CN110144045B - A kind of sulfone-containing polysiloxane fiber and preparation method thereof - Google Patents
A kind of sulfone-containing polysiloxane fiber and preparation method thereof Download PDFInfo
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- CN110144045B CN110144045B CN201910408768.5A CN201910408768A CN110144045B CN 110144045 B CN110144045 B CN 110144045B CN 201910408768 A CN201910408768 A CN 201910408768A CN 110144045 B CN110144045 B CN 110144045B
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- Prior art keywords
- sulfone
- containing polysiloxane
- acid
- polysiloxane
- siloxane
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- -1 polysiloxane Polymers 0.000 title claims abstract description 105
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 85
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 title abstract description 34
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 20
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229920002994 synthetic fiber Polymers 0.000 claims description 13
- 239000012209 synthetic fiber Substances 0.000 claims description 13
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 150000007529 inorganic bases Chemical group 0.000 claims description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007818 Grignard reagent Substances 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 125000001174 sulfone group Chemical group 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000010041 electrostatic spinning Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical group C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- IZLKCUUFOKTMFD-UHFFFAOYSA-N 3-(2-hydroxy-2-phenylacetyl)phthalic acid Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC(C(O)=O)=C1C(O)=O IZLKCUUFOKTMFD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101150096408 P2OX gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- UNQHMFJVBBWADE-UHFFFAOYSA-N butane-1,1-dithiol Chemical compound CCCC(S)S UNQHMFJVBBWADE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
本发明涉及一种含砜聚硅氧烷纤维及其制备方法。本发明的含砜聚硅氧烷纤维，以大环含砜硅氧烷作为原料，在碱或酸催化下，开环聚合得到含砜聚硅氧烷，这一含砜聚硅氧烷可用简单的纺丝工艺进行纺丝，制备出可纺性好，性能优良的聚硅氧烷纤维。本发明的合成方法简单，砜基的引入加大了聚硅氧烷的结晶性与刚性，所制备的聚硅氧烷纤维可以在特定条件下以高产量循环回原来的大环单体，绿色环保。The invention relates to a sulfone-containing polysiloxane fiber and a preparation method thereof. The sulfone-containing polysiloxane fiber of the present invention uses macrocyclic sulfone-containing siloxane as a raw material, and is catalyzed by alkali or acid to undergo ring-opening polymerization to obtain sulfone-containing polysiloxane. The sulfone-containing polysiloxane can be obtained by simple The polysiloxane fiber with good spinnability and excellent performance is prepared by the spinning process. The synthesis method of the invention is simple, the introduction of the sulfone group increases the crystallinity and rigidity of the polysiloxane, the prepared polysiloxane fiber can be recycled back to the original macrocyclic monomer with high yield under specific conditions, and the green Environmental friendly.
Description
Technical Field
The invention relates to the field of synthetic fibers, in particular to a sulfone-containing polysiloxane fiber and a preparation method thereof.
Background
The synthetic fiber is prepared by polymerizing organic synthetic monomers to obtain corresponding polymers and then spinning. At present, the development of synthetic fibers is very rapid, wherein the common synthetic fibers are mainly divided into three categories, namely polyamide fibers (nylon), polyester fibers (terylene) and polyacrylonitrile fibers (acrylon). Synthetic fibers are strong, abrasion resistant, and elastic, but have the common disadvantage of poor moisture absorption and heat resistance, and are petroleum-based products. At present, petroleum resources are limited, and the existing fibers cannot be effectively recycled, so that high requirements are put on the supply of monomers.
Unlike the above polymers, polysiloxanes are elementary organic polymers consisting of alternating silicon and oxygen atoms in the main chain, the silicon atoms containing an organic group (R). Because of the performances of high and low temperature resistance, aging resistance, weather resistance, physiological inertia, good air permeability and the like, the composite material plays an irreplaceable role in the fields of aerospace, chemical engineering, electronics and electricity and the like. Through the development of eighty years, the polysiloxane mainly comprises four major varieties of silicone oil, silicone rubber, silicone resin and a silane coupling agent. However, synthetic fibers are commonly used, but silicone products are rare. This is due to the very soft, ultra-low siloxane rotational barrier (0.8kJ mol) of the polysiloxane backbone-1) And has a large free volume, thereby causing a problem that the polysiloxane is not easily spun.
