CN112251240A - Quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance and preparation method and application thereof - Google Patents
Quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance and preparation method and application thereof Download PDFInfo
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- CN112251240A CN112251240A CN202011124640.5A CN202011124640A CN112251240A CN 112251240 A CN112251240 A CN 112251240A CN 202011124640 A CN202011124640 A CN 202011124640A CN 112251240 A CN112251240 A CN 112251240A
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- China
- Prior art keywords
- liquid crystal
- ionic liquid
- crystal polymer
- quaternary ammonium
- ammonium salt
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 119
- 239000004992 Ionic Liquid Crystal Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 52
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 70
- -1 polysiloxane Polymers 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 28
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical group CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 63
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- 238000010992 reflux Methods 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 239000000543 intermediate Substances 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 239000004990 Smectic liquid crystal Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- XPWMIGFSEWFXEZ-UHFFFAOYSA-N 2-prop-2-enoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OCC=C XPWMIGFSEWFXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 7
- UCVODTZQZHMTPN-UHFFFAOYSA-N heptanoyl chloride Chemical compound CCCCCCC(Cl)=O UCVODTZQZHMTPN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 claims description 6
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 claims description 6
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- NTQYXUJLILNTFH-UHFFFAOYSA-N nonanoyl chloride Chemical compound CCCCCCCCC(Cl)=O NTQYXUJLILNTFH-UHFFFAOYSA-N 0.000 claims description 3
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PDWBGRKARJFJGI-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1C1=CC=CC=C1 PDWBGRKARJFJGI-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 125000001924 fatty-acyl group Chemical group 0.000 claims 5
- 150000007513 acids Chemical class 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 48
- 239000000463 material Substances 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 11
- 230000009477 glass transition Effects 0.000 abstract description 9
- 150000003839 salts Chemical group 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000002329 infrared spectrum Methods 0.000 description 37
- 239000010408 film Substances 0.000 description 32
- 238000001228 spectrum Methods 0.000 description 32
- 239000011324 bead Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- OOKUTCYPKPJYFV-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;bromide Chemical compound [Br-].CN1C=C[NH+]=C1 OOKUTCYPKPJYFV-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- 229940006460 bromide ion Drugs 0.000 description 8
- UJWVKWKGJHCBCX-UHFFFAOYSA-N 1-butyl-1h-imidazol-1-ium;bromide Chemical compound [Br-].CCCCN1C=C[NH+]=C1 UJWVKWKGJHCBCX-UHFFFAOYSA-N 0.000 description 6
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 6
- DYDWKSVZHZNBLO-UHFFFAOYSA-N 4-prop-2-enoxybenzoic acid Chemical compound OC(=O)C1=CC=C(OCC=C)C=C1 DYDWKSVZHZNBLO-UHFFFAOYSA-N 0.000 description 6
- 150000002190 fatty acyls Chemical group 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- KGWVFQAPOGAVRF-UHFFFAOYSA-N 1-hexylimidazole Chemical compound CCCCCCN1C=CN=C1 KGWVFQAPOGAVRF-UHFFFAOYSA-N 0.000 description 5
- UWSNRJHXDNLVTK-UHFFFAOYSA-N 3-hexyl-1H-imidazol-3-ium bromide Chemical compound [Br-].CCCCCC[n+]1cc[nH]c1 UWSNRJHXDNLVTK-UHFFFAOYSA-N 0.000 description 5
- WYMVIVUKHYHNBN-UHFFFAOYSA-N 4-prop-2-enoxybenzoyl chloride Chemical compound ClC(=O)C1=CC=C(OCC=C)C=C1 WYMVIVUKHYHNBN-UHFFFAOYSA-N 0.000 description 5
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 5
- 239000004988 Nematic liquid crystal Substances 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- UXDAIPRCZFIVFZ-UHFFFAOYSA-N 1H-imidazol-3-ium-3-yl(trimethyl)silane bromide Chemical compound [Br-].C[Si](C)(C)N1C=C[NH+]=C1 UXDAIPRCZFIVFZ-UHFFFAOYSA-N 0.000 description 4
- 229920000831 ionic polymer Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- JYJHZYIDOQMNOW-UHFFFAOYSA-N CCCCC(=O)OC1CCC(O)CC1 Chemical compound CCCCC(=O)OC1CCC(O)CC1 JYJHZYIDOQMNOW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- MZXNOAWIRQFYDB-UHFFFAOYSA-N 4-(4-hydroxycyclohexyl)cyclohexan-1-ol Chemical compound C1CC(O)CCC1C1CCC(O)CC1 MZXNOAWIRQFYDB-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- UPYVYJSWGZMBOU-UHFFFAOYSA-N 1-pentylimidazole Chemical compound CCCCCN1C=CN=C1 UPYVYJSWGZMBOU-UHFFFAOYSA-N 0.000 description 1
- IPIORGCOGQZEHO-UHFFFAOYSA-N 1-propan-2-ylimidazole Chemical compound CC(C)N1C=CN=C1 IPIORGCOGQZEHO-UHFFFAOYSA-N 0.000 description 1
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 1
- VWUCIBOKNZGWLX-UHFFFAOYSA-N 1h-imidazol-1-ium;bromide Chemical group [Br-].C1=C[NH+]=CN1 VWUCIBOKNZGWLX-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- USVUMWSMZMQXIZ-UHFFFAOYSA-N phenyl heptanoate Chemical compound CCCCCCC(=O)OC1=CC=CC=C1 USVUMWSMZMQXIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H37/00—Thermally-actuated switches
- H01H37/02—Details
- H01H37/32—Thermally-sensitive members
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
- C09K2219/13—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the technical field of thermotropic switches
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance and a preparation method and application thereof belong to the field of ionic liquid crystal materials. The quaternary ammonium salt ionic liquid crystal polymer with the temperature control electronic switch performance has a structural general formula as follows:
the ionic liquid crystal compound is based on a polysiloxane main chain structure, contains an imidazole bromoonium salt group and a mesogen, and is constructed by polymethylhydrosiloxane, bromopropylene, N-alkyl imidazole and micromolecular liquid crystal containing terminal group olefinic bond. The ionic liquid crystal compound is prepared by reactingThe chemical structure of the polymer is changed to regulate and control the glass transition temperature, the conductivity and the liquid crystallinity, thereby realizing the temperature control electronic switch performance.
