 (ii) d,p=8.5 (iii) dh=10.4 (iv) R=6 (v) d=22.0 The following Table 2 sets forth the Hansen Parameters of various liquids which have been shown to be solvents for unsubstituted and undoped polyaniline base.
WO~2/18572 PCT/US92/03022 ~ ~ sJ v ~ ` 2 Table 2 Hansen Parameters of Solvents For Unsubstituted Undo~ed Polvaniline Base Liguid d~ d~ d~_ r Morpholine 16.0 11.410.1 4.0 Piperidine 16.2 8.7 5.8 5.2 Pyridine 17.6 10.1 7.7 3.2 Dimethylsulfoxide 1~.416.4 10.2 8.2 N-methylpyrrolidone 16.510.4 13.5 4.1 Dimethylformamide 17.413.7 11.3 5.3 Dimethylhydrazine lS.3 5.9 11.0 5.0 Propylamine 17.0 4.9 8.6 4.1 Butylamine 16.2 4.9 8.0 4.9 Picoline 18.2 7.8 6.8 4.0 Aniline 19.4 5.110.0 5.3 Quinoline 19.4 7.0 7.6 5.1 2-Pyrrolidone 19.4 17.411.3 9.8 Dimethylacetamide 16.811.5 10.2 3.2 Tetramethylurea16.8 8.211.1 1.4 Ethylene Diamine 16.6 8.8 17.0 6.8 ~examethyl Phosphoramide 18.3 8.6 11.3 2.0 m-Cresol 18.7 4.813.5 5.5 Benzylalcohol 18.5 4.913.9 5.5 The average values of the Parameters, dd, dp and dh, in Table 2 determine the approximate center of the solubility sphere (2d d, dp, d b) and the span of r values determine the approximate radius.
(2) Examples:
(i) Methano~:
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~6 dd=ll.60, dp=13.0, dh=24.0 r=[4(16-17.4)2 + (13-8.5)2 + (24-10.4) 2] , 18.4 Since r>>R, methanol should be a nonsolvent which was observed.
(ii) Methvl Ethyl Ketone (MEK!:
dd=14 .1, dp=9.3, dh=9.5 t4(14.1 17.4) + (9.3-8 5) 2 + ( 9 5 1 0 A ) 2 Since r>R, methylethylketone should not be a solvent. It was found in accordance with the prediction that although methylethylXetone swells undoped polyaniline it does not dissolve it to a noticeable degree.
(il) Pi~eridine:
dd=16.2, dp=8.7, dh=9.5 r=~4(16.2-17.4)2 + (8.7-8.5)2 + (5.8-10.4)2] = 5.2 Since r<R, piperidine should be a solvent which was observed.
A number of prospective solvents were examined and found to be non-solvents for undoped polyaniline.
These non-solvents are summarized in the following Table 3 along with the predicted interaction distance ~r) of the Hansen Method.
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Non-Solvents of PolYaniline Tosvlate and Polyaniline Base Non-Solvents Non-Solvent _ _ ar _m~ d d~
Acetonitrile 11.2 24.4 15.3 Dipropylamine - - 16.3 14.0 Triethylamine - 2.2 15.3 14.6 Tributylamine - 2.3 lS.9 15.1 Diisopropylamine - - 15.2 13.8 Cyclohexanone38.0 9.3 20.2 17.7 Methylene Chloride - 5.0 20.2 13.4 Chloroform - 6.2 18.7 11.0 Methylethylketone 31.0 9.0 19.3 14.1 Tetrahydrofuran 32.0 5.4 18.5 13.3 1,4-Dioxane 46.0 0.0 19.8 18.3 1,3-Dioxolane - - 23.2 14.8 Diethyl Ether24.0 3.8 15.6 14.4 Methanol 72.0 5.7 29.7 11.6 Ethanol 38.0 5.6 26.1 12.6 Acetone 29.0 9.1 19.7 13.0 Water lO0.0 6.1 47.9 12.3 N-Ethylaniline - - 21.5 17.1 4-Butylaniline - - 20.4 16.9 Toluene 27.0 1.2 18.2 17.9 Hexane 24.0 0.3 14.9 14.9 Nitrobenzene - 14.1 22.5 17.6 Ethyl Acetate29.0 6.0 18.2 13.4 2-(Ethylamino)ethanol -1,3-Dioxane In the Table, "-" denotes that the data is not available.
