JP6843378B2 - Sulfur-containing polymer - Google Patents
Sulfur-containing polymer Download PDFInfo
- Publication number
- JP6843378B2 JP6843378B2 JP2016227839A JP2016227839A JP6843378B2 JP 6843378 B2 JP6843378 B2 JP 6843378B2 JP 2016227839 A JP2016227839 A JP 2016227839A JP 2016227839 A JP2016227839 A JP 2016227839A JP 6843378 B2 JP6843378 B2 JP 6843378B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- sulfur
- ethylene
- carbon atoms
- containing polymer
- 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.)
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- 229910052717 sulfur Inorganic materials 0.000 title claims description 147
- 239000011593 sulfur Substances 0.000 title claims description 147
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 143
- 229920000642 polymer Polymers 0.000 title claims description 98
- -1 alkoxy compound Chemical class 0.000 claims description 213
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000001641 gel filtration chromatography Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 239000002033 PVDF binder Substances 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JLQNHALFVCURHW-UHFFFAOYSA-N cyclooctasulfur Chemical compound S1SSSSSSS1 JLQNHALFVCURHW-UHFFFAOYSA-N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- JBWIUQLVXOBHBF-UHFFFAOYSA-N (4-ethenylphenyl)silane Chemical compound [SiH3]C1=CC=C(C=C)C=C1 JBWIUQLVXOBHBF-UHFFFAOYSA-N 0.000 description 1
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical group CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 1
- 125000004375 1,1-dimethylbutylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000004822 1,1-dimethylpropylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000004376 1,2-dimethylbutylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000004823 1,2-dimethylpropylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- CIISBYKBBMFLEZ-UHFFFAOYSA-N 1,2-oxazolidine Chemical compound C1CNOC1 CIISBYKBBMFLEZ-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 125000004842 1,3-dimethylbutylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- 125000004824 1,3-dimethylpropylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([*:2])C([H])([H])[H] 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000004818 1-methylbutylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- XWIYUCRMWCHYJR-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyridine Chemical compound C1=CC=C2NC=CC2=N1 XWIYUCRMWCHYJR-UHFFFAOYSA-N 0.000 description 1
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004819 2-methylbutylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004820 3-methylbutylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、分子状硫黄（Ｓ８）とシリルエーテル骨格を有するアルケニル化合物を反応させて得られる含硫黄ポリマーと、当該含硫黄ポリマーを含む正極及び当該正極を備える二次電池に関する。 The present invention relates to a sulfur-containing polymer obtained by reacting molecular sulfur (S 8 ) with an alkenyl compound having a silyl ether skeleton, a positive electrode containing the sulfur-containing polymer, and a secondary battery including the positive electrode.
石油精製時の回収等で生産される硫黄は、硫酸等の工業製品、ゴム等の添加剤、肥料等の多岐にわたる用途に使用される。しかし、これらの用途で消費される硫黄の量は、硫黄の生産量を下回っており、余剰の硫黄の保管が問題となっている。そこで、硫黄の新たな用途が検討され、硫黄が二次電池の正極の材料として利用されるようになった。硫黄の理論電池容量は、リチウム二次電池の正極活物質として通常使用されているＬｉＣｏＯ２の理論電池容量より大きい。そのため、リチウム又はナトリウムが負極の材料とされ、硫黄が正極活物質とされる二次電池が数多く報告されている。このうち、ナトリウム−硫黄電池は実用化されているが、硫黄正極の活性が高められるよう、その動作温度が３００℃と高温になる必要があり、電池デバイス自体の大きさとも相俟って、通常の環境下で使用され難い。更に、硫黄正極を備える二次電池の充放電が繰り返されると、硫黄が電解液中に溶出して電池を構成する金属と化学反応し金属硫化物を生成するため、電池容量が低下し、二次電池の寿命は短かった。 Sulfur produced by recovery during petroleum refining is used in a wide range of applications such as industrial products such as sulfuric acid, additives such as rubber, and fertilizers. However, the amount of sulfur consumed in these applications is less than the amount of sulfur produced, and storage of excess sulfur has become a problem. Therefore, new uses of sulfur have been studied, and sulfur has come to be used as a material for positive electrodes of secondary batteries. The theoretical battery capacity of sulfur is larger than the theoretical battery capacity of LiCoO 2 , which is usually used as the positive electrode active material of the lithium secondary battery. Therefore, many secondary batteries have been reported in which lithium or sodium is used as the negative electrode material and sulfur is used as the positive electrode active material. Of these, sodium-sulfur batteries have been put into practical use, but their operating temperature must be as high as 300 ° C so that the activity of the sulfur positive electrode can be enhanced, and in combination with the size of the battery device itself, Difficult to use under normal circumstances. Further, when the secondary battery provided with the sulfur positive electrode is repeatedly charged and discharged, sulfur elutes into the electrolytic solution and chemically reacts with the metal constituting the battery to generate metal sulfide, which reduces the battery capacity. The life of the next battery was short.
そこで、含硫黄ポリマーの、金属硫化物の電解液への溶出が抑制された正極活物質としての使用が提案され、分子状硫黄（Ｓ８）とビニル化合物とのラジカル重合（逆加硫）によって合成された含硫黄ポリマーが検討された（例えば、非特許文献１参照）。更に、特定のジアリル化合物又は炭素数５〜２０のアルキル基を有する特定のモノアリル化合物と分子状硫黄（Ｓ８）が混合され加熱されて得られる含硫黄ポリマーが正極の材料として使用される二次電池（例えば、特許文献１参照）、イオン性基を有する特定のモノアリル化合物と分子状硫黄（Ｓ８）が混合され加熱されて得られる含硫黄ポリマーが正極の材料として使用される二次電池（例えば、特許文献２参照）が検討された。 Therefore, it has been proposed to use a sulfur-containing polymer as a positive electrode active material in which elution of metal sulfide into an electrolytic solution is suppressed, and by radical polymerization (reverse vulcanization) of molecular sulfur (S 8) and a vinyl compound. Synthesized sulfur-containing polymers were investigated (see, for example, Non-Patent Document 1). Further, a sulfur-containing polymer obtained by mixing and heating a specific diallyl compound or a specific monoallyl compound having an alkyl group having 5 to 20 carbon atoms and molecular sulfur (S 8 ) is used as a material for the positive electrode. A battery (see, for example, Patent Document 1), a secondary battery in which a sulfur-containing polymer obtained by mixing and heating a specific monoallyl compound having an ionic group and molecular sulfur (S 8) is used as a material for a positive electrode (see, for example, Patent Document 1). For example, see Patent Document 2).
近年、二次電池の正極として利用可能な含硫黄ポリマーの硫黄含有量の更なる増大と、含硫黄ポリマーを含有する正極を備える二次電池のサイクル性（充放電が繰り返されても、電池容量が低下しないという性能）の更なる向上が期待されている。 In recent years, the sulfur content of the sulfur-containing polymer that can be used as the positive electrode of the secondary battery has been further increased, and the cycleability of the secondary battery having the positive electrode containing the sulfur-containing polymer (battery capacity even if charging and discharging are repeated). It is expected that the performance) will be further improved.
本発明は、このような事情に鑑みてなされており、本発明が解決しようとする課題は、硫黄含有量が大きな、二次電池の正極活物質として利用可能な含硫黄ポリマーの提供である。更に、本発明が解決しようとする別の課題は、当該含硫黄ポリマーを含有する正極を備え、サイクル性が高い二次電池の提供である。 The present invention has been made in view of such circumstances, and the problem to be solved by the present invention is to provide a sulfur-containing polymer which has a large sulfur content and can be used as a positive electrode active material of a secondary battery. Further, another problem to be solved by the present invention is to provide a secondary battery having a positive electrode containing the sulfur-containing polymer and having high cycleability.
本発明の発明者らは、上記課題を解決するために鋭意検討した結果、特定のアルケニル化合物と分子状硫黄（Ｓ８）を反応させて得られる含硫黄ポリマーの硫黄含有量は大きく、当該含硫黄ポリマーは二次電池の正極活物質として利用可能であり、当該含硫黄ポリマーを含有する正極を備える二次電池のサイクル性は高いことを見出し、本発明を完成させるに至った。 As a result of diligent studies to solve the above problems, the inventors of the present invention have found that the sulfur-containing polymer obtained by reacting a specific alkenyl compound with molecular sulfur (S 8) has a large sulfur content. The sulfur polymer can be used as a positive electrode active material of a secondary battery, and it has been found that the secondary battery including the positive electrode containing the sulfur-containing polymer has high cycleability, and the present invention has been completed.
すなわち、本発明は、
［１］ 以下の式（１）
［２］Ｒ１は−ＣＨ３、−ＯＣＨ３又は−ＯＣＨ２ＣＨ２ＯＣＨ３であり、Ｒ２は１，４−フェニレン基、−ＣＨ２−、−（ＣＨ２）６−又は−ＣＯＯ−（ＣＨ２）３−であり、Ｒ３は−ＣＨ３又は−Ｈである、［１］に記載されている含硫黄ポリマー、
［３］含硫黄ポリマーに対する硫黄含有量が５０〜９５質量％である、請求項１又は２に記載されている含硫黄ポリマー、
［４］［１］〜［３］のいずれかに記載されている含硫黄ポリマーを含有する二次電池用正極、
［５］［４］に記載されている二次電池用正極を備える二次電池に関する。
That is, the present invention
[1] The following equation (1)
[2] R 1 is -CH 3 , -OCH 3 or -OCH 2 CH 2 OCH 3 , and R 2 is a 1,4-phenylene group, -CH 2 -,-(CH 2 ) 6- or -COO-. (CH 2 ) The sulfur-containing polymer according to [1], which is 3 − and R 3 is −CH 3 or −H.