Description
Technical Field
The invention belongs to the field of ionic liquid crystal materials, and particularly relates to a quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switching performance, and a preparation method and application thereof.
Background
The ionic liquid crystal polymer is a polymer with an ionic group on a chemical structure and liquid crystal property on performance, and is a novel polymer developed on the basis of substances such as traditional ionic liquid, ionic polymer, liquid crystal polymer and the like. The ionic liquid and the ionic polymer both contain ionic groups, the ionic liquid is an organic salt which shows a liquid state at a low temperature, and the ionic polymer is an organic polymer containing ionic groups, and both have conductivity under certain conditions. Liquid crystals are a class of condensed substances between fully isotropic liquids and three-dimensionally ordered crystals, which have both the flow properties of liquids and the anisotropic properties of crystals. With the temperature changing from low to high, most of the traditional small molecular liquid crystal displays solid crystalline state, liquid crystal state, complete liquid state and other state changes; wherein the temperature for changing from solid state to liquid crystal state corresponds to melting point temperature, and the temperature for changing from liquid crystal state to isotropic liquid corresponds to clearing point temperature; the temperature interval between the melting point temperature and the clearing point temperature is a liquid crystal state temperature interval in which the substance exhibits liquid crystallinity. Liquid crystal polymers are a class of polymers that exhibit liquid crystal properties, most of which are prepared from small molecule liquid crystals by various polymerization methods. Compared with the traditional micromolecular liquid crystal, the liquid crystal polymer integrates the characteristics of the polymer and the functionality of the liquid crystal; as the temperature is increased from low to high, they enter a liquid crystalline state at a temperature higher than the glass transition temperature of the polymer, which is the temperature corresponding to the glass transition to the high elastic state. Ionic liquid crystalline polymers have attracted attention because they combine the properties of ionic liquids, ionic polymers, liquid crystalline polymers and the like, particularly, conductivity and liquid crystallinity. The reports of ionic liquid crystal polymers cover aspects of functional thin film materials, optoelectronic devices, solid electrolytes, battery electrolytes, and the like. However, there is no report on the performance of the temperature-controlled electronic switch.
Disclosure of Invention
The invention aims to provide a quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switching performance, and a preparation method and application thereof. The glass transition temperature, the conductivity and the liquid crystallinity are regulated and controlled by changing the chemical structure of the polymer on the chemical structure, so that the temperature control electronic switch performance is realized.
The invention relates to a quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, which has a structural general formula as follows:
in the formula: b is cyclohexane
Phenyl radical
Dicyclohexyl alkyl
Or biphenyl
One of (1);
x and y are mole fractions in 1 mole of polymethylhydrosiloxane, 0< x <1, 0< y <1, and x + y is 1;
alkyl- (CH)2)mCH3Wherein m is an integer, and m is 1-9;
r is C1-C6 alkyl or 1-trimethylsilyl, wherein the C1-C6 alkyl is preferably one of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl or n-hexyl.
Polysiloxane backbone based on average molecular weight Mn1,700-3,200 of a commercially available polymethylhydrosiloxane;
n is the number of silicon-hydrogen bonds in polymethylhydrosiloxane molecules, n is an integer, and n is 25-53; the number average molecular weight range of the quaternary ammonium salt ionic liquid crystal polymer with the temperature control electronic switch performance is 0.5-5 ten thousand.