There are also some patent documents reporting on silicone fibers, for example: chinese patent document CN101838863B discloses a method for preparing polysiloxane fiber, wherein polysiloxane fiber stock solution is formed by polycondensation of polysiloxane terminated by alkoxy or amino alkyl and organic silicon resin, and then by melt spinning and winding. However, the method does not change the main chain structure of polysiloxane, the intermolecular force is small, and the obtained fiber cannot be recycled once being crosslinked. For another example: chinese patent document CN1710162A discloses a process for producing silicone fiber, wherein the polysiloxane fiber stock solution is an addition type silicone system composed of vinyl-terminated polysiloxane, a vulcanization crosslinking agent containing silicon-hydrogen bond, and a platinum-series catalyst. The disadvantage of this system is that when compounds containing sulfur, nitrogen and phosphorus are present, the catalyst is deactivated, which affects the final spinning.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the problem that the polysiloxane is not easy to spin, and simultaneously, the invention solves the problem that the existing polysiloxane fiber cannot be recycled, and provides the sulfone-containing polysiloxane fiber and the preparation method thereof. The invention introduces sulfonyl group with larger polarity into the siloxane chain segment, changes the property of the main chain, prepares novel organic silicon fiber, and solves the problem that the existing siloxane is not easy to spin. The resulting sulfone-containing polysiloxanes are easy to spin and have very good thermal stability and, in particular cases, permit high-yield recycling of the monomers. The synthesis route of the sulfone-containing polysiloxane is simple and efficient, and the prepared sulfone-containing polysiloxane is easy to spin and has excellent temperature resistance and recyclability.
The technical scheme of the invention is as follows:
a sulfone-containing polysiloxane having the following structural formula:
wherein: r1Alkylene, arylene, alkylene ether, biphenylene, or diphenylene sulfide which is a linear or branched structure;
R2is hydrogen, methyl, ethyl, phenyl or trifluoropropyl, R in different positions2The substituents are the same or different;
n is 2 to 10, and m is 10 to 3000.
According to the invention, when R1When the alkyl or alkyl ether is used, the alkyl or alkyl ether is preferably C1-C10; further preferred R1Is butylene, 3, 6-dioxo-1, 8-octyl, 1, 4-xylylene or diphenylene sulfide.
According to the invention, it is preferred that the sulfone-containing polysiloxane has the formula:
R1is butylene, 3, 6-dioxo-1, 8-octyl, 1, 4-xylylene or diphenylene sulfide group;
R2is hydrogen, methyl, ethyl, phenyl or trifluoropropyl, R in different positions2The substituents are the same or different;
n is 3 to 9, and m is 50 to 2500.
According to the present invention, preferably, the polymerization degree m of the sulfone-containing polysiloxane is 100, and the weight average molecular weight is 42000.
According to the invention, the preparation method of the sulfone-containing polysiloxane comprises the following steps:
the preparation method comprises the steps of taking macrocyclic siloxane containing sulfone as a raw material, dissolving the macrocyclic siloxane in an organic solvent, and carrying out ring-opening polymerization reaction under the protection of protective gas and catalysis of a catalyst to obtain the macrocyclic siloxane.
According to the present invention, preferably, said sulfone-containing macrocyclic siloxane has the following structure:
wherein: r1、R2The same meanings as above, and n is 2 to 10.
Further preferably, said sulfone-containing macrocyclic siloxane has the following structure:
according to the present invention, the organic solvent is preferably one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, and 1, 4-dioxane, and is more preferably dimethyl sulfoxide.
According to the present invention, the catalyst is preferably an inorganic base (hydroxides of lithium, sodium, potassium, ammonium, barium, sodium fluoride, etc.); organic bases (alkali metal salts of alcohols (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide), organometallic compounds, such as alkyllithium reagents (e.g., butyllithium, diisopropylaminolithium, hexamethyldisilaaminolithium), grignard reagents (e.g., methylmagnesium iodide), quaternary ammonium hydroxides, lewis bases (e.g., organophosphorus, azacyclo-carbene and azacyclo-carbene, and phosphazene superbases)); inorganic acids (sulfuric acid, hydrochloric acid, nitric acid, boric acid, carbonic acid, phosphoric acid); or organic acids (trifluoromethanesulfonic acid, trifluoroacetic acid, mellitic acid, nitrilotriacetic acid, trichloroacetic acid, trinitrobenzenesulfonic acid or Lewis acids (e.g. Al (C)6F5)3、Zn(C6F5)3、B(C6F5)3) Indium chloride)). Further preferably, the inorganic base is KOH, the organic base is 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, the inorganic acid is sulfuric acid, and the organic acid is trifluoroacetic acid.
According to the present invention, the ring-opening polymerization reaction temperature is preferably 0 to 250 ℃, more preferably 80 to 110 ℃, and most preferably 100 ℃.