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;~ 2 TABLE 3 ~cont'd) Non-Solvent d~_ dh r Acetonitrile18.0 6.1 11.2 Dipropylamine6.2 5.8 8.5 Triethylamine3.7 1.9 11.3 Tributylamine2.8 4.0 9.7 Diisopropylamine 6.2 2.0 11. 3 Cyclohexanone8.9 5.1 5.3 lo Methylene Chloride 11.7 9.6 ~.7 Chloroform 13.7 6.3 14.4 Methylethylketone 9.3 9.5 6.7 Tetrahydrofuran11.0 6.7 9.3 1,4-Dioxane 1.3 7.4 8.0 1,3-Dioxolane11.3 13.9 6.9 Diethyl Ether2.9 5.1 9.8 Methanol 13.0 24.0 18 . 4 Ethanol 11.2 20.0 13.8 Acetone 9.8 11.0 8.9 Water 31.3 34.2 34.5 N-ethylaniline10.5 7.7 3.4 4-butylaniline9.1 6.6 4.0 Toluene 1.1 2~1 11.2 Hexane 0.0 0.0 14O3 Nitrobenzene14.0 0.0 11.8 Ethyl Acetate8.6 8.9 8.1 1,3-Dioxane - - -~-(Ethylamino)ethanol -In the table, "-" denotes that the data is not available.
The Hansen Parameters of these non-solvents are graphically compared to those for the solvents of Example 4 in Figure 2. The majority of non-solvents in Table 3 have as expected,~ r>R (R_6 from Example 4);
however, there are also a few exceptions. Such exceptions are frequently seen and can stem from inaccurately known Hansen Parameters. Refexence to Table 1 reveals that solvents of polyaniline possess hydrogen bonding parameters , g~, in cases where they are known, that are greater than 68. The only non-solvents with g~ > 68 in Table 3 are methanol and water which both have r ~> R and are not expected to be solvents.
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~ 3~ w Doped polyaniline tosylate was prepared as in Example l. Undoped polyaniline base was prepared as in Example 2. A few milligrams of these powdered polyanilines were added to 2 ml of the prospective solvents and solvent mixtures listed below in Table 4.
lO sOlubility of Polyaniline Base (PAni Base) and Polyaniline Tosylate (PAni tosylate) in Selected Solvents Solvent Solubility for Solubility for PAni Base PAni Tosvlate -l,3-Dioxane l,4-Dioxane 20 Tetrahydrofuran (THF) 2-Ethylaminoethanol (EAE) i s EAE/l,3-Dioxane ss EA~/l/4-Dioxane ss EAE/THF s . s In the Table, "i~ is insoluble; "s" is soluble;
and "ss" is slightly soluble.
The results obtained with 2-ethylaminoethanol in combination with selected ethers demonstrated that polyaniline base can be soluble in mixtures of solvents even when it in insoluble in the neat constituents.
: .
W092/~8572 PCT/US92/03022 ~ .., ,~
i~la^~2 Undoped polyaniline in its base form was dissolved in dimethylformamide (DMFI and filtered to give a deep blue solution. Likewise polyaniline base was dissolved in pyrrolidine to give a deep blue solution. Phenyl hydrazine was added to each solution in an amount sufficient to render the solutions very light yellow and pale brown, respectively, indicating thereby that the polyaniline base had been reduced in each case to its leuco form (poly(phenylene amine), Formula IV). No clouding or precipitate was observed after 48 hours of standing which demonstrated t~at the leuco form is also at least equivalently soluble in these solvents.
Several pieces of polyethylene terephthalate film (5 inches x 4 inches) were coated with a 1.5 wt%
solution of neutral polyaniline base in pyrrolidine by a transfer coating technigue. In this technique, polyaniline solution was homogeneously laid down on the plastic films by a metal screen roller which contained hundreds of regularly engraved cells per sguare inch.