[3] The sulfur-containing polymer according to
[4] A positive electrode for a secondary battery containing the sulfur-containing polymer according to any one of [1] to [3].
[5] The present invention relates to a secondary battery including the positive electrode for the secondary battery described in [4].
また、本発明は、
［６］以下の式（２）
Ｈ２Ｃ＝ＣＲ３（Ｒ２）ｎ−Ｓｉ（Ｒ１）３ （２）
（式中、Ｒ１は置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキル基、主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルコキシ基及び−Ｃｌからなる群より選ばれるいずれかの基を表す。各Ｒ１は、同一であっても異なっていてもよい。Ｒ２は置換又は非置換の芳香族基、置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基、−ＣＯＯ−を有する置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基及び−ＣＯＯ−からなる群より選ばれるいずれか１つを表す。Ｒ３は置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキル基若しくは−Ｈを表す。ｎは０又は１である。）で表される骨格を有するアルケニル化合物と分子状硫黄（Ｓ８）を反応させる、以下の式（１）で表される繰り返し単位を有する含硫黄ポリマーの製造方法に関する。
In addition, the present invention
[6] The following equation (2)
H 2 C = CR 3 (R 2 ) n −Si (R 1 ) 3 (2)
(In the formula, R 1 is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted linear or branched alkyl group having 1 or more -O− in the main chain. Represents any group selected from the group consisting of ~ 20 alkoxy groups and −Cl. Each R 1 may be the same or different; R 2 is a substituted or unsubstituted aromatic group, substituted. Alternatively, it is selected from the group consisting of an unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms having −COO−, and −COO−. R 3 represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or −H. N is 0 or 1). The present invention relates to a method for producing a sulfur-containing polymer having a repeating unit represented by the following formula (1), in which the alkoxy compound having is reacted with molecular sulfur (S 8).
（式中、Ｒ１、Ｒ２、Ｒ３及びｎは前記されるとおりであり、Ｘは１以上の正の整数を表し、各単位中のＸの数は異なっていてよい。） (In the equation, R 1 , R 2 , R 3 and n are as described above, X represents a positive integer of 1 or more, and the number of X in each unit may be different.)
本発明の含硫黄ポリマーは、融解された分子状硫黄（Ｓ８）と上記アルケニル化合物の１段階の反応で合成される。本発明の含硫黄ポリマーの硫黄含有量は大きく、二次電池の正極活物質として利用可能である。更に、本発明の含硫黄ポリマーを含有する正極を備える本発明の二次電池のサイクル性は高い。 The sulfur-containing polymer of the present invention is synthesized by a one-step reaction of molten molecular sulfur (S 8) and the alkenyl compound. The sulfur-containing polymer of the present invention has a large sulfur content and can be used as a positive electrode active material for a secondary battery. Further, the secondary battery of the present invention provided with the positive electrode containing the sulfur-containing polymer of the present invention has high cycleability.
本発明の含硫黄ポリマーは、以下の式（２）
Ｈ２Ｃ＝ＣＲ３（Ｒ２）ｎ−Ｓｉ（Ｒ１）３ （２）
（式中、Ｒ１は置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキル基、主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルコキシ基及び−Ｃｌからなる群より選ばれるいずれかの基を表す。各Ｒ１は、同一であっても異なっていてもよい。Ｒ２は置換又は非置換の芳香族基、置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基、−ＣＯＯ−を有する置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基及び−ＣＯＯ−からなる群より選ばれるいずれか１つを表す。Ｒ３は置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキル基若しくは−Ｈを表す。ｎは０又は１である。）で表される骨格を有するアルケニル化合物と分子状硫黄（Ｓ８）を反応させて製造される。
The sulfur-containing polymer of the present invention has the following formula (2).
H 2 C = CR 3 (R 2 ) n −Si (R 1 ) 3 (2)
(In the formula, R 1 is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted linear or branched alkyl group having 1 or more -O− in the main chain. Represents any group selected from the group consisting of ~ 20 alkoxy groups and −Cl. Each R 1 may be the same or different; R 2 is a substituted or unsubstituted aromatic group, substituted. Alternatively, it is selected from the group consisting of an unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms having −COO−, and −COO−. R 3 represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or −H. N is 0 or 1). It is produced by reacting the alkenyl compound having it with molecular sulfur (S 8).
上記Ｒ１及びＲ３の「置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキル基」の「直鎖又は分岐の炭素数１〜２０のアルキル基」の具体例は、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、１−メチルブチル基、２−メチルブチル基、３−メチルブチル基、１，１−ジメチルプロピル基、１，２−ジメチルプロピル基、２，２−ジメチルプロピル基、３−ペンチル基、ｎ−ヘキシル基、１−メチルヘプチル基、２−メチルヘプチル基、３−メチルヘプチル基、４−メチルヘプチル基、１，１−ジメチルブチル基、１，２−ジメチルブチル基、１，３−ジメチルブチル基、２，２−ジメチルブチル基、２，３−ジメチルブチル基、３，３−ジメチルブチル基、３，３−ジメチルブタン−２−イル基、２，３−ジメチルブタン−２−イル基、３−ヘキシル基、２−エチルペンチル基、２−メチルペンタン−３−イル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等である。 Specific examples of the "linear or branched alkyl group having 1 to 20 carbon atoms" of the "substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms" of R 1 and R 3 are methyl groups. , Ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1 -Dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 3-pentyl group, n-hexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4 -Methyl heptyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethyl Butyl group, 3,3-dimethylbutane-2-yl group, 2,3-dimethylbutane-2-yl group, 3-hexyl group, 2-ethylpentyl group, 2-methylpentane-3-yl group, heptyl group , Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group and the like.
上記Ｒ１及びＲ３の「置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキル基」の置換基は、水酸基、フッ素原子、下記に示す芳香族基、ジアルキルアミノ基、アルキルオキシカルボニル基、アルコキシ基、含窒素ヘテロ環基等である。上記ジアルキルアミノ基、アルキルオキシカルボニル基及びアルコキシ基におけるアルキルは、直鎖又は分岐の炭素数１〜４のアルキルであり、具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓ−ブチル、ｔ−ブチル、イソブチルである。上記含窒素ヘテロ環基は、具体的には、ピロリジン、ピラゾリジン、イミダゾリジン、オキサゾリジン、イソオキサゾリジン、ピペリジン、ピペラジン、モルホリン、チオモルホリン等である。 The substituents of the "substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms" of R 1 and R 3 are hydroxyl groups, fluorine atoms, aromatic groups shown below, dialkylamino groups, and alkyloxys. It is a carbonyl group, an alkoxy group, a nitrogen-containing heterocyclic group, or the like. The alkyl in the dialkylamino group, alkyloxycarbonyl group and alkoxy group is a linear or branched alkyl having 1 to 4 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. They are s-butyl, t-butyl and isobutyl. Specific examples of the nitrogen-containing heterocyclic group include pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isooxazolidine, piperidine, piperazine, morpholine, and thiomorpholine.