The quaternary ammonium salt ionic liquid crystal polymer with the temperature-controlled electronic switching performance is an ionic liquid crystal polymer which is formed by grafting liquid crystal elements on a polysiloxane main chain and also grafting cations and bromine anions of imidazole elements, and sequentially generates solid-state liquid crystal, smectic phase liquid crystal, nematic phase liquid crystal and liquid along with the rise of temperature, wherein the quaternary ammonium salt ionic liquid crystal polymer with the temperature-controlled electronic switching performance has textures of smectic phase and nematic phase.
The invention relates to a preparation method of a quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, which comprises the following steps:
step 1: preparation of small molecule liquid crystal with terminal olefinic bond
The micromolecular liquid crystal with terminal group olefinic bond is prepared by allyloxybenzoyl chloride and monophenol intermediates through esterification reaction; or prepared by esterification reaction of allyloxybenzoyl chloride and hydroxyl-containing intermediate;
in the step 1, allyloxybenzoyl chloride is prepared by reacting allyloxybenzoic acid with thionyl chloride.
The allyl benzoic acid is prepared by the following preparation method:
(1) molar ratio, p-hydroxybenzoic acid: potassium hydroxide: potassium iodide ═ 1: (2-3): (0.05-0.1) weighing raw materials, fully dissolving the raw materials in an ethanol-water mixed solvent, and dropwise adding bromopropylene with stirring, wherein the molar amount of the bromopropylene is equal to that of the p-hydroxybenzoic acid; after the dropwise addition is finished, uniformly stirring, and heating for reflux reaction for 16-32 hours;
(2) and after the reflux reaction is finished, removing impurities from the reaction liquid, carrying out solid-liquid separation, and recrystallizing the solid phase by using ethanol to obtain the allyloxy benzoic acid.
In the step (1), in the ethanol-water mixed solvent, the volume ratio of ethanol: water (2-4): 1, the amount of the ethanol-water mixed solvent is controlled in such a manner that all the reaction materials can be dissolved.
In the step (1), the dropping rate of the bromopropylene is as follows: 0.15-10 mL/min, and a stirring speed of 200-300 rpm.
In the step (2), the impurity removal post-treatment comprises the following steps: distilling the reaction liquid to remove ethanol, then mixing the reaction residual liquid with water with the volume of 3-5 times that of the reaction residual liquid, adding dilute hydrochloric acid to adjust the pH value to 3-5, uniformly mixing, and carrying out solid-liquid separation.
In the step 1, the preparation method of allyloxybenzoyl chloride specifically comprises the following steps:
dripping thionyl chloride into allyloxy benzoic acid at room temperature, wherein the molar ratio of the allyloxy benzoic acid: thionyl chloride is 1: (3-5); and after the dropwise addition is finished, stirring at room temperature for reaction for 2-3 h, then heating to 60-66 ℃ for reaction for 5-8 h, and after the reaction is finished, carrying out reduced pressure distillation to remove excessive thionyl chloride to obtain a yellow transparent liquid, namely allyloxybenzoyl chloride, and sealing for later use.
In the preparation method of the allyloxybenzoyl chloride, the dropping speed of the thionyl chloride is 5-10 mL/min, and the stirring speed is 200-300 rpm.
The monophenol intermediate is prepared by the following preparation method:
according to the functional group of B in the prepared quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, selecting a dihydric phenol compound, and dissolving the dihydric phenol compound and triethylamine in tetrahydrofuran to obtain a mixed solution; and (2) dropwise adding fatty acyl chloride into the mixed solution with stirring, reacting at room temperature for 2-3 h after dropwise adding is completed, heating for reflux reaction for 16-32 h, removing impurities after the reflux reaction is completed, carrying out solid-liquid separation, and recrystallizing a solid phase by using acetone to obtain a monophenol intermediate, wherein the molar ratio of the fatty acyl chloride to the dihydric phenol compound to the triethylamine is 1 to (3-5) to 1.
Wherein the dosage of the tetrahydrofuran is controlled by the standard of dissolving all reaction principles.
The fatty acyl chloride is one of acetyl chloride, propionyl chloride, butyryl chloride, valeryl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride or decanoyl chloride.
And removing impurities, namely distilling a product after the reflux reaction to remove 1/2-4/5 volume of tetrahydrofuran, cooling residual liquid, mixing the residual liquid with 5 times of water, adding dilute hydrochloric acid to adjust the pH value to 3-5, carrying out solid-liquid separation, washing a filter cake for at least 2 times by using solid-phase ethanol, and recrystallizing by using acetone.
The hydroxyl-containing intermediate is prepared by the following preparation method:
according to the functional group of B in the prepared quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, dihydroxy alcohol compounds are selected, and the dihydroxy alcohol compounds and triethylamine are dissolved in tetrahydrofuran to obtain mixed liquor; dropwise adding fatty acyl chloride into the mixed solution with stirring, reacting at room temperature for 2-3 h after dropwise adding is completed, heating and performing reflux reaction for 16-32 h, removing impurities after the reflux reaction is completed, and recrystallizing a solid phase with acetone to obtain a monophenol intermediate; wherein the molar ratio of the fatty acyl chloride to the dihydroxy alcohol compound to the triethylamine is 1: 3-5: 1.