~;~ The coated films were blue and nonconductive. After doping with an acid dopant solution, the films turned green and conductive.
When p-toluene sulfonic acid was used as the dopant, the surface resistances, measured by a disc probe (Xeithley 610S), of these films ranged from 106 to 107 ohm/sq. When dodecylbenzenesulfonic acid was used, the surface resistance ranged from 107 to lOa ohm/sq.
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Claims (9)
1. A solution or plasticized composition comprising:
(a) a substituted or unsubstituted polyaniline;
and (b) a solvent which has a relative dielectric constant equal to or greater than 5, and a dipole moment equal to or greater than about 3.5x10-30Cm, said solvent other than dimethylformamide, N-methylpyrrolidone, pyridine and dimethylsulfoxide.
(a) a substituted or unsubstituted polyaniline;
and (b) a solvent which has a relative dielectric constant equal to or greater than 5, and a dipole moment equal to or greater than about 3.5x10-30Cm, said solvent other than dimethylformamide, N-methylpyrrolidone, pyridine and dimethylsulfoxide.
2. A solution to claim 1 wherein said polyaniline is a homopolymer or copolymer comprising a substituted or unsubstituted polyaniline of the type derived from polymerizing an aniline of the formula:
wherein:
n is an integer from 0 to 5;
m is an integer from 0 to 5, with the proviso that the sum of n and m is 5; and R1 is phosphinic acid, phosphonic acid, sulfonic acid, boric acid, phosphoric acid, amino, sulfonate, borate, hydroxy, phosphonate, phosphinate, phosphate, sulfinic acid, nitro, sulfinate, carboxylic acid, halo, carboxylate, cyano, deuterium, or substituted or unsubstituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkynyl, dialkylamine, arylamino, diarylamino, alkylarylamino, aryloxy, hydroxy, alkylthioalkyl, alkylaryl, arylalkyl, aryloxy, amino, alkylthioalkyl, alkylaryl, arylalkyl, alkylsufinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxycarbonyl, alkylsilane, or arylsulfonyl, wherein permissible substituents are one or more amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phosphonic acid, sulfonic acid, boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, carboxylate, phosphonate, phosphate, carboxylic acid, halo, nitro, hydroxy, cyano or epoxy moieties; or any two R1 substituents or any one R1 substituent and R2 substituent taken together may form substituted or unsubstitued alkylene, alkynylene or alkenylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroalicyclic, heteroaromatic or alicyclic carbon ring, which ring may optionally include one or more divalent ester, carbonyl, nitrogen, sulfur, sulfinyl, sulfonyl or oxygen wherein permissible substituents are one or more amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phosphonic acid, sulfonic acid, boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, carboxylate, phosphonate, phosphate, carboxylic acid, halo, nitro, hydroxy, cyano or epoxy moieties, or R1 or R2 is an aliphatic moiety having repeat units of the formula:
(OCH2CH2)q O-CH3, (OCH2CH(CH3))qO-CH3, (CH2)qCF3, (CF2)qCF3 or (CH2)q CH3 wherein q is a positive whole number; and R2 is the same or different at each occurrence and is R1 substituents or hydrogen.