上記Ｒ１の「主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルコキシ基」として、具体的には、メチル−Ｏ−、エチル−Ｏ−、プロピル−Ｏ−、ｎ−ブチル−Ｏ−、ｓ−ブチル−Ｏ−、ｔ−ブチル−Ｏ−、ｎ−ペンチル−Ｏ−、１-メチルブチル−Ｏ−、２-メチルブチル−Ｏ−、３-メチルブチル−Ｏ−、１，１-ジメチルプロピル−Ｏ−、１，２-ジメチルプロピル−Ｏ−、２，２-ジメチルプロピル−Ｏ−、３−ペンチル−Ｏ−、ｎ−ヘキシル−Ｏ−、１-メチルヘプチル−Ｏ−、２-メチルヘプチル−Ｏ−、３-メチルヘプチル−Ｏ−、４-メチルヘプチル−Ｏ−、１，１-ジメチルブチル−Ｏ−、１，２-ジメチルブチル−Ｏ−、１，３-ジメチルブチル−Ｏ−、２，２-ジメチルブチル−Ｏ−、２，３-ジメチルブチル−Ｏ−、３，３-ジメチルブチル−Ｏ−、３，３-ジメチルブタン−２−イル−Ｏ−、２，３-ジメチルブタン−２−イル−Ｏ−、３−ヘキシル−Ｏ−、２-エチルペンチル−Ｏ−、２-メチルペンタン−３−イル−Ｏ−、ヘプチル−Ｏ−、オクチル−Ｏ−、ノニル−Ｏ−、デシル−Ｏ−、ウンデシル−Ｏ−、ドデシル−Ｏ−、トリデシル−Ｏ−、テトラデシル−Ｏ−、ペンタデシル−Ｏ−、ヘキサデシル−Ｏ−、ヘプタデシル−Ｏ−、オクタデシル−Ｏ−、ノナデシル−Ｏ−、イコシル−Ｏ−、メチル−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−へキシレン−Ｏ−、エチル−Ｏ−ヘプチレン−Ｏ−、エチル−Ｏ−オクチレン−Ｏ−、エチル−Ｏ−ノニレン−Ｏ−、エチル−Ｏ−デシレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−ヘキシレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−ヘプチレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−ペンチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−ヘキシレン−Ｏ−、エチル−Ｏ−ペンチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−ペンチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−ペンチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−ペンチレン−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−ヘキシレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−ヘキシレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−ヘキシレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−ヘプチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−ヘプチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−オクチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ヘキシレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−プロピレン−Ｏ−ペンチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、エチル−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−、プロピル−Ｏ−ブチレン−Ｏ−、プロピル−Ｏ−ペンチレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−へキシレン−Ｏ−、プロピル−Ｏ−へキシレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−ヘプチレン−Ｏ−、プロピル−Ｏ−ヘプチレン−Ｏ−、プロピル−Ｏ−ノニレン−Ｏ−、プロピル−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−、プロピル−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−、プロピル−Ｏ−エチレン−Ｏ−ヘキシレン−Ｏ−、プロピル−Ｏ−エチレン−Ｏ−ヘプチレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−ブチレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−ペンチレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−ヘキシレン−Ｏ−、プロピル−Ｏ−ブチレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−、プロピル−Ｏ−ブチレン−Ｏ−ペンチレン−Ｏ−、プロピル−Ｏ−ペンチレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−ペンチレン−Ｏ−ブチレン−Ｏ−、プロピル−Ｏ−ヘキシレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−、プロピル−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−、ブチル−Ｏ−ブチレン−Ｏ−、ブチル−Ｏ−ペンチレン−Ｏ−、ブチル−Ｏ−ヘキシレン−、ブチル−Ｏ−ヘプチレン−Ｏ−、ブチル−Ｏ−オクチレン−Ｏ−、ブチル−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−、ブチル−Ｏ−プロピレン−Ｏ−ブチレン−Ｏ−、ブチル−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−、ブチル−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−、ブチル−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−、ペンチル−Ｏ−ペンチレン−Ｏ−、ペンチル−Ｏ−へキシレン−Ｏ−、ペンチル−Ｏ−へキシレン−Ｏ−、ペンチル−Ｏ−ヘプチレン−Ｏ−、ペンチル−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−、ペンチル−Ｏ−ペンチレン−Ｏ−ペンチレン−Ｏ−、ペンチル−Ｏ−ペンチレン−Ｏ−ペンチレン−Ｏ−ペンチレン−Ｏ−、へキシル−Ｏ−へキシレン−Ｏ−、へキシル−Ｏ−へキシレン−Ｏ−へキシレン−Ｏ−、ヘプチル−Ｏ−ヘプチレン−Ｏ−、オクチル−Ｏ−オクチレン−Ｏ−、ノニル−Ｏ−ノニレン−Ｏ−、デシル−Ｏ−デシレン−Ｏ−等が挙げられる。 Specifically, as "a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms having 1 or more -O- in the main chain" of R 1, specifically, methyl-O- and ethyl-O. -, propyl-O-, n-butyl-O-, s-butyl-O-, t-butyl-O-, n-pentyl-O-, 1-methylbutyl-O-, 2-methylbutyl-O-, 3 -Methylbutyl-O-, 1,1-dimethylpropyl-O-, 1,2-dimethylpropyl-O-, 2,2-dimethylpropyl-O-, 3-pentyl-O-, n-hexyl-O-, 1-Methylheptyl-O-, 2-Methylheptyl-O-, 3-Methylheptyl-O-, 4-Methylheptyl-O-, 1,1-dimethylbutyl-O-, 1,2-dimethylbutyl-O -, 1,3-dimethylbutyl-O-, 2,2-dimethylbutyl-O-, 2,3-dimethylbutyl-O-, 3,3-dimethylbutyl-O-, 3,3-dimethylbutane-2 -Il-O-, 2,3-dimethylbutane-2-yl-O-, 3-hexyl-O-, 2-ethylpentyl-O-, 2-methylpentan-3-yl-O-, heptyl-O -, Octyl-O-, Nonyl-O-, Decyl-O-, Undecyl-O-, Dodecyl-O-, Tridecyl-O-, Tetradecyl-O-, Pentadecyl-O-, Hexadecyl-O-, Heptadecyl-O. -, Octadecyl-O-, Nonadecil-O-, Icosyl-O-, Methyl-O-ethylene-O-, Ethyl-O-ethylene-O-, Ethyl-O-propylene-O-, Ethyl-O-Butylene- O-, ethyl-O-pentylene-O-, ethyl-O-hexylene-O-, ethyl-O-heptylene-O-, ethyl-O-octylene-O-, ethyl-O-nonylene-O-, ethyl -O-decylene-O-, ethyl-O-ethylene-O-ethylene-O-, ethyl-O-propylene-O-ethylene-O-, ethyl-O-propylene-O-propylene-O-, ethyl-O -Propropylene-O-Butylene-O-, Ethyl-O-Protin-O-Pentylene-O-, Ethyl-O-Protin-O-Hexylene-O-, Ethyl-O-Protin-O-Heptylene-O-, Ethyl -O-butylene-O-ethylene-O-, ethyl-O-pentylene-O-ethylene-O-, ethyl-O-butylene-O-propylene-O-, ethyl-O-butylene-O-butylene-O- , Ethyl-O-Butylene-O-Pentylene-O-, Ethyl-O-Butylene-O-Hexylene -O-, ethyl-O-pentylene-O-ethylene-O-, ethyl-O-pentylene-O-propylene-O-, ethyl-O-pentylene-O-butylene-O-, ethyl-O-pentylene-O -Pentylene-O-, Ethylene-O-Hexylene-O-Ethylene-O-, Ethylene-O-Hexylene-O-Protin-O-, Ethyl-O-Hexylene-O-Butylene-O-, Ethylene-O-Heptylene -O-Ethylene-O-, Ethylene-O-Heptylene-O-Protin-O-, Ethylene-O-octylene-O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O- , Ethylene-O-Ethylene-O-Ethylene-O-Protin-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Pentylene-O -, Ethylene-O-ethylene-O-propylene-O-ethylene-O-, ethyl-O-ethylene-O-propylene-O-propylene-O-, ethyl-O-ethylene-O-propylene-O-butylene- O-, ethyl-O-ethylene-O-propylene-O-pentylene-O-, ethyl-O-ethylene-O-ethylene-O-ethylene-O-, ethyl-O-ethylene-O-butylene-O-propylene -O-, ethyl-O-ethylene-O-butylene-O-butylene-O-, ethyl-O-ethylene-O-pentylene-O-ethylene-O-, ethyl-O-ethylene-O-pentylene-O- Propropylene-O-, Ethylene-O-Ethylene-O-Hexylene-O-Ethylene-O-, Ethylene-O-Protin-O-Ethylene-O-Ethylene-O-, Ethylene-O-Protin-O-Ethylene-O -Butylene-O-, ethyl-O-propylene-O-ethylene-O-pentylene-O-, ethyl-O-propylene-O-propylene-O-ethylene-O-, ethyl-O-propylene-O-butylene- O-ethylene-O-, ethyl-O-propylene-O-pentylene-O-ethylene-O-, ethyl-O-butylene-O-ethylene-O-propylene-O-, ethyl-O-butylene-O-ethylene -O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Protin-O-, Ethylene-O-ethylene-O-ethylene-O-ethylene-O-butylene-O-, ethyl-O-ethylene-O-ethylene-O-propylene- O-ethylene-O-, ethyl-O-ethylene-O-ethylene-O-butylene-O-ethylene-O-, ethyl-O-ethylene-O-propylene-O-ethylene-O-ethylene-O-, ethyl -O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-, Ethylene-O-Ethylene -O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene- O-Ethylene-O-, Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-Ethylene-O-, Ethylene-O-Ethylene- O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-, propyl-O-butylene-O-, propyl-O-pentylene- O-, propyl-O-propylene-O-hexylene-O-, propyl-O-hexylene-O-, propyl-O-propylene-O-heptylene-O-, propyl-O-heptylene-O-, propyl -O-Nonylene-O-, propyl-O-ethylene-O-propylene-O-, propyl-O-ethylene-O-butylene-O-, propyl-O-ethylene-O-pentylene-O-, propyl-O -Ethylene-O-Hexylene-O-, propyl-O-Ethylene-O-Heptylene-O-, propyl-O-propylene-O-propylene-O-, propyl-O-propylene-O-butylene-O-, propyl -O-propylene-O-pentylene-O-, propyl-O-propylene-O-hexylene-O-, propyl-O-butylene-O-propylene-O-, propyl-O-butylene-O-butylene-O- , Propyl-O-butylene-O-pentylene-O-, propyl-O-pentylene-O-propylene-O-, propyl-O-pentylene-O-butylene-O-, propyl-O-hexylene-O-propylene- O-, propyl-O-propylene-O-propylene-O-propylene-O-, propyl-O-propylene-O-propylene-O-propylene-O-propylene-O-, propyl-O-propylene-O-propylene -O-propylene-O-propylene-O-propylene-O-, butyl-O-butylene -O-, Butyl-O-Pentylene-O-, Butyl-O-Hexylene-, Butyl-O-Heptylene-O-, Butyl-O-octylene-O-, Butyl-O-ethylene-O-butylene-O- , Butyl-O-propylene-O-butylene-O-, butyl-O-butylene-O-butylene-O-, butyl-O-butylene-O-butylene-O-butylene-O-, butyl-O-butylene- O-butylene-O-butylene-O-butylene-O-, pentyl-O-pentylene-O-, pentyl-O-hexylene-O-, pentyl-O-hexylene-O-, pentyl-O-heptylene- O-, pentyl-O-ethylene-O-pentylene-O-, pentyl-O-pentylene-O-pentylene-O-, pentyl-O-pentylene-O-pentylene-O-pentylene-O-, hexylene-O -Hexylene-O-, hexyl-O-hexylene-O-hexylene-O-, heptyl-O-heptylene-O-, octyl-O-octylene-O-, nonyl-O-nonylene-O-, Examples thereof include decyl-O-decylene-O-.