Wherein the dosage of the tetrahydrofuran is controlled by the standard of dissolving all reaction principles.
The dihydric phenol compound or the dihydric alcohol compound is one of 1, 4-cyclohexanediol, hydroquinone, 4 '-dihydroxydicyclohexyl and 4,4' -dihydroxybiphenyl.
The fatty acyl chloride is one of acetyl chloride, propionyl chloride, butyryl chloride, valeryl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride or decanoyl chloride.
And removing impurities, namely distilling a product after the reflux reaction to remove 1/2-4/5 volume of tetrahydrofuran, cooling residual liquid, mixing the residual liquid with 5 times of water, adding dilute hydrochloric acid to adjust the pH value to 3-5, carrying out solid-liquid separation, washing a filter cake for at least 2 times by using solid-phase ethanol, and recrystallizing by using acetone.
The micromolecular liquid crystal with terminal group olefinic bond is prepared by the following preparation method, and the preparation method comprises the following specific steps:
the monophenol intermediate or the hydroxyl group-containing intermediate as a raw material and triethylamine were dissolved in tetrahydrofuran, and allyloxybenzoyl chloride was added dropwise with stirring, wherein the molar ratio of allyloxybenzoyl chloride: monophenol intermediate or hydroxyl group-containing intermediate: triethylamine (1-1.5): 1: 1;
and after the dropwise addition is finished, reacting at room temperature for 2-3 h, heating and refluxing for 16-32 h, removing impurities after the refluxing reaction is finished, carrying out solid-liquid separation, and recrystallizing a solid phase by using ethanol to obtain the micromolecule liquid crystal with terminal olefinic bonds.
Wherein the dosage of the tetrahydrofuran is controlled by the standard that all reaction raw materials can be dissolved.
Wherein the impurities are removed by distilling a product after the reflux reaction is finished to remove 1/2-4/5 volume of tetrahydrofuran, cooling the residual liquid, mixing the residual liquid with 5 times of water, adding dilute hydrochloric acid to adjust the pH value to 3-5, filtering, washing a filter cake for at least 2 times by using ethanol, and performing ethanol recrystallization.
Step 2: preparation of bromopolysiloxanes
The bromopolysiloxane is prepared by carrying out graft polymerization on micromolecular liquid crystal with terminal olefinic bond, bromopropylene and Polymethylhydrosiloxane (PMHS) by adopting a platinum catalyst; wherein, the adding proportion of bromopropylene and micromolecular liquid crystal with terminal group olefinic bond is determined according to the proportion of x and y in the quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance; and the sum of the number of moles of bromopropene and the number of moles of terminal ethylenic small molecular liquid crystals is equal to the number of moles of Si-H bonds in Polymethylhydrosiloxane (PMHS);
the preparation method comprises the following steps: under the protection of nitrogen, dissolving micromolecular liquid crystal of end group olefinic bond, bromopropylene and Polymethylhydrosiloxane (PMHS) by using toluene, wherein the dosage of the toluene is controlled by taking the micromolecular liquid crystal of the end group olefinic bond and the bromopropylene completely dissolved as a standard to obtain a mixed solution;
adding a platinum catalyst into the mixed solution, carrying out reflux reaction for 35-40 h under the protection of nitrogen, carrying out reduced pressure distillation to remove a toluene solvent of 3/4, mixing the residual liquid with methanol, separating out a precipitate, carrying out solid-liquid separation, washing a filter cake with ethanol, and drying to obtain bromopolysiloxane; wherein, the addition amount of the platinum catalyst is 0.01-1 percent of the mass of the polymethylhydrosiloxane.
In the step 2, the ratio of methanol: a reaction solution of bromopolysiloxane (10-20): 1.
and step 3: preparation of quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance
Taking bromopolysiloxane and 1-alkyl imidazole as raw materials, taking toluene as a solvent, and obtaining the following components in molar ratio: bromine element in brominated polysiloxane: 1-alkylimidazole ═ 1: (1-1.2) weighing raw materials, mixing the raw materials in a toluene solvent, carrying out microwave heating reflux reaction for 0.5-1 h, and carrying out reduced pressure distillation to remove the toluene solvent after the reaction is finished to obtain a crude product of the quaternary ammonium salt ionic liquid crystal polymer;
and adding acetone into the crude product of the quaternary ammonium salt ionic liquid crystal polymer, separating out, and filtering to obtain the quaternary ammonium salt ionic liquid crystal polymer with the temperature control electronic switch performance.
In the step 3, the molar concentration of the toluene solution is 0.1-0.3 mol/L.
In the step 3, the heating is carried out by microwave heating, wherein the microwave frequency is 300 MHz-300 KMHz.