wherein:
n is an integer from 0 to 5;
m is an integer from 0 to 5, with the proviso that the sum of n and m is 5; and R1 is phosphinic acid, phosphonic acid, sulfonic acid, boric acid, phosphoric acid, amino, sulfonate, borate, hydroxy, phosphonate, phosphinate, phosphate, sulfinic acid, nitro, sulfinate, carboxylic acid, halo, carboxylate, cyano, deuterium, or substituted or unsubstituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkynyl, dialkylamine, arylamino, diarylamino, alkylarylamino, aryloxy, hydroxy, alkylthioalkyl, alkylaryl, arylalkyl, aryloxy, amino, alkylthioalkyl, alkylaryl, arylalkyl, alkylsufinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxycarbonyl, alkylsilane, or arylsulfonyl, wherein permissible substituents are one or more amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phosphonic acid, sulfonic acid, boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, carboxylate, phosphonate, phosphate, carboxylic acid, halo, nitro, hydroxy, cyano or epoxy moieties; or any two R1 substituents or any one R1 substituent and R2 substituent taken together may form substituted or unsubstitued alkylene, alkynylene or alkenylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroalicyclic, heteroaromatic or alicyclic carbon ring, which ring may optionally include one or more divalent ester, carbonyl, nitrogen, sulfur, sulfinyl, sulfonyl or oxygen wherein permissible substituents are one or more amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phosphonic acid, sulfonic acid, boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, carboxylate, phosphonate, phosphate, carboxylic acid, halo, nitro, hydroxy, cyano or epoxy moieties, or R1 or R2 is an aliphatic moiety having repeat units of the formula:
(OCH2CH2)q O-CH3, (OCH2CH(CH3))qO-CH3, (CH2)qCF3, (CF2)qCF3 or (CH2)q CH3 wherein q is a positive whole number; and R2 is the same or different at each occurrence and is R1 substituents or hydrogen.
3. A solution according to claim 2 wherein said homopolymer or copolymer is of the formula II:
wherein:
x is an integer equal to or greater than 1;
y is equal to or greater than 1, with the proviso that the ratio of x to y is greater than abut 0.5;
z is an integer equal to or greater than about 1;
n is an integer from 0 to 3;
m is an integer from 1 to 4, with the proviso that the sum of n and m is 4;
R1 is the same or different at each occurrence and is alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylaminoalkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arythio, arylsulfinyl, alkoxycarbonyl, phosphinic acid, phosphonic acid, alkylsilyl, boric acid, arylsulfonyl, carboxylic acid, halo, hydroxy, phosphate, sulfonate, phosphonate, borate, phosphinate, carboxylate, nitro, cyano, sulfonic acid, phosphoric acid or aryl, alkyl or alkoxy substituted with one or more sulfonic acid, carboxylic acid, sulfinate, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonic acid or borate substituents; or any two R1 groups or any one R1 group and R2 group together may form a substituted or unsubstituted alkylene or alkenylene chain completing a 3, 5, 5, 6, 7, 8, 9 or 10 membered heteroaromatic, heteroalicyclic, aromatic or alicyclic carbon ring, which chain may optionally include one or more divalent nitrogen, ester, carbonyl, sulfur, sulfinyl, sulfonyl or oxygen group wherein permissible substituents are one or more sulfonic acid, carboxylic acid, sulfinate, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonic acid or borate substituents; and R2 is the same of different at each occurrence and is alkyl.
wherein:
x is an integer equal to or greater than 1;
y is equal to or greater than 1, with the proviso that the ratio of x to y is greater than abut 0.5;
z is an integer equal to or greater than about 1;
n is an integer from 0 to 3;
m is an integer from 1 to 4, with the proviso that the sum of n and m is 4;
R1 is the same or different at each occurrence and is alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylaminoalkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arythio, arylsulfinyl, alkoxycarbonyl, phosphinic acid, phosphonic acid, alkylsilyl, boric acid, arylsulfonyl, carboxylic acid, halo, hydroxy, phosphate, sulfonate, phosphonate, borate, phosphinate, carboxylate, nitro, cyano, sulfonic acid, phosphoric acid or aryl, alkyl or alkoxy substituted with one or more sulfonic acid, carboxylic acid, sulfinate, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonic acid or borate substituents; or any two R1 groups or any one R1 group and R2 group together may form a substituted or unsubstituted alkylene or alkenylene chain completing a 3, 5, 5, 6, 7, 8, 9 or 10 membered heteroaromatic, heteroalicyclic, aromatic or alicyclic carbon ring, which chain may optionally include one or more divalent nitrogen, ester, carbonyl, sulfur, sulfinyl, sulfonyl or oxygen group wherein permissible substituents are one or more sulfonic acid, carboxylic acid, sulfinate, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonic acid or borate substituents; and R2 is the same of different at each occurrence and is alkyl.