According to the present invention, the ring-opening polymerization reaction time is preferably 4 to 48 hours, and more preferably 6 to 12 hours.
According to the present invention, preferably, the protective gas is any one of nitrogen, helium or argon, and further preferably nitrogen.
According to the invention, the molar ratio of the sulfone-containing macrocyclic siloxane to the catalyst is preferably 10-3000: 1, more preferably 50 to 100: 1.
the reaction scheme of the above preparation method of the sulfone-containing polysiloxane according to the present invention is as follows:
according to the invention, the preparation method of the sulfone-containing macrocyclic siloxane comprises the following steps:
mixing a monomer with sulfydryl at two ends, a vinyl siloxane monomer at two ends and a photoinitiator benzoin dimethyl ether (DMPA), wherein the molar ratio of the monomer with sulfydryl at two ends to the monomer with vinyl siloxane at two ends to the photoinitiator is 1: 0.5-1.5: 0.01, preferably 1: 1: 0.001, carrying out step-by-step mercaptoalkene polymerization reaction under ultraviolet light for 5-30 min, preferably 15min to obtain polysiloxane containing thioether; and dissolving the thioether-containing polysiloxane in a solvent, adding tetrahydrofuran as a preferable solvent, adding oxone, reacting at the temperature of 25-100 ℃, preferably 30 ℃ for 10-48h, preferably 24h under the protection of nitrogen, and obtaining the sulfone-containing macrocyclic siloxane as a polymeric monomer of the sulfone-containing polysiloxane.
The reaction route of the preparation method of the sulfone-containing macrocyclic siloxane is as follows:
wherein R is1、R2The same meanings as above, and n is 2 to 10.
According to the invention, the sulfone-containing polysiloxane can be prepared into the sulfone-containing polysiloxane fiber through a spinning process. The selectable spinning processes comprise electrostatic spinning, melt spinning, wet spinning, dry and wet spinning and the like, and electrostatic spinning is preferred;
further preferably, the electrostatic spinning conditions comprise that the spinning temperature is 20-50 ℃, the environmental humidity is 20-40%, the spinning voltage is 10-25 kV, the receiving distance is 15-20 cm, and the spinning speed is 0.05-0.5 mm/min; most preferably, the spinning temperature is 30 ℃, the ambient humidity is 20%, the spinning voltage is 18kV, the receiving distance is 15cm, and the spinning speed is 0.05 mm/min.
According to the invention, the sulfone-containing polysiloxane has good degradation cycle performance.
Further, a method for recycling the degradation of sulfone-containing polysiloxanes to give the initial sulfone-containing macrocyclic siloxane monomer, comprising the steps of:
dissolving sulfone-containing polysiloxane with solvent, preferably tetrahydrofuran, adding KHSO4The reaction temperature is 25-100 ℃, preferably 30 ℃, the reaction time is 10-48h, preferably 24h, and the sulfone-containing macrocyclic siloxane monomer is obtained through degradation.
The above reaction route for recycling of degradation to sulfone-containing macrocyclic siloxane monomers is as follows:
the invention has not been described in detail, but is in accordance with the state of the art.
The invention has the following beneficial effects:
1. according to the invention, sulfone groups with relatively high polarity are introduced into the siloxane chain segment, so that the properties of the main chain of the siloxane chain segment are changed, and further, the crystallinity and intermolecular action of polysiloxane are improved, thus the spinnability of the polymer is improved, novel organic silicon fibers are prepared, and the problem that the existing siloxane is difficult to spin is solved.
2. The sulfone-containing polysiloxane prepared by the invention is easy to spin, has good thermal stability, and is simple and efficient in synthetic route.
3. The sulfone-containing polysiloxane can be degraded and recycled, and the utilization rate of raw materials is greatly improved.
4. The raw materials of the invention are cheap and easy to obtain, the synthetic method has simple route, and the production process has no pollution.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of the macrocyclic sulfone-containing polysiloxane prepared in example 1.
FIG. 2 is a digital photograph of fibers of the sulfone-containing polysiloxane prepared in example 1.
FIG. 3 is a scanning electron micrograph of fibers of the sulfone-containing polysiloxane prepared in example 1.
FIG. 4 is a NMR spectrum of the sulfone-containing polysiloxane prepared in example 1.
FIG. 5 is a thermogravimetric analysis curve of the fibers of the sulfone-containing polysiloxane prepared in example 1.
Detailed Description
The present invention will now be described in further detail by way of specific examples, which are provided for illustration purposes and are not intended to limit the scope of the invention, in conjunction with the following drawings.