In the step 3, the 1-alkyl imidazole is selected from C1-C6 alkyl or trimethylsilylimidazole, and the C1-C6 alkyl is preferably one of 1-methylimidazole, 1-ethylimidazole, 1-n-propylimidazole, 1-isopropylimidazole, 1-n-butylimidazole, 1-pentylimidazole or 1-hexylimidazole.
In the step 3, the volume ratio of acetone: reaction liquid of quaternary ammonium salt ionic liquid crystal polymer (1-10): 1.
in the reflux reaction, the reflux temperature is determined according to the property proportion of the solution, and is preferably 60-66 ℃.
In the preparation of the brominated polysiloxane, the performances of the polymer, such as glass transition temperature, conductivity, liquid crystallinity and the like, are regulated and controlled by changing the mole ratio of micromolecular liquid crystal of terminal olefinic bonds to bromopropylene. Namely, the mole number of Si-H bonds in the PMHS is 1, the mole number of bromopropylene is x, and the mole number of the micromolecule liquid crystal with terminal olefinic bonds is y, so that x + y is 1, wherein 0< x <1, and 0< y < 1.
A temperature-controlled electronic switch is prepared from quaternary ammonium salt ion liquid crystal polymer with temperature-controlled electronic switch performance.
The reaction equation of the invention is as follows:
preparing a small molecular liquid crystal with terminal olefinic bonds:
b is cyclohexane
Phenyl radical
Dicyclohexyl alkyl
Or biphenyl
m is an integer, and m is 1-9.
Preparing bromopolysiloxane:
polymethylhydrosiloxane average molecular weight Mn1,700-3,200, wherein the mole number of Si-H bonds in 1 mole of polymethylhydrosiloxane is n, and n is 25-53;
the number of moles of bromopropene reacted is n times x, wherein x is in the range of 0< x < 1;
the reaction mole number of the small molecular liquid crystal of the terminal olefinic bond is n multiplied by y, wherein the value range of y is 0< y < 1.
Preparing the target product of the ionic liquid crystal polymer containing the imidazolium bromide salt group:
r is methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl or trimethylsilyl.
The ionic liquid crystal polymer is one of liquid crystal polymers, and consists of anions, cations, liquid crystal elements, a polymer matrix and the like, and has adjustable ionic conductivity. The imidazole salt group is combined with the brominated liquid crystal polymer structural unit to prepare a novel adjustable conductive material, the chemical structure of the polymer is regulated and controlled to adjust the glass transition temperature, the liquid crystal property and the conductivity, so that the temperature control electronic switch performance is realized, and the preparation method is simple. The regulation and control mode of the chemical structure comprises the steps of selecting polymethylhydrosiloxane with different molecular weights as a polymer grafting reaction raw material, changing the feeding reaction ratio of micromolecular liquid crystal and bromopropylene, the length of alkyl linkage at the end group of the micromolecular liquid crystal, the length and type of alkyl in an imidazole monomer and the type of a liquid crystal element.
Drawings
FIG. 1 is an infrared spectrum of 4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl;
FIG. 2 is a drawing of 4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl1H-NMR spectrum;
FIG. 3 is an infrared spectrum of brominated polysiloxane P-Br;
FIG. 4 is a representation of brominated polysiloxane P-Br1H-NMR spectrum;
FIG. 5 is an infrared spectrum of 1-methylimidazolium bromide ionic liquid crystal polymer P1;
FIG. 6 shows 1-methylimidazolium bromide salt ionic liquid crystal polymer P11H-NMR spectrum;
FIG. 7 is a DSC of 1-methylimidazolium bromide ion liquid crystal polymer P1;
FIG. 8 is a photograph (200X) of 1-methylimidazolium bromide ion liquid-crystalline polymer P1 showing its polarization; (a) a smectic phase liquid crystal texture heated to 76 ℃; (b) raising the temperature to 98 ℃ to obtain a nematic liquid crystal texture;
FIG. 9 is a graph showing the dependence of the electric conductivity of a 1-methylimidazolium bromide ionic liquid crystal polymer P1 film on temperature.
FIG. 10 is an infrared spectrum of brominated polysiloxane P2-Br;
FIG. 11 shows bromo-polysiloxane P2-Br1H-NMR spectrum;
FIG. 12 is an infrared spectrum of 1-butylimidazolium bromide ionic liquid crystal polymer P2;
FIG. 13 shows 1-butylimidazolium bromide salt ionic liquid crystal polymer P21H-NMR spectrum;
FIG. 14 is a photograph (200X) of 1-butylimidazolium bromide salt-based liquid-crystalline polymer P2; (a) smectic phase liquid crystal texture; (b) nematic liquid crystal texture.
FIG. 15 is an infrared spectrum of brominated polysiloxane P3-Br;
FIG. 16 is a representation of brominated polysiloxane P3-Br1H-NMR spectrum;
FIG. 17 is an infrared spectrum of 1-hexylimidazolium bromide ionic liquid crystal polymer P3;
FIG. 18 shows 1-hexylimidazolium bromide salt ionic liquid crystal polymer P31H-NMR spectrum;
FIG. 19 is a photograph (200X) of 1-hexylimidazolium bromide ion liquid crystal polymer P3; (a) smectic phase liquid crystal texture; (b) nematic liquid crystal texture.