4. A solution according to claim 3 wherein m is from about 3 to about 4 and n is 0 or 1.
5. A solution according to claim 4 wherein R1 is the same or different at each occurrence and is alkyl or alkoxy having from 1 to about 30 carbon atoms and R2 is hydrogen.
6. A solution according to claim 5 wherein n is 0.
7. A solution according to claim 6 wherein z is equal to or greater than about S and x is equal to or greater than about 2, with the proviso that the ratio of x to y is at least about 2.
8. A solution according to claim 6 wherein said solvent has a volatilization temperature equal to or less than about 250°C at 760mm of Hg; a hydrogen bonding capability (gw) of greater than about 50; net Hansen parameters which satisfy the condition that the expression [4(dd-17.4)2 + (dp-8.5)2 + (dh-10.4)2] is less than about 7 MPa.
9. A solution according to claim 8 wherein said solvent is selected from the group consisting of dimethylacetamide, dimethylpropionamide, 2-pyrrolidone, capryl lactams, caprolactam, piperidine, morpholine, ethylene diamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, quinoline, 2-picoline, 4-picoline, butylamine,propylamine, aniline, 2,3-cyclohexenopyridine, 1-(3-aminopropyl)-2-picoline, tetrahydrofurfurylamine, 1,2,3,4-tetrahydroisoquinoline, dimethylhydrazine, hexamethylphosphoramide, 1,1,3,3-tetramethyl urea, m-cresol, benzylamine, benzyl alcohol, 2-methyoxy ethylamine, and 3-methoxy propylamine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/689,420 | 1991-04-22 | ||
US07/689,420 US5278213A (en) | 1991-04-22 | 1991-04-22 | Method of processing neutral polyanilines in solvent and solvent mixtures |
Publications (1)
Publication Number | Publication Date |
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CA2108552A1 true CA2108552A1 (en) | 1992-10-23 |
Family
ID=24768384
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002108552A Abandoned CA2108552A1 (en) | 1991-04-22 | 1992-04-15 | Method of processing neutral polyanilines in solvent and solvent mixtures |
Country Status (6)
Country | Link |
---|---|
US (1) | US5278213A (en) |
EP (1) | EP0581886B1 (en) |
JP (1) | JP3245420B2 (en) |
CA (1) | CA2108552A1 (en) |
DE (1) | DE69228603T2 (en) |
WO (1) | WO1992018572A2 (en) |
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JP3108894B2 (en) * | 1991-12-05 | 2000-11-13 | ネスト オイ | Electrically conductive and solid plastic material and its manufacturing method |
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US5370825A (en) * | 1993-03-03 | 1994-12-06 | International Business Machines Corporation | Water-soluble electrically conducting polymers, their synthesis and use |
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WO1995006685A1 (en) * | 1993-09-03 | 1995-03-09 | Neste Oy | Electrically conducting compositions |
US5783111A (en) * | 1993-09-03 | 1998-07-21 | Uniax Corporation | Electrically conducting compositions |
US5641841A (en) * | 1995-01-10 | 1997-06-24 | International Business Machines Corporation | Conductive lubricant for magnetic disk drives |
US5716550A (en) * | 1995-08-10 | 1998-02-10 | Eastman Kodak Company | Electrically conductive composition and elements containing solubilized polyaniline complex and solvent mixture |
US5834540A (en) * | 1996-10-01 | 1998-11-10 | Kt Holdings, Llc | Process and composition for soil remediation |
DE69722264D1 (en) * | 1996-05-31 | 2003-06-26 | Univ California Los Alamos | STABLE CONCENTRATED SOLUTIONS OF POLYANILINE WITH HIGH MOLECULAR WEIGHT AND ARTICLES MADE THEREOF |
US6797325B2 (en) * | 1996-05-31 | 2004-09-28 | The Regents Of The University Of California | Permeable polyaniline articles for gas separation |
US6429282B1 (en) * | 1996-05-31 | 2002-08-06 | The Regents Of The University Of California | Stable, concentrated solutions of polyaniline using amines as gel inhibitors |