Example 1
(1) 8.6g (50mmol) of α, α' -dimercaptop-xylene, 9.2g (50mmol) of a vinyl-bis-head, and 0.2g of benzoin dimethyl ether (DMPA) were added to the round-bottom flask. After sealing, the mixture was placed under an ultraviolet lamp and stirred for reaction for 15min, and the system became viscous to obtain a crude product as a yellow viscous liquid. After drying under vacuum, a yellowish, transparent viscous liquid was obtained with a yield of 16.3g and a yield of 92%. 16.3g (46mmol) of the above viscous liquid was weighed and dissolved in a flask with tetrahydrofuran. Then, 14.1g (46mmol) of the oxidizing agent oxone was added thereto, and the reaction was stirred at room temperature for 12 hours under a nitrogen atmosphere. Thereafter, 14.1g (46mmol) of oxone was added to the system, and the reaction was stirred at room temperature for further 12 hours. After completion of the reaction, white plate-like crystals of P1OX were obtained in a yield of 8.3g and a yield of 55%.
The result of the nuclear magnetic resonance hydrogen spectrum test of the product is shown in figure 1, and as can be seen from figure 1, the corresponding attribution can be found in each peak, which indicates that the sulfone-containing macrocyclic siloxane monomer is successfully synthesized.
(2) Sulfone-containing macrocyclic siloxane monomer (2.9g, 7mmol) was dissolved in a three-necked flask containing anhydrous dimethylsulfoxide, followed by addition of KOH (39.0mg, 0.7mmol), reaction at 100 ℃ for 8h under nitrogen protection, followed by addition of benzoic acid (85.0mg, 0.7mmol) to quench the reaction and remove dimethylsulfoxide to give sulfone-containing polysiloxane as a yellow solid in 90% yield. The obtained sulfone-containing polysiloxane is easy to be drawn into fibers due to the introduction of main chain sulfone groups, and the obtained fiber photo is shown in figure 2. Meanwhile, uniform sulfone-containing polysiloxane fibers can be obtained through electrostatic spinning, and a scanning electron microscope of the spun fibers is shown in figure 3, so that the fibers are uniform, smooth in surface and good in spinnability.
The product was subjected to nmr spectroscopy, as shown in fig. 4. As can be seen from FIG. 4, the peaks can find the corresponding assignments, indicating that ring-opening polymerization has occurred to give a sulfone-containing polysiloxane.
The thermogravimetric analysis of the obtained sulfone-containing silicone fiber is shown in fig. 5. As can be seen from FIG. 5, the sulfone-containing silicone fiber of the present invention has good heat resistance, a thermal weight loss temperature of 328 ℃ and a maximum permanent temperature of 382 ℃.
(3) The sulfone-containing polysiloxane (5.3g) obtained above was taken and dissolved in a single-neck flask containing 15ml of tetrahydrofuran, followed by addition of a solution in 15ml of H2KHSO of O4(27.2g, 0.2mol), stirring at 30 ℃ for 24h to give the sulfone-containing macrocyclic siloxane monomer as a white solid in 87% yield. So that the sulfone-containing polysiloxane is successfully degraded and recycled to obtain the sulfone-containing macrocyclic siloxane monomer.
Example 2
(1) 6.1g (50mmol) of butanedithiol, 9.2g (50mmol) of a vinyl-bis-head, and 0.2g of Benzonic acid (DMPA) were charged into a round-bottomed flask. After sealing, the mixture is placed under an ultraviolet lamp and stirred for reaction for 15min, and the system becomes viscous to obtain a crude product which is colorless viscous liquid. After drying under vacuum, a yellowish, transparent viscous liquid was obtained with a yield of 14.3g and a yield of 94%. 14.1g (46mmol) of the above viscous liquid was weighed and dissolved in a flask with tetrahydrofuran. Then, 14.1g (46mmol) of the oxidizing agent oxone was added thereto, and the reaction was stirred at room temperature for 12 hours under a nitrogen atmosphere. Thereafter, 14.1g (46mmol) of oxone was added to the system, and the reaction was stirred at room temperature for 12 hours. After completion of the reaction, white plate-like crystals of P2OX were obtained in 51% yield.
(2) Sulfone-containing macrocyclic siloxane monomer (2.6g, 7mmol) was dissolved in a three-necked flask containing anhydrous dimethylsulfoxide, followed by addition of KOH (39.0mg, 0.7mmol), reaction at 100 ℃ for 8h under nitrogen, followed by addition of benzoic acid (85.0mg, 0.7mmol) to quench the reaction and remove dimethylsulfoxide to give sulfone-containing polysiloxane as a yellow solid in 93% yield.