FIG. 20 is an infrared spectrum of 1-methylimidazolium bromide ion liquid crystal polymer P4;
FIG. 21 is a drawing showing a 1-methylimidazolium bromide salt ionic liquid crystal polymer P41H-NMR spectrum;
FIG. 22 is a photograph (200X) of 1-methylimidazolium bromide ion liquid-crystalline polymer P4 showing its polarization; (a) smectic phase liquid crystal texture; (b) nematic liquid crystal texture.
FIG. 23 is an infrared spectrum of 1-trimethylsilylimidazolium bromide ion liquid crystal polymer P5;
FIG. 24 is a drawing showing a 1-trimethylsilylimidazolium bromide ionic liquid crystal polymer P51H-NMR spectrum;
FIG. 25 is a photograph (200X) of 1-trimethylsilylimidazolium bromide ion liquid crystal polymer P5; (a) smectic phase liquid crystal texture; (b) nematic liquid crystal texture.
Detailed Description
The present invention will be described in further detail with reference to examples.
The number average molecular weight Mn of the commercially available polymethylhydrosiloxane adopted in the embodiment of the invention is approximately equal to 1,700-3,200 (CAS:63148-57-2), and the Mn is approximately equal to 2300 (the mole number n of Si-H bonds in 1 mole of polymethylhydrosiloxane is approximately equal to 35) and the Mn is approximately equal to 1700 (the mole number n of Si-H bonds in 1 mole of polymethylhydrosiloxane is approximately equal to 25) are obtained by methods such as reduced pressure distillation and the like.
In the examples of the present invention, biphenol (CAS:92-88-6), 4' -dihydroxybicyclohexane (CAS:20601-38-1), 1, 4-cyclohexanediol (CAS:556-48-9) and hydroquinone (CAS:123-31-9) were used as the starting materials for the preparation of the mesogen.
The small molecule liquid crystal in the embodiment of the invention is prepared by adopting heptanoyl chloride (CAS:2528-61-2), valeryl chloride (CAS:638-29-9), hexanoyl chloride (CAS:142-61-0) and octanoyl chloride (CAS:111-64-8) as reaction raw materials.
The 1-alkylimidazole used in the embodiment of the invention is 1-methylimidazole (CAS:616-47-7), 1-butylimidazole (CAS:4316-42-1), 1-hexylimidazole (CAS:33529-01-0) or trimethylsilylimidazole (CAS: 18156-74-6).
In the following examples, the reaction mixture ratios are not shown for the stoichiometric addition of the reaction formula. The amount of the solvent not indicated is added in an amount sufficient to dissolve the reaction materials.
In the following examples, the reflux temperature is not indicated, and the temperature capable of achieving reflux is used as the reflux temperature, which is determined according to the size of the reaction system, the ratio of the reaction materials and other factors.
The embodiment of the invention comprises the following testing instruments and types:
(1) infrared spectrometer (FT-IR) used a Spectrum One infrared spectrometer from PE, USA.
(2) The nuclear magnetic analysis was performed using a WH-90PFT nuclear magnetic resonance apparatus from Varian, USA.
(3) DSC-204 differential calorimeter from NETZSCH, Germany was used for differential scanning calorimetry.
(4) Polarization microscopy was performed using a polarization microscope of LEICA DMRX type with a THMSE600 thermal stage from Linam, UK.
(5) The conductivity was measured using an RTS-9 type dual electric test four-probe tester from Guangzhou four-probe technology, Inc.
(6) The LED lamp bead that self-control electronic switch experimental apparatus adopted is 3V.
Example 1
A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, in particular to a quaternary ammonium salt ionic liquid crystal polymer P1 containing 1-methylimidazole group, the chemical structural formula of which is as follows:
the preparation and test methods were as follows:
step 1: preparation of terminal olefinic bond small molecule liquid crystal M
(1) Preparation of 4-allyloxybenzoic acid: 24.0g of parahydroxybenzoic acid was weighed into a 250mL flask, and dissolved in 86mL of ethanol to obtain an ethanol solution of parahydroxybenzoic acid. 22.86g of potassium hydroxide and 0.172g of potassium iodide were dissolved in 28.6mL of water, cooled to room temperature, and then added dropwise to the above-mentioned alcoholic solution of p-hydroxybenzoic acid in a constant pressure dropping funnel at a rate of 5 to 10 mL/min. After stirring for 2h at normal temperature, 20mL of 3-bromopropylene (1-2 h) is added dropwise. Stirring for 1h at normal temperature, and heating and refluxing for reaction for 18 h. Cooling, pouring the reaction solution into a beaker filled with 500mL of water, adjusting the pH value to 4 by using dilute hydrochloric acid, generating a large amount of white precipitate, filtering, washing a filter cake by using water, and recrystallizing by using ethanol. Obtaining white needle-shaped crystals, namely 4-allyloxybenzoic acid, and the melting point is 168.7-171.1 ℃.