上記Ｒ１の「主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数１〜２０のアルキコキシ基」の置換基は、上記Ｒ１及びＲ３の「置換又は非置換の直鎖の炭素数１〜２０のアルキル基」の置換基と同様である。 The substituent of the above-mentioned R 1 "substituted or unsubstituted linear or branched alkyloxy group having 1 to 20 carbon atoms having 1 or more -O- in the main chain" is the above-mentioned R 1 and R 3 "substituent or It is the same as the substituent of the "unsubstituted straight chain alkyl group having 1 to 20 carbon atoms".
上記Ｒ２の「置換又は非置換の芳香族基」の「芳香族基」は、二価の芳香族環である。芳香族環は、単環又は多環の炭素数６−１０のアリール基、ヘテロ原子として窒素原子、酸素原子、又は硫黄原子を１〜４個有する５〜７員の単環又は多環のヘテロアリール基、及び、ベンゼン環とヘテロ原子として窒素原子、酸素原子、又は硫黄原子を１〜４個有する５〜７員の複素環が縮合した縮合環からなるヘテロアリール基を包含する。 The "aromatic group" of the "substituted or unsubstituted aromatic group" of R 2 is a divalent aromatic ring. The aromatic ring is a 5- to 7-membered monocyclic or polycyclic hetero having 1 to 4 aryl groups having 6 to 10 carbon atoms and 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms. It includes an aryl group and a heteroaryl group consisting of a fused ring in which a benzene ring and a 5- to 7-membered heterocycle having 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms are condensed.
芳香族環として具体的には、ベンゼン、ナフタレン、アズレン、アントラセン、テトラセン、ペンタセン、フェナントレン、ピレン、ピロール、フラン、チオフェン、ピラゾール、イミダゾール、オキサゾール、チアゾール、トリアゾール、オキサジアゾール、チアジアゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、トリアジン、インドール、イソインドール、ベンズオキサゾール、ベンズチアゾール、ベンゾイソキサゾール、ベンズイソチアゾール、ベンゾオキサジアゾール、ベンズチアジアゾール、ピロロピリジン、ピロロピラジン、プリン、キノリン、イソキノリン、シノリン、キナゾリン、キノキサリン等が挙げられる。 Specifically, as an aromatic ring, benzene, naphthalene, azulene, anthracene, tetracene, pentacene, phenanthrene, pyrene, pyrrol, furan, thiophene, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazol, thiadiazol, pyridine, pyridazine. , Pyrazine, pyrazine, triazole, indol, isoindole, benzoxazole, benzthiazole, benzoisoxazole, benzisothiazole, benzoxaziazole, benzthiazazole, pyrrolopyridine, pyrrolopyrazine, purine, quinoline, isoquinoline, sinolin, quinazoline , Quinoline and the like.
上記Ｒ２の「置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基」及び「−ＣＯＯ−を有する置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基」の「直鎖又は分岐の炭素数１〜２０のアルキレン基」の具体例は、メチレン基、エチレン基、ｎ−プロピレン基、イソプロピレン基、ｎ−ブチレン基、ｓ−ブチレン基、ｎ−ペンチレン基、１−メチルブチレン基、２−メチルブチレン基、３−メチルブチレン基、ｎ−ペンチレン基、１，１−ジメチルプロピレン基、１，２−ジメチルプロピレン基、２，２−ジメチルプロピレン基、１，３−ジメチルプロピレン基、ｎ−ヘキシレン基、１−メチルヘプチレン基、２−メチルヘプチレン基、３−メチルヘプチレン基、１，１−ジメチルブチレン基、１，２−ジメチルブチレン基、１，３−ジメチルブチレン基、２，２−ジメチルブチレン基、２，３−ジメチルブチレン基、３，３−ジメチルブチレン基、３，３−ジメチルブタン−２−イレン基、２，３−ジメチルブタン−２−イレン基、３−ヘキシレン基、２−エチルペンチレン基、２−メチルペンタン−３−イレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ウンデシレン基、ドデシレン基、トリデシレン基、テトラデシレン基、ペンタデシレン基、ヘキサデシレン基、ヘプタデシレン基、オクタデシレン基、ノナデシレン基、イコシレン基等である。 The R 2 'substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, "" substituted or unsubstituted straight or branched alkylene group having 1 to 20 carbon atoms having a -COO- "and Specific examples of the "straight or branched alkylene group having 1 to 20 carbon atoms" include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an s-butylene group and an n-pentylene group. , 1-Methylbutylene group, 2-Methylbutylene group, 3-Methylbutylene group, n-pentylene group, 1,1-dimethylpropylene group, 1,2-dimethylpropylene group, 2,2-dimethylpropylene group, 1, 3-Dimethylpropylene group, n-hexylene group, 1-methylheptylene group, 2-methylheptylene group, 3-methylheptylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 1,3-dimethylbutylene group, 2,2-Dimethylbutylene group, 2,3-dimethylbutylene group, 3,3-dimethylbutylene group, 3,3-dimethylbutane-2-ylene group, 2,3-dimethylbutane-2-ylene group, 3- Hexylene group, 2-ethylpentylene group, 2-methylpentane-3-ylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, It is a heptadecylene group, an octadecylene group, a nonadesilene group, an icosilene group and the like.
上記Ｒ２の「−ＣＯＯ−を有する置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基」の「−ＣＯＯ−」は「アルキレン基」の末端にあっても、２つの「アルキレン基」の間にあってもよい。好ましくは、「−ＣＯＯ−」は「アルキレン基」の末端にある。 The above R 2 "-COO-" of the "substituted or unsubstituted straight or branched alkylene group having 1 to 20 carbon atoms having a -COO-" is even the end of the "alkylene group", two " It may be between "alkylene groups". Preferably, "-COO-" is at the end of the "alkylene group".
上記Ｒ２の「置換又は非置換の芳香族基」、「置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基」及び「−ＣＯＯ−を有する置換又は非置換の直鎖又は分岐の炭素数１〜２０のアルキレン基」の置換基として、上記Ｒ１及びＲ３の「置換又は非置換の直鎖の炭素数１〜２０のアルキル基」の置換基と同様の置換基が挙げられる。 R 2 above in the "substituted or unsubstituted aromatic group", "substituted or unsubstituted straight or branched alkylene group having 1 to 20 carbon atoms" and "linear substituted or unsubstituted having -COO- or As the substituent of the branched alkylene group having 1 to 20 carbon atoms, the same substituent as the substituent of the above-mentioned R 1 and R 3 "substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms" can be used. Can be mentioned.
本発明の含硫黄ポリマーの製造方法は特定の方法に限定されない。当該製造方法の具体例は以下のとおりである。
分子状硫黄（Ｓ８）は、有機溶媒に不溶又は溶解しづらいため、本発明の含硫黄ポリマー合成の第一段階は、硫黄の反応容器中での加熱による融解である。硫黄は多くの同素体（Ｓ8、Ｓ6、Ｓ１２、Ｓ１８、Ｓ２０等）を持ち、それぞれが融点を有する。硫黄の最安定な同素体は環状構造をした分子状硫黄（Ｓ８）であり、分子状硫黄（Ｓ８）は３つの結晶形（α硫黄、β硫黄及びγ硫黄）をもち、それらの融点はそれぞれ１１２．８℃、１１９．６℃、１０６．８℃である。そのため、１２０℃以上の温度での加熱が分子状硫黄（Ｓ８）の融解のために必要である。また、分子状硫黄（Ｓ８）は安定構造のα硫黄から温度の上昇とともにβ硫黄、λ硫黄、μ硫黄へと転移していき、１５９．４℃以上で環状硫黄のラジカル開裂が進み、２価のラジカルができる。このようにして、分子状硫黄（Ｓ８）は１５９．４℃以上の温度でラジカルを発生するため、融解温度は上記温度より低く設定する必要がある。分子状硫黄（Ｓ８）の融解温度は、好ましくは１２０℃〜１５５℃、より好ましくは１３５℃〜１５５℃、更に好ましくは１４５℃〜１５５℃、最も好ましくは１５０℃〜１５５℃である。
The method for producing the sulfur-containing polymer of the present invention is not limited to a specific method. Specific examples of the manufacturing method are as follows.
Since molecular sulfur (S 8 ) is insoluble or difficult to dissolve in an organic solvent, the first step in synthesizing a sulfur-containing polymer of the present invention is melting by heating in a sulfur reaction vessel. Sulfur has many allotropes (S 8 , S 6 , S 12 , S 18 , S 20, etc.), each with a melting point. The most stable allotrope of sulfur is molecular sulfur (S 8 ) with a cyclic structure, and molecular sulfur (S 8 ) has three crystalline forms (α-sulfur, β-sulfur and γ-sulfur), and their melting points are It is 112.8 ° C., 119.6 ° C., and 106.8 ° C., respectively. Therefore, heating at a temperature of 120 ° C. or higher is required for melting molecular sulfur (S 8). In addition, molecular sulfur (S 8 ) is transferred from α-sulfur, which has a stable structure, to β-sulfur, λ-sulfur, and μ-sulfur as the temperature rises, and radical cleavage of cyclic sulfur progresses at 159.4 ° C or higher, 2 Valuable radicals are formed. In this way, molecular sulfur (S 8 ) generates radicals at a temperature of 159.4 ° C. or higher, so that the melting temperature needs to be set lower than the above temperature. The melting temperature of the molecular sulfur (S 8 ) is preferably 120 ° C. to 155 ° C., more preferably 135 ° C. to 155 ° C., further preferably 145 ° C. to 155 ° C., and most preferably 150 ° C. to 155 ° C.