(3) GetThe sulfone-containing polysiloxane (4.7g) obtained above was dissolved in a single-neck flask containing 15ml of tetrahydrofuran, and then dissolved in 15ml of H2KHSO of O4(27.2g, 0.2mol), stirring at 30 ℃ for 24h to give a white crystalline sulfone-containing macrocyclic siloxane in 87% yield.
Example 3
(1) 12.5g (50mmol) of 4', 4-dimercaptodiphenylsulfide, 9.2g (50mmol) of a vinyl-bis-head, and 0.2g of benzoin dicarboxylic acid (DMPA) were charged into a round-bottomed flask. After sealing, the mixture was placed under an ultraviolet lamp and stirred for reaction for 15min, and the system became viscous to obtain a crude product as a yellow viscous liquid. After drying under vacuum, a yellowish, transparent viscous liquid was obtained with a yield of 19.5g and a yield of 91%. 20.0g (46mmol) of the above viscous liquid was weighed and dissolved in a flask with tetrahydrofuran. Then, 21.1g (69mmol) of the oxidizing agent oxone was added thereto, and the reaction was stirred at room temperature for 12 hours under a nitrogen atmosphere. Thereafter, 21.1g (69mmol) of oxone was added to the system, and the reaction was further stirred at room temperature for 12 hours. After completion of the reaction, white flaky crystals were obtained in 55% yield.
(2) Sulfone-containing macrocyclic siloxane monomer (3.5g, 7mmol) was dissolved in a three-necked flask containing anhydrous dimethylsulfoxide, followed by addition of KOH (39.0mg, 0.7mmol), reaction at 100 ℃ for 8h under nitrogen, followed by addition of benzoic acid (85.0mg, 0.7mmol) to quench the reaction and remove dimethylsulfoxide to give sulfone-containing polysiloxane as a yellow solid in 89% yield.
(3) The sulfone-containing polysiloxane (6.3g) obtained above was taken and dissolved in a single-neck flask containing 15ml of tetrahydrofuran, followed by addition of a solution in 15ml of H2KHSO of O4(27.2g, 0.5mol), stirring at 30 ℃ for 24h to give the sulfone-containing macrocyclic siloxane as a white solid in 85% yield.
Comparative example 1
According to patent CN101838863B, alpha, beta-dimethoxy polydimethylsiloxane with weight-average molecular weight of about 50 ten thousand is dissolved in toluene and mixed with aminopropyl triethoxysilane, and then the mixture is subjected to polycondensation reaction at 140 ℃ for 3 hours, and the product is electrospun, so that the solidification is easy, the fiber is easy to deform and break, and the re-dissolution spinning cannot be carried out.
Comparative example 2
Reacting octamethylcyclotetrasiloxane under the catalysis of alkali glue at 110 ℃, then heating to 130 ℃ for 30min to inactivate the catalyst to obtain linear polydimethylsiloxane with the weight-average molecular weight of 70 ten thousand, and then carrying out electrostatic spinning on the polysiloxane to find that the polysiloxane has high viscosity, cannot be molded and is easy to break.
Comparative example 3
Uniformly mixing polydimethylsiloxane containing vinyl, oligosiloxane containing silicon-hydrogen bonds and 0.1% chloroplatinic acid catalyst, crosslinking at 150 ℃, and then carrying out electrospinning, wherein fibers are easy to deform and cannot be re-dissolved for spinning.
The above are only preferred embodiments of the present invention and are not intended to limit the present invention. It should be noted that, for those skilled in the art, modifications can be made without departing from the invention, and these modifications should also be construed as the scope of the invention.
Claims (7)
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| EP2468798A1 (en) * | 2009-08-20 | 2012-06-27 | Central Glass Company, Limited | Solid electrolyte membrane for fuel cell and process for producing same |
| CN110144045A (en) * | 2019-05-16 | 2019-08-20 | 山东大学 | A kind of sulfone-containing polysiloxane fiber and its preparation method |
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| Title |
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| From Polymer to Monomer: Cleavage and Rearrangement of Si-O-Si Bonds after Oxidation Yielded an Ordered Cyclic Crystallized Structure;Yujing Zuo等;《chemistry A European Journal Communication》;20150617;第21卷;第10972-10977页 * |
| Yujing Zuo等.From Polymer to Monomer: Cleavage and Rearrangement of Si-O-Si Bonds after Oxidation Yielded an Ordered Cyclic Crystallized Structure.《chemistry A European Journal Communication》.2015,第21卷第10972-10977页. * |
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