(2) Preparation of 4-allyloxybenzoyl chloride: weighing 35.6g (0.100mol) of 4-allyloxybenzoic acid into a 250mL three-neck flask, adding 50mL of thionyl chloride, stirring at normal temperature for 2h, heating to below 60 ℃ for reaction for 6h, and distilling under reduced pressure to remove excessive thionyl chloride to obtain light yellow liquid, namely 4-allyloxybenzoyl chloride.
(3) Preparation of a monophenol heptanoate intermediate: in a 250mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 18.6g (0.100mol) of biphenyldiol was charged, dissolved in 160mL of tetrahydrofuran and 0.030mL of triethylamine, and 4.5g (0.030mol, 4.625mL) of heptanoyl chloride was added dropwise with vigorous stirring, and after reacting the above materials at room temperature for 2 hours, the reaction was heated under reflux for 18 hours, 120mL of tetrahydrofuran was distilled off, cooled, and the reaction solution was poured into 200mL of water, adjusted to pH 4 with dilute hydrochloric acid, and filtered. Washing the filter cake with ethanol for 2 times, and recrystallizing the filter cake with acetone to obtain the intermediate of the heptanoic acid biphenyl monophenol.
(4) Preparation of terminal ethylenic small molecule liquid crystals M4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl: in a 250mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 14.9g (0.050mol) of biphenylmonophenol heptanoate intermediate was charged, dissolved in 160mL of tetrahydrofuran and 0.050mol of triethylamine, and 14.7g (0.075mol) of 4-allyloxybenzoyl chloride was added dropwise under vigorous stirring, and after reacting the above materials at room temperature for 2 hours, the reaction was refluxed for 32 hours, and 120mL of tetrahydrofuran was distilled off. Cooling residual liquid, pouring into 200mL of water, adjusting the pH value to 4 by using diluted hydrochloric acid, cooling, filtering, and recrystallizing by using ethanol to obtain the micromolecule liquid crystal 4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl with terminal olefinic bond.
A series of measurements were made of 4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl, which showed an infrared spectrum in FIG. 1 and the following infrared data: IR (KBr, cm)-1):2930，1721，1660，1601，1502，1106，1017，948。
The hydrogen nuclear magnetic spectrum is shown in figure 2, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(CDCl3,δ,ppm):0.65-0.75(3H)；1.10-1.18(6H)；1.43-1.51(2H)；2.35-2.41(2H)；4.48-4.50(2H)；5.11-5.28(2H)；5.82-5.95(1H)；6.91-7.06(6H)；7.55-7.64(4H)；7.89-7.91(2H).
as can be seen from fig. 2: the chemical shift value and the peak intensity in the nuclear magnetic spectrum are consistent with the chemical structure, and the prepared substance is 4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl is confirmed by combining the infrared spectrum information of the figure 1.
Step 2: preparation of bromopolysiloxane P-Br
After 4- (4-allyloxybenzoyloxy) -4'- (heptanoyloxy) -1,1' -biphenyl (1.60g,3.5mmol), bromopropene (3.78g,31.5mmol) were dissolved in 32mL of toluene, the mixture was poured into a 50mL three-necked flask, and after being magnetically stirred and heated to 45.0 ℃, polymethylhydrosiloxane (2.3g,1mmol) and 1.5mL of hexachloroplatinic acid catalyst hexachloroplatinic acid were added under nitrogen protection, and the mixture was heated under reflux for 36 hours under nitrogen protection. And distilling 24mL of toluene from the reaction mixed solution, pouring 100mL of methanol into residual liquid, standing the precipitate overnight, pouring out the methanol, performing suction filtration, washing a filter cake with hot ethanol to remove unreacted monomers, and performing vacuum drying at room temperature to obtain 6.5g of bromopolysiloxane P-Br.
The test analysis result of the brominated polysiloxane P-Br is as follows:
the IR spectrum of P-Br is shown in FIG. 3, with the following IR data:
IR(KBr,cm-1):2926,1729,1667,1606,1499,1172,820。
the hydrogen nuclear magnetic spectrum P1 of P-Br is shown in FIG. 4, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(CDCl3,δ,ppm):0.14(11.4H)；0.58-0.64(7.6H)；0.79-0.97(1.9H)；1.31-1.35(3.9H)；1.64-1.80(8.9H)；2.53-2.59(1.2H)；3.43-3.48(6.4H)；4.08-4.13(1.0H)；7.09-7.13(0.9H)；7.14-7.16(0.8H)；7.21-7.24(1.3H)；7.72-7.78(1.1H)；7.79-7.82(1.2H)；8.08-8.11(1.3H).
the chemical structural formula of brominated polysiloxane P1 is:
as can be seen from fig. 4: the chemical shift value in the nuclear magnetic spectrum is consistent with the peak intensity and the chemical structure, and the prepared substance is brominated polysiloxane P-Br which is confirmed by combining the infrared spectrum information of figure 3.