次いで、上記式（２）で表されるアルケニル化合物が溶融された分子状硫黄（Ｓ８）に加えられ、上記式（１）で表される本発明の含硫黄ポリマーが１段階で合成される。その際、上記式（２）で表されるアルケニル化合物が溶融された分子状硫黄（Ｓ８）に均一に分散されるよう、反応中、攪拌が行われてよい。 Next, the alkenyl compound represented by the above formula (2) is added to the molten molecular sulfur (S 8 ), and the sulfur-containing polymer of the present invention represented by the above formula (1) is synthesized in one step. .. At that time, stirring may be performed during the reaction so that the alkenyl compound represented by the above formula (2) is uniformly dispersed in the molten molecular sulfur (S 8).
上記反応の温度は、分子状硫黄（Ｓ８）がラジカルを発生させる温度範囲であり、好ましくは１６０℃〜１７５℃である。 The temperature of the reaction is in the temperature range in which molecular sulfur (S 8 ) generates radicals, and is preferably 160 ° C to 175 ° C.
本発明の含硫黄ポリマーは、式（１） The sulfur-containing polymer of the present invention has the formula (1).
で表わされる繰り返し単位を有する。ここで、Ｒ１、Ｒ２、Ｒ３及びｎは上記式（２）で表わされるアルケニル化合物におけるＲ１、Ｒ２、Ｒ３及びｎと同じである。Ｘの上限値は１００である。 It has a repeating unit represented by. Here, R 1 , R 2 , R 3 and n are the same as R 1 , R 2 , R 3 and n in the alkenyl compound represented by the above formula (2). The upper limit of X is 100.
本発明の含硫黄ポリマーは、クロロホルム、ジクロロメタン、テトラヒドロフラン、Ｎ−メチル−２−ピロリドン等の有機溶媒に可溶である。上記方法で合成された本発明の含硫黄ポリマーは通常精製される必要はないが、高純度の含硫黄ポリマーが必要とされる場合、反応生成物が上記有機溶媒に溶解され、ろ過されて、有機溶媒に不溶の硫黄が除かれる。また、ろ過後の溶液が、ゲルろ過クロマトグラフィー等の分子ふるいに供され、ポリマーとモノマーが分離される。 The sulfur-containing polymer of the present invention is soluble in organic solvents such as chloroform, dichloromethane, tetrahydrofuran and N-methyl-2-pyrrolidone. The sulfur-containing polymer of the present invention synthesized by the above method usually does not need to be purified, but when a high-purity sulfur-containing polymer is required, the reaction product is dissolved in the above organic solvent, filtered, and then filtered. Sulfur insoluble in organic solvents is removed. In addition, the filtered solution is subjected to molecular sieving such as gel filtration chromatography to separate the polymer and the monomer.
本発明の含硫黄ポリマーに対する硫黄含有量は、好ましくは５０〜９５質量％であり、より好ましくは５５〜９５質量％であり、更に好ましくは６０〜９５質量％である。
本発明の含硫黄ポリマーの数平均分子量（Ｍｎ）は、好ましくは１０００〜２００００、更に好ましくは２０００〜１５０００、最も好ましくは５０００〜１００００である。また、本発明の含硫黄ポリマーの数平均分子量（Ｍｎ）は、ＧＰＣによって測定され得る。
The sulfur content with respect to the sulfur-containing polymer of the present invention is preferably 50 to 95% by mass, more preferably 55 to 95% by mass, and further preferably 60 to 95% by mass.
The number average molecular weight (Mn) of the sulfur-containing polymer of the present invention is preferably 1000 to 20000, more preferably 2000 to 15000, and most preferably 5000 to 10000. In addition, the number average molecular weight (Mn) of the sulfur-containing polymer of the present invention can be measured by GPC.
本発明の含硫黄ポリマーにおける、分子状硫黄（Ｓ８）と上記式（２）で表される化合物とのモル比は、好ましくは１：０．０１〜１：１００であり、より好ましくは、１：０．２５〜１：１０であり、更に好ましくは１：０．２５〜１：５である。 In the sulfur-containing polymer of the present invention, the molar ratio of molecular sulfur (S 8 ) to the compound represented by the above formula (2) is preferably 1: 0.01 to 1: 100, and more preferably. It is 1: 0.25 to 1:10, more preferably 1: 0.25 to 1: 5.
本発明の含硫黄ポリマーは、建築、自動車産業等のエラストマー、ゴム材料として利用され得る。 The sulfur-containing polymer of the present invention can be used as an elastomer or rubber material for the construction and automobile industries.
更に、本発明の含硫黄ポリマーは上記有機溶媒に溶解され、含硫黄ポリマーの有機溶媒溶液が導電助剤に含浸された後、シランカップリング処理が有機酸の存在下で行われ、含硫黄ポリマーが導電助剤表面に固定された複合材料が得られる。当該複合材料がバインダーと混練され、二次電池用正極に成形される。 Further, the sulfur-containing polymer of the present invention is dissolved in the above organic solvent, and after the organic solvent solution of the sulfur-containing polymer is impregnated with the conductive auxiliary agent, a silane coupling treatment is performed in the presence of an organic acid, and the sulfur-containing polymer is used. A composite material is obtained in which the solvent is fixed to the surface of the conductive additive. The composite material is kneaded with a binder and formed into a positive electrode for a secondary battery.
導電助剤として、具体的には、気相法炭素繊維（Vapor Grown Carbon Fiber：ＶＧＣＦ）、カーボンブラック（ＣＢ）、キャパシタ用活性炭、カーボンナノチューブ、グラフェン、フラーレン、黒鉛等の炭素粉末；アルミニウム、チタン等の正極電位において安定な金属の微粉末等が挙げられる。好ましいカーボンブラックは、アセチレンブラック（ＡＢ、デンカ株式会社製）、ケッチェンブラック（ＫＢ、ライオン株式会社）、クノーベル（東洋炭素株式会社製）である。 Specific examples of the conductive auxiliary agent include carbon powders such as Vapor Grown Carbon Fiber (VGCF), carbon black (CB), activated carbon for capacitors, carbon nanotubes, graphene, fullerenes, and graphite; aluminum and titanium. Examples thereof include fine powders of metals that are stable at positive potentials such as. Preferred carbon blacks are acetylene black (AB, manufactured by Denka Co., Ltd.), Ketjen black (KB, manufactured by Lion Corporation), and Knobel (manufactured by Toyo Tanso Co., Ltd.).
本発明の二次電池用正極が含有する本発明の含硫黄ポリマーと導電助剤の配合割合は、本発明の含硫黄ポリマー：導電助剤（質量比）として好ましくは１〜２０：１であり、より好ましくは５〜１０：１である。 The blending ratio of the sulfur-containing polymer of the present invention and the conductive auxiliary agent contained in the positive electrode for the secondary battery of the present invention is preferably 1 to 20: 1 as the sulfur-containing polymer: conductive auxiliary agent (mass ratio) of the present invention. , More preferably 5 to 10: 1.
上記シランカップリング処理で使用される有機酸として、具体的には、トリフルオロ酢酸、トリフルオロメタンスルホン酸等が挙げられる。 Specific examples of the organic acid used in the silane coupling treatment include trifluoroacetic acid and trifluoromethanesulfonic acid.
上記バインダーの具体例として、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレン−ブタジエンゴム（ＳＢＲ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、カルボキシメチルセルロース（ＣＭＣ）、ポリ塩化ビニル（ＰＶＣ）、メタクリル樹脂（ＰＭＡ）、ポリアクリロニトリル（ＰＡＮ）、変性ポリフェニレンオキシド（ＰＰＯ）、ポリエチレンオキシド（ＰＥＯ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、アルギン酸（Ａｌｇ）等が挙げられる。 Specific examples of the above binder include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyimide (PI), polyamideimide (PAI), carboxymethyl cellulose (CMC), and polyvinyl chloride. (PVC), methacrylic resin (PMA), polyacrylonitrile (PAN), modified polyvinylidene oxide (PPO), polyethylene oxide (PEO), polyethylene (PE), polypropylene (PP), alginic acid (Alg) and the like.
本発明の二次電池用正極を備える本発明の二次電池の負極の好ましい材料は、リチウム、マグネシウム、アルミニウム、ナトリウム、シリコン及び人造黒鉛などの炭素材料から選ばれるいずれか一つであり、より好ましい当該材料はリチウムである。 The preferred material for the negative electrode of the secondary battery of the present invention provided with the positive electrode for the secondary battery of the present invention is any one selected from carbon materials such as lithium, magnesium, aluminum, sodium, silicon and artificial graphite, and more. The preferred material is lithium.
本発明の二次電池の集電体は、二次電池用正極で一般に用いられる集電体である。本発明の二次電池の集電体として、具体的には、ステンレス箔、ステンレスメッシュ、アルミニウム箔、アルミニウムメッシュ、パンチングアルミニウムシート、アルミニウムエキスパンドシート、ステンレススチール箔、ステンレススチールメッシュ、パンチングステンレススチールシート、ステンレススチールエキスパンドシート、発泡ニッケル、ニッケル不織布、銅箔、銅メッシュ、パンチング銅シート、銅エキスパンドシート、チタン箔、チタンメッシュ、カーボン不織布、カーボン織布等が挙げられる。好ましい集電体はステンレスメッシュである。 The current collector of the secondary battery of the present invention is a current collector generally used in a positive electrode for a secondary battery. Specific examples of the current collector of the secondary battery of the present invention include stainless foil, stainless mesh, aluminum foil, aluminum mesh, punching aluminum sheet, aluminum expanding sheet, stainless steel foil, stainless steel mesh, and punching stainless steel sheet. Examples thereof include stainless steel expanding sheet, expanded nickel foam, nickel non-woven fabric, copper foil, copper mesh, punching copper sheet, copper expanding sheet, titanium foil, titanium mesh, carbon non-woven fabric, and carbon woven fabric. A preferred current collector is a stainless mesh.