US6099756A (en) * | 1996-07-25 | 2000-08-08 | International Business Machines Corporation | Vibrational methods of deaggregation of electrically conductive polymers and precursors thereof |
CA2266056A1 (en) * | 1996-09-13 | 1998-03-19 | Mohammad W. Katoot | Graded index polymer optical fibers and process for manufacture thereof |
US6200503B1 (en) | 1996-09-13 | 2001-03-13 | Mohammad W. Katoot | Graded index polymer optical fibers and process for manufacture thereof |
US5972499A (en) * | 1997-06-04 | 1999-10-26 | Sterling Chemicals International, Inc. | Antistatic fibers and methods for making the same |
US6001281A (en) * | 1998-09-04 | 1999-12-14 | Kemet Electronics Corporation | Preparation of conductive polymers from stabilized precursor solutions |
US6806349B2 (en) * | 1999-01-12 | 2004-10-19 | International Business Machines Corporation | Methods of fabrication of deaggregated electrically conductive polymers and precursors thereof |
US6365072B1 (en) | 1999-03-19 | 2002-04-02 | Mk Industries, Inc. | Polymer optical fibers and process for manufacturing thereof |
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US6391509B1 (en) | 2000-08-17 | 2002-05-21 | Xerox Corporation | Coated carriers |
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US6759474B1 (en) * | 2003-03-03 | 2004-07-06 | Ferro Corporation | Glass reinforced nylon blend with improved knitline strength |
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DE102004030388A1 (en) * | 2004-06-23 | 2006-01-26 | Ormecon Gmbh | An article with a coating of electrically conductive polymer and process for its preparation |
DE102005010162B4 (en) * | 2005-03-02 | 2007-06-14 | Ormecon Gmbh | Conductive polymers of particles with anisotropic morphology |
US7645399B2 (en) * | 2005-05-31 | 2010-01-12 | Xerox Corporation | Electroconductive composition |
DE102005039608A1 (en) * | 2005-08-19 | 2007-03-01 | Ormecon Gmbh | Composition with intrinsically conductive polymer |
US8153271B2 (en) * | 2006-09-13 | 2012-04-10 | Ormecon Gmbh | Article with a coating of electrically conductive polymer and precious/semiprecious metal and process for production thereof |
EP3498364A1 (en) | 2008-12-11 | 2019-06-19 | The Regents of The University of California | Filtration membrane and methods for making and using them |
US20100010119A1 (en) * | 2009-09-19 | 2010-01-14 | Davood Zaarei | Corrosion-Resistant Epoxy Nanocomposite Coatings containing Submicron Emeraldine-Base Polyaniline and Organomodified Montmorrilonite |
JP6546462B2 (en) * | 2015-06-24 | 2019-07-17 | 東京応化工業株式会社 | Composition |
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US5135682A (en) * | 1990-03-15 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Stable solutions of polyaniline and shaped articles therefrom |
-
1991
- 1991-04-22 US US07/689,420 patent/US5278213A/en not_active Expired - Lifetime
-
1992
- 1992-04-15 EP EP92912462A patent/EP0581886B1/en not_active Expired - Lifetime
- 1992-04-15 DE DE69228603T patent/DE69228603T2/en not_active Expired - Fee Related
- 1992-04-15 JP JP51173392A patent/JP3245420B2/en not_active Expired - Fee Related
- 1992-04-15 WO PCT/US1992/003022 patent/WO1992018572A2/en active IP Right Grant
- 1992-04-15 CA CA002108552A patent/CA2108552A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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WO1992018572A2 (en) | 1992-10-29 |
JP3245420B2 (en) | 2002-01-15 |
DE69228603T2 (en) | 1999-11-04 |
WO1992018572A3 (en) | 1992-11-26 |
US5278213A (en) | 1994-01-11 |
EP0581886B1 (en) | 1999-03-10 |
DE69228603D1 (en) | 1999-04-15 |
JPH06507434A (en) | 1994-08-25 |
EP0581886A1 (en) | 1994-02-09 |
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