本発明の二次電池の電解液は、二次電池で一般に用いられる電解液である。本発明の二次電池の電解液の溶媒の具体的は、１，２−ジメトキシエタン、アセトニトリル、プロピレンカーボネート、エチレンカーボネート、３−メトキシプロピオニトリル、メトキシアセトニトリル、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチルロラクトン、ジメトキシエタン、ジメチルカーボネート、１，３−ジオキソラン、メチルホルメート、２−メチルテトラハイドロフラン、３−メトキシ−オキサゾリデン−２−オン、スルホラン、テトラハイドロフラン、トリエチレングリコールジメチルエーテ、水等である。これらは単独で又は２種以上混合されて使用される。好ましい溶媒は１，２−ジメトキシエタンと１，３−ジオキソランが１：１（体積比）で混合されている混合物である。 The electrolytic solution of the secondary battery of the present invention is an electrolytic solution generally used in a secondary battery. Specific examples of the solvent for the electrolytic solution of the secondary battery of the present invention include 1,2-dimethoxyethane, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, and tri. Ethylene glycol, butyllolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazoliden-2-one, sulfolane, tetrahydrofuran, triethylene glycol dimethyl Ethylene, water, etc. These are used alone or in admixture of two or more. A preferred solvent is a mixture of 1,2-dimethoxyethane and 1,3-dioxolane in a 1: 1 (volume ratio) mixture.
本発明の二次電池の電解液の溶媒はイオン液体であってもよい。イオン液体は、有機カチオンとアニオンとを組み合わせたイオンからなる液体である。有機カチオンの具体例は、ジアルキルイミダゾリウムカチオン、トリアルキルイミダゾリウムカチオン等のイミダゾリウムイオン、テトラアルキルアンモニウムイオン、アルキルピリジニウムイオン、ジアルキルピロリジニウムイオン、ジアルキルピペリジニウムイオン等である。 The solvent of the electrolytic solution of the secondary battery of the present invention may be an ionic liquid. An ionic liquid is a liquid composed of ions in which an organic cation and an anion are combined. Specific examples of the organic cations include imidazolium ions such as dialkylimidazolium cations and trialkylimidazolium cations, tetraalkylammonium ions, alkylpyridinium ions, dialkylpyrrolidinium ions, and dialkylpiperidinium ions.
これらの有機カチオンのカウンターイオンとなるアニオンの具体例は、ＰＦ6アニオン、ＰＦ3（Ｃ2Ｆ5）3アニオン、ＰＦ3（ＣＦ3）3アニオン、ＢＦ4アニオン、ＢＦ2（ＣＦ3）2アニオン、ＢＦ3（ＣＦ3）アニオン、ビスオキサレートホウ酸アニオン、Ｔｆ（トリフルオロメタンスルホニル）アニオン、Ｎｆ（ノナフルオロブタンスルホニル）アニオン、ビス（フルオロスルホニル）イミドアニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、ビス（ペンタフルオロエタンスルホニル）イミドアニオン、ジシアノアミンアニオン等である。 Specific examples of anions that serve as counter ions for these organic cations are PF 6 anion, PF 3 (C 2 F 5 ) 3 anion, PF 3 (CF 3 ) 3 anion, BF 4 anion, and BF 2 (CF 3 ) 2. Anion, BF 3 (CF 3 ) anion, bisoxalate borate anion, Tf (trifluoromethanesulfonyl) anion, Nf (nonaflatebutanesulfonyl) anion, bis (fluorosulfonyl) imide anion, bis (trifluoromethanesulfonyl) imide anion , Bis (pentafluoroethanesulfonyl) imide anion, dicyanoamine anion and the like.
本発明の二次電池の電解液の電解質の具体例は、ＮａＰＦ６、ＮａＢＦ４、ＮａＣｌＯ４、ＮａＣＦ３ＣＯＮＳＯ２ＣＦ３、ＮａＮ（ＳＯ２Ｃ２Ｆ５）２、ＮａＮ（ＳＯ２ＣＦ３）２、ＮａＣＦ３ＳＯ３、ＮａＣ（ＣＦ３ＳＯ２）３等のナトリウム塩；ＬｉＣｌ、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＢ（Ｃ６Ｈ５）４、ＬｉＣＨ３ＳＯ３、ＬｉＣＦ３ＳＯ３、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＢｒ等のリチウム塩；Ｍｇ（ＣｌＯ４）２、Ｍｇ（ＣＦ３ＳＯ３）２等のマグネシウム塩；オルトリン酸、ピロリン酸、次亜リン酸、次二リン酸、亜リン酸、二亜リン酸、ピロ亜リン酸、イソ次リン酸、次リン酸等のリン酸化合物のアルミニウム塩等である。 Specific examples of the electrolyte of the electrolyte of the secondary battery of the present invention are NaPF 6 , NaBF 4 , NaClO 4 , NaCF 3 CONSO 2 CF 3 , NaN (SO 2 C 2 F 5 ) 2 , NaN (SO 2 CF 3 ). 2 , NaCF 3 SO 3 , NaC (CF 3 SO 2 ) 3 and other sodium salts; LiCl, LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiB (C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 Lithium salts such as SO 3 , Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 2 N, LiC (CF 3 SO 2 ) 3 , LiBr, etc .; Mg (ClO 4 ) 2 , Mg (CF) 3 SO 3 ) 2nd grade magnesium salts; orthophosphoric acid, pyrophosphoric acid, hypophosphoric acid, hypophosphoric acid, phosphorous acid, diphosphoric acid, pyrophosphoric acid, isophosphoric acid, hypophosphoric acid, etc. An aluminum salt of a phosphoric acid compound or the like.
本発明の二次電池の形状は制限されない。本発明の二次電池は、コイン形、ボタン形、シート形、積層形、円筒形、偏平形、角形、電気自動車等に用いる大型二次電池であり得る。 The shape of the secondary battery of the present invention is not limited. The secondary battery of the present invention can be a large secondary battery used for coin type, button type, sheet type, laminated type, cylindrical type, flat type, square type, electric vehicle and the like.
以下に、実施例により本発明をより詳細に説明するが、本発明の技術範囲は、これらに限定されない。合成された含硫黄ポリマーの分析方法は以下のとおりである。 Hereinafter, the present invention will be described in more detail by way of examples, but the technical scope of the present invention is not limited thereto. The method for analyzing the synthesized sulfur-containing polymer is as follows.
（１）１Ｈ ＮＭＲ分析及び１３Ｃ ＮＭＲ分析
試料が溶媒である重水素化クロロホルムに濃度０．１Ｍとなるように溶解され、日本電子（株）製JNM-ECA（１Ｈ ＮＭＲ、１３Ｃ ＮＭＲ）により、内部標準物質としてトリメチルシランを用いて測定された。
(1) 1 H NMR analysis and 13 C NMR analysis The sample was dissolved in deuterated chloroform as a solvent to a concentration of 0.1 M, and JNM-ECA ( 1 H NMR, 13 C NMR) manufactured by JEOL Ltd. ), The measurement was carried out using trimethylsilane as an internal standard substance.
（２）ゲル濾過クロマトグラフィー（ＧＰＣ）分析
Shodex GPC KF-804 L（昭和電工株式会社製）のカラム管が、（株）島津製作所製 Prominence システムに対して取り付けられ、溶離液としてテトラヒドロフラン（ＴＨＦ）が４０℃、１．０ ml/minの速度で流された。検量線はポリスチレン標準により作成された。
(2) Gel filtration chromatography (GPC) analysis
A column tube of Shodex GPC KF-804 L (manufactured by Showa Denko KK) was attached to the Prominence system manufactured by Shimadzu Corporation, and tetrahydrofuran (THF) was used as an eluent at 40 ° C. and 1.0 ml / min. It was swept away at speed. The calibration curve was prepared according to the polystyrene standard.
（３）示差走査熱量（ＤＳＣ）分析
（株）日立ハイテクノロジーズ製DSC7020が使用され、試料が昇温速度１０℃／ｍｉｎで加熱され、分析された。
(3) Differential Scanning Calorimetry (DSC) Analysis A DSC7020 manufactured by Hitachi High-Technologies Corporation was used, and the sample was heated at a heating rate of 10 ° C./min and analyzed.
（４）熱重量測定
（株）島津製作所製Thermo Plus Evo IIが使用され、試料が昇温速度１０℃／ｍｉｎで加熱され、分析された。
(4) Thermogravimetric analysis Thermo Plus Evo II manufactured by Shimadzu Corporation was used, and the sample was heated at a heating rate of 10 ° C./min and analyzed.
含硫黄ポリマー製造例１
分子状硫黄（Ｓ８）（キシダ化学（株）製）１質量部とシリルエーテル骨格を有するアルケニル化合物であるトリメトキシ（４-ビニルフェニル）シラン（ＶｐｈＳｉ）（東京化成工業株式会社（株）製）０．２１９質量部（分子状硫黄とシリルエーテル骨格を有するアルケニル化合物のモル比＝４：１）がサンプル瓶に加えられ、１６０℃で１時間、次いで１７０℃で２．５時間攪拌された。その後、反応生成物が室温になるまで放置され、固化されたポリマー［Ｓ−ＶｐｈＳｉ（０．２５）］が回収された。ＶｐｈＳｉ、Ｓ−ＶｐｈＳｉ（０．２５）及び分子状硫黄（Ｓ８）が試料とされ、１Ｈ ＮＭＲ分析、１３Ｃ ＮＭＲ分析、ＧＰＣ分析、ＤＳＣ分析及び熱重量測定が行われた。１Ｈ ＮＭＲスペクトル、１３Ｃ ＮＭＲスペクトルが、それぞれ、図１、図２に示されている。ＧＰＣチャート、ＤＳＣチャートがそれぞれ、図３、図４に示されている。熱重量測定の結果が図５及び図６に示されている。
Sulfur-containing polymer production example 1
Molecular sulfur (S 8 ) (manufactured by Kishida Chemical Co., Ltd.) Trimethoxy (4-vinylphenyl) silane (VphSi), which is an alkenyl compound having 1 part by mass and a silyl ether skeleton (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.219 parts by mass (molar ratio of alkenyl compound having molecular sulfur and silyl ether skeleton = 4: 1) was added to the sample bottle and stirred at 160 ° C. for 1 hour and then at 170 ° C. for 2.5 hours. Then, the reaction product was allowed to stand until it reached room temperature, and the solidified polymer [S-VphSi (0.25)] was recovered. VphSi, is the S-VphSi (0.25) and molecular sulfur (S 8) is a sample, 1 H NMR analysis, 13 C NMR analysis, GPC analysis and DSC analysis and thermogravimetry were made. The 1 H NMR spectrum and the 13 C NMR spectrum are shown in FIGS. 1 and 2, respectively. The GPC chart and the DSC chart are shown in FIGS. 3 and 4, respectively. The results of thermogravimetric analysis are shown in FIGS. 5 and 6.
図１及び図２より、ＶｐｈＳｉの二重結合に由来するピーク（図１及び図２の上段に示されるスペクトルのａ及びｂ）が、Ｓ−ＶｐｈＳｉ（０．２５）のスペクトルから消失していることが分かる。よって、Ｓ−ＶｐｈＳｉ（０．２５）は、上記式（１）のＲ１がメトキシ基、Ｒ２がベンゼン環、Ｒ３が水素、ｎ＝１である含硫黄ポリマーであることが分かる。Ｓ−ＶｐｈＳｉ（０．２５）の分子量分布が図３のＧＰＣチャートに示されている。図４より、１００℃過ぎの斜方硫黄から単斜硫黄の遷移に由来する温度において２℃の差異が観察され、このことより有機硫黄にすることで結晶構造に変化が表れていることが分かる。図５より、Ｓ−ＶｐｈＳｉ（０．２５）の質量が、分子状硫黄の質量と同様、２００〜３００℃において大幅に減少したことが分かる。よって、Ｓ−ＶｐｈＳｉ（０．２５）の主鎖中に−Ｓｘ−で示される繰り返し単位（繰り返し単位毎にＸの数は異なっていてよい）が存在することが分かる。Ｓ−ＶｐｈＳｉ（０．２５）の硫黄の含有量は約８９質量％と見積もられた。また、ＤＴＡ曲線において、硫黄の融点である吸熱ピークが１１５℃付近に観察されており、ＤＳＣ測定のデータと相関がみられる。 From FIGS. 1 and 2, the peaks (a and b of the spectra shown in the upper part of FIGS. 1 and 2) derived from the double bond of VphSi disappear from the spectrum of S-VphSi (0.25). You can see that. Therefore, it can be seen that S-VphSi (0.25) is a sulfur-containing polymer in which R 1 of the above formula (1) is a methoxy group, R 2 is a benzene ring, R 3 is hydrogen, and n = 1. The molecular weight distribution of S-VphSi (0.25) is shown in the GPC chart of FIG. From FIG. 4, a difference of 2 ° C is observed in the temperature derived from the transition from orthorhombic sulfur to monoclinic sulfur after 100 ° C, and it can be seen from this that the crystal structure is changed by using organic sulfur. .. From FIG. 5, it can be seen that the mass of S-VphSi (0.25) was significantly reduced at 200 to 300 ° C., similar to the mass of molecular sulfur. Therefore, it can be seen that the repeating unit represented by -Sx- (the number of X may be different for each repeating unit) exists in the main chain of S-VphSi (0.25). The sulfur content of S-VphSi (0.25) was estimated to be about 89% by weight. Further, in the DTA curve, an endothermic peak, which is the melting point of sulfur, is observed around 115 ° C., which is correlated with the data of DSC measurement.
二次電池製造例１
含硫黄ポリマー製造例１で製造されたＳ−ＶｐｈＳｉ（０．２５）０．０８質量部が、４．０質量部のテトラヒドロフランに溶解された。次いで、得られた４．０８質量部の溶液が、０．０４質量部のカーボンブラック（東洋炭素（株）製クーベル）に含浸された。その後、当該Ｓ−ＶｐｈＳｉ（０．２５）で処理されたカーボンブラックが、約１３ｍｏｌ／ｌのトリフルオロ酢酸水溶液に含浸され、シランカップリング処理が行われた。得られた０．０９質量部の硫黄−カーボン複合材料及び０．０１質量部のＰＴＦＥ（（株）ダイキン製ポリフロンＰＴＦＥファインパウダー）が混練され、正極が成形された。リチウムビス（トリフルオロメタンスルホニル）アミド（ＬｉＴＦＳＡ）が１、２−ジメトキシエタン（ＤＭＥ）と１、３−ジオキソラン（ＤＯＸ）が体積比１：１で混合されている溶媒に溶解されている電解液（濃度１Ｍ）と当該正極が使用される、図６に示されるようなコインセル型二次電池が作製された。当該コインセル型二次電池の定電流充放電試験が、電気化学測定システム（北斗電工（株）製ＨＪ１００１ＳＤ８）が使用され、測定環境２５℃においてＣレートが０．１Ｃ（１６７．５ｍＡｇ−１）として行われた。結果が図７に示されている。
Secondary battery manufacturing example 1
0.08 parts by mass of S-VphSi (0.25) produced in Production Example 1 of the sulfur-containing polymer was dissolved in 4.0 parts by mass of tetrahydrofuran. Next, the obtained 4.08 parts by mass of the solution was impregnated with 0.04 parts by mass of carbon black (Coubel manufactured by Toyo Tanso Co., Ltd.). Then, the carbon black treated with the S-VphSi (0.25) was impregnated with a trifluoroacetic acid aqueous solution of about 13 mol / l, and a silane coupling treatment was performed. The obtained 0.09 parts by mass of sulfur-carbon composite material and 0.01 parts by mass of PTFE (Polyflon PTFE fine powder manufactured by Daikin Corporation) were kneaded to form a positive electrode. An electrolytic solution in which lithium bis (trifluoromethanesulfonyl) amide (LiTFSA) is dissolved in a solvent in which 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOX) are mixed in a volume ratio of 1: 1. A coin cell type secondary battery as shown in FIG. 6 was produced in which the positive electrode having a concentration of 1 M) was used. In the constant current charge / discharge test of the coin cell type secondary battery, an electrochemical measurement system (HJ1001SD8 manufactured by Hokuto Denko Co., Ltd.) was used, and the C rate was 0.1 C (167.5 mAg -1 ) in a measurement environment of 25 ° C. It was conducted. The results are shown in FIG.
比較例１
Ｓ−ＶｐｈＳｉ（０．２５）で処理されたカーボンブラックがトルフルオロ酢酸水溶液に含浸されず、シランカップリング処理が行われなかった以外は、実施例１と同様の操作が行われ、コインセル型二次電池が作製されて、定電流充放電試験が行われた。結果が図７に示されている。
Comparative Example 1
The same operation as in Example 1 was performed except that the carbon black treated with S-VphSi (0.25) was not impregnated with the tolfluoroacetic acid aqueous solution and the silane coupling treatment was not performed, and the coin cell type secondary was performed. A battery was manufactured and a constant current charge / discharge test was performed. The results are shown in FIG.
シランカップリング処理が行われていない硫黄−カーボン複合材料を含有する正極を備える二次電池の容量は、硫黄成分の電解液への溶出により低下し、溶出した硫黄成分が充電側で反応して、当該二次電池が過充電された。 The capacity of the secondary battery including the positive electrode containing the sulfur-carbon composite material that has not been subjected to the silane coupling treatment is reduced by the elution of the sulfur component into the electrolytic solution, and the eluted sulfur component reacts on the charging side. , The secondary battery was overcharged.
一方、シランカップリング処理が行われている硫黄−カーボン複合材料を含有する正極を備える二次電池は、初期サイクルにおいて高い放電容量を示し、サイクルの進行による放電容量の低下も小さかった。更に、当該二次電池の過充電は抑制されていた。これらの効果は、シランカップリング処理による硫黄成分のカーボンブラックへの固定により得られたと推認される。 On the other hand, the secondary battery provided with the positive electrode containing the sulfur-carbon composite material subjected to the silane coupling treatment showed a high discharge capacity in the initial cycle, and the decrease in the discharge capacity due to the progress of the cycle was small. Further, overcharging of the secondary battery was suppressed. It is presumed that these effects were obtained by fixing the sulfur component to carbon black by the silane coupling treatment.
含硫黄ポリマー製造例２
ＶｐｈＳｉ０．２１９質量部に代えて、アリルクロロジメチルシラン（東京化成工業株式会社（株）製）０．２６３質量部（分子状硫黄とアリルクロロジメチルシランのモル比＝２：１）を使用する以外、含硫黄ポリマー製造例１と同様にして固化されたポリマーが回収された。回収されたポリマーの１Ｈ ＮＭＲ分析が行われ、１Ｈ ＮＭＲスペクトルが図８に示されている。
Sulfur-containing polymer production example 2
Except for using 0.263 parts by mass of allylchlorodimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio of molecular sulfur to allylchlorodimethylsilane = 2: 1) instead of 0.219 parts by mass of VphSi. , The polymer solidified in the same manner as in Production Example 1 of the sulfur-containing polymer was recovered. A 1 H NMR analysis of the recovered polymer was performed and a 1 H NMR spectrum is shown in FIG.
含硫黄ポリマー製造例３
ＶｐｈＳｉ０．２１９質量部に代えて、アリルトリメトキシシラン（東京化成工業株式会社（株）製）０．３１７質量部（分子状硫黄とアリルクロロジメチルシランのモル比＝２：１）を使用する以外、含硫黄ポリマー製造例１と同様にして固化されたポリマーが回収された。回収されたポリマーの１Ｈ ＮＭＲ分析が行われ、１Ｈ ＮＭＲスペクトルが図９に示されている。
Sulfur-containing polymer production example 3
Except for using 0.317 parts by mass of allyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio of molecular sulfur to allylchlorodimethylsilane = 2: 1) instead of 0.219 parts by mass of VphSi. , The polymer solidified in the same manner as in Production Example 1 of the sulfur-containing polymer was recovered. A 1 H NMR analysis of the recovered polymer was performed and a 1 H NMR spectrum is shown in FIG.
含硫黄ポリマー製造例４
ＶｐｈＳｉ０．２１９質量部に代えて、トリメトキシ（７−オクテン−１−イル）シラン（東京化成工業株式会社（株）製）０．４５４質量部（分子状硫黄とアリルクロロジメチルシランのモル比＝２：１）を使用する以外、含硫黄ポリマー製造例１と同様にして固化されたポリマーが回収された。回収されたポリマーの１Ｈ ＮＭＲ分析が行われ、１Ｈ ＮＭＲスペクトルが図１０に示されている。
Sulfur-containing polymer production example 4
Instead of 0.219 parts by mass of VphSi, 0.454 parts by mass of trimethoxy (7-octen-1-yl) silane (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio of molecular sulfur to allylchlorodimethylsilane = 2) A polymer solidified in the same manner as in Production Example 1 of a sulfur-containing polymer was recovered except that 1) was used. A 1 H NMR analysis of the recovered polymer was performed and a 1 H NMR spectrum is shown in FIG.
含硫黄ポリマー製造例５
ＶｐｈＳｉ０．２１９質量部に代えて、アクリル酸３−（トリメトキシシリル）プロピル（東京化成工業株式会社（株）製）０．４５８質量部（分子状硫黄とアリルクロロジメチルシランのモル比＝２：１）を使用する以外、含硫黄ポリマー製造例１と同様にして固化されたポリマーが回収された。回収されたポリマーの１Ｈ ＮＭＲ分析が行われ、１Ｈ ＮＭＲスペクトルが図１１に示されている。
Sulfur-containing polymer production example 5
Instead of 0.219 parts by mass of VphSi, 0.458 parts by mass of 3- (trimethoxysilyl) propyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio of molecular sulfur to allylchlorodimethylsilane = 2: A polymer solidified in the same manner as in Production Example 1 of a sulfur-containing polymer was recovered except that 1) was used. A 1 H NMR analysis of the recovered polymer was performed and a 1 H NMR spectrum is shown in FIG.
含硫黄ポリマー製造例６
ＶｐｈＳｉ０．２１９質量部に代えて、メタクリル酸３−（トリメトキシシリル）プロピル（東京化成工業株式会社（株）製）０．４８５質量部（分子状硫黄とアリルクロロジメチルシランのモル比＝２：１）を使用する以外、含硫黄ポリマー製造例１と同様にして固化されたポリマーが回収された。回収されたポリマーの１Ｈ ＮＭＲ分析が行われ、１Ｈ ＮＭＲスペクトルが図１２に示されている。
Sulfur-containing polymer production example 6
Instead of 0.219 parts by mass of VphSi, 0.485 parts by mass of 3- (trimethoxysilyl) propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio of molecular sulfur to allylchlorodimethylsilane = 2: A polymer solidified in the same manner as in Production Example 1 of a sulfur-containing polymer was recovered except that 1) was used. A 1 H NMR analysis of the recovered polymer was performed and a 1 H NMR spectrum is shown in FIG.
図８〜図１２より、含硫黄ポリマー製造例２〜６で使用されたアルケニル化合物の二重結合に由来するピーク（図８〜図１２に示されるスペクトルのａ及びｂ）が、回収された各ポリマーのスペクトルから消失していることが分かる。よって、含硫黄ポリマー製造例２で回収されたポリマーは、上記式（１）のＲ１が２つのメチル基と１つのＣｌ、Ｒ２がメチレン基、Ｒ３が水素、ｎ＝１である含硫黄ポリマーであること、含硫黄ポリマー製造例３で回収されたポリマーは、上記式（１）のＲ１がメトキシ基、Ｒ２がメチレン基、Ｒ３が水素、ｎ＝１である含硫黄ポリマーであること、含硫黄ポリマー製造例４で回収されたポリマーは、上記式（１）のＲ１がメトキシ基、Ｒ２がｎ−ヘキシレン基、Ｒ３が水素、ｎ＝１である含硫黄ポリマーであること、含硫黄ポリマー製造例５で回収されたポリマーは、上記式（１）のＲ１がメトキシ基、Ｒ２が−エステル−ｎ−プロピレン基であってｎ−プロピレン基とトリメトキシシラン基が結合しており、Ｒ３が水素、ｎ＝１である含硫黄ポリマーであること、含硫黄ポリマー製造例６で回収されたポリマーは、上記式（１）のＲ１がメトキシ基、Ｒ２が−エステル−ｎ−プロピレン基であってｎ−プロピレン基とトリメトキシシラン基が結合しており、Ｒ３がメチル基、ｎ＝１である含硫黄ポリマーであることが分かる。 From FIGS. 8 to 12, the peaks (a and b in the spectra shown in FIGS. 8 to 12) derived from the double bond of the alkenyl compound used in the sulfur-containing polymer production examples 2 to 6 were recovered. It can be seen that it disappears from the spectrum of the polymer. Therefore, the recovered polymer with a sulfur-containing polymer Preparation Example 2 is R 1 is two methyl groups and one Cl, R 2 is a methylene group, R 3 is hydrogen, n = 1 in the above formula (1) including Being a sulfur polymer, the polymer recovered in Production Example 3 of a sulfur-containing polymer has a sulfur-containing polymer of the above formula (1) in which R 1 is a methoxy group, R 2 is a methyl group, R 3 is hydrogen, and n = 1. The polymer recovered in Production Example 4 of the sulfur-containing polymer is a sulfur-containing polymer having R 1 of the above formula (1) having a methoxy group, R 2 having an n-hexylene group, and R 3 having hydrogen and n = 1. In the polymer recovered in Production Example 5 of a sulfur-containing polymer, R 1 of the above formula (1) is a methoxy group and R 2 is a -ester-n-propylene group, which is an n-propylene group and a trimethoxysilane. The polymer to which the group is bonded and R 3 is hydrogen and n = 1 is a sulfur-containing polymer, and the polymer recovered in Production Example 6 of the sulfur-containing polymer has R 1 of the above formula (1) having a methoxy group and R. It can be seen that 2 is a -ester-n-propylene group, the n-propylene group and the trimethoxysilane group are bonded, and R 3 is a methyl group and n = 1 is a sulfur-containing polymer.
本発明の含硫黄ポリマーは、電池材料、特に二次電池の正極材料として利用可能である。 The sulfur-containing polymer of the present invention can be used as a battery material, particularly as a positive electrode material for a secondary battery.
Claims (6)
含硫黄ポリマーに対する硫黄含有量が６０〜９５質量％である含硫黄ポリマー。 The following formula ( 1' )
A sulfur-containing polymer having a sulfur content of 60 to 95% by mass with respect to the sulfur-containing polymer.
Ｈ２Ｃ＝ＣＲ３（Ｒ２）ｎ−Ｓｉ（Ｒ１）３ （２）
（式中、Ｒ１ は直鎖又は分岐の炭素数１〜２０のアルキル基、主鎖中に−Ｏ−を１以上有する直鎖又は分岐の炭素数１〜２０のアルコキシ基及び−Ｃｌからなる群より選ばれるいずれかの基を表す。各Ｒ１は、同一であっても異なっていてもよい。Ｒ２ は芳香族基、直鎖又は分岐の炭素数１〜２０のアルキレン基、−ＣＯＯ−を有する直鎖又は分岐の炭素数１〜２０のアルキレン基及び−ＣＯＯ−からなる群より選ばれるいずれか１つを表す。Ｒ３ は直鎖又は分岐の炭素数１〜２０のアルキル基若しくは−Ｈを表す。ｎは０又は１である。）で表される骨格を有するアルケニル化合物と分子状硫黄（Ｓ８）を反応させる、請求項４に記載の含硫黄ポリマーの製造方法。
The following formula (2)
H 2 C = CR 3 (R 2 ) n −Si (R 1 ) 3 (2)
(Wherein, R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, that Yusuke -O- one or more in the main chain straight-chain or branched alkoxy group, and -Cl having 1 to 20 carbon atoms represents any one group selected from the group consisting of. each R 1 are identical a good .R 2 be different even if the fang Kozokumoto, linear or branched alkylene group having 1 to 20 carbon atoms , -COO- a selected from linear or branched alkylene group having 1 to 20 carbon atoms and the group consisting of -COO- that Yusuke represents any one .R 3 is 1 to the number of carbon atoms of straight-chain or branched The sulfur-containing polymer according to claim 4 , which comprises reacting an alkoxy compound having a skeleton represented by (n is 0 or 1) with an alkyl group of 20 or —H with molecular sulfur (S 8). Production method.
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