And step 3: preparation of 1-methylimidazolium Bronium salt Ionic liquid Crystal Polymer P1
Dissolving the brominated polysiloxane P-Br7.48g (31.5mmol) in 50ml of toluene to obtain solution I; 2.58g (31.5mmol) of 1-methylimidazole was dissolved in 50ml of toluene to obtain a solution II. Mixing the two under stirring, and heating and refluxing for reaction for 1 hour by using a microwave reactor with 300 MHz; and distilling the reaction liquid under reduced pressure to remove the toluene solvent, adding the toluene solvent into 200ml of acetone, separating out a solid phase, filtering to obtain a filtrate and a filter cake containing the quaternary ammonium salt ionic liquid crystal polymer, and drying the filter cake containing the quaternary ammonium salt ionic liquid crystal polymer to obtain the 1-methylimidazolium bromide ionic liquid crystal polymer P1.
The test analysis result of the 1-methylimidazolium bromide ionic liquid crystal polymer P1 is as follows:
the infrared spectrum of P1 is shown in FIG. 5, with the following infrared data:
IR(KBr,cm-1):2927,1729,1665,1601,1569,1598,1465,1237,1162,1082,1029,880。
the hydrogen nuclear magnetic spectrum of P1 is shown in FIG. 6, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(DMSO-d6,δ,ppm):0.14(17.20H)；0.58-0.64(11.84H)；0.84-0.95(2.91H)；1.24-1.39(5.90H)；1.61-1.73(3.99H)；1.94-2.04(12.84H)；2.53-2.59(1.96H)；3.17-3.34(4.98H)；3.49-3.58(5.00H)；3.73(14.33H)；4.09-4.13(1.96H)；4.94-5.03(9.83H)；7.07-7.14(4.16H)；7.16-7.24(1.80H)；7.73-7.82(3.97H)；8.09-8.11(1.97H)；8.92(4.78H).
as can be seen from fig. 6: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is the 1-methylimidazolium bromide ionic liquid crystal polymer P1 according to the infrared spectrum information of figure 5.
The DSC chart of P1 is shown in FIG. 7. The phase transition temperature (deg.C) and corresponding enthalpy change (J/g) are: a curve rising occurs between room temperature (25 ℃) and 59.2 ℃, indicating that 59.2 ℃ is the glass transition temperature; an endothermic peak appears at an elevated temperature of 94.6 ℃ indicating that a liquid crystal phase transition has occurred: a smectic phase at 59.2 ℃ to 94.6 ℃, a nematic phase at 94.6 ℃ to 158.6 ℃, a smectic-nematic transition temperature at 94.6 ℃, and an enthalpy change of 4.20J/g; when the temperature is increased to 158.6 ℃, an endothermic peak appears, which indicates that liquid crystal phase-isotropic transformation occurs, and the temperature of 158.6 ℃ is the clearing point temperature (T)i) The enthalpy change was 3.18J/g.
A representative photograph of P1 is shown in FIG. 8, from which it can be seen that: the material has liquid crystal texture of smectic phase and nematic phase during the temperature rising process.
And 4, step 4: determination of the temperature dependence of the conductivity of the P1 film
P1 was pressed into a film having a thickness of 0.5mm and kept in a dry atmosphere. The dependence of the electrical conductivity of the P1 film on temperature as measured by a dual electrical four-probe tester is shown in fig. 9. It can be seen that below the glass transition temperature, the conductivity is essentially zero; within a certain temperature interval (glass transition temperature to clearing point temperature), the conductivity gradually increases with the increase of temperature, and shows sudden increases at 60 ℃ and 100 ℃ respectively.
And 5: measurement of the electronic switching Performance of the P1 film
A P1 thin film with the thickness of 0.5mm, 2W LED lamp beads and a 3V dry battery pack are connected into a series circuit through leads, and the P1 thin film is placed on a temperature control hot table. The lamp beads are not bright at room temperature, the conductivity of the ionic liquid crystal polymer film is increased along with the increase of the temperature of the ionic liquid crystal polymer film, when the ionic liquid crystal polymer film is heated to 99 ℃, the lamp beads display weak bright light and twinkle, and when the ionic liquid crystal polymer film is continuously heated to 100 ℃, the lamp beads are full bright. Therefore, the temperature transition temperature of the P1 film for switching is 94.6 ℃ which is the smectic-nematic transition temperature, and the critical temperature for showing the electronic switching performance in this example is 99 ℃.
Example 2
A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, in particular to a quaternary ammonium salt ionic liquid crystal polymer P2 containing 1-butyl imidazole group, the chemical structural formula of which is as follows:
the preparation and test methods were as follows:
step 1: preparation of terminal olefinic bond small molecule liquid crystal N
(1) Preparation of the hydroxy-containing intermediate 4- (valeryloxy) cyclohexanol: in a 250mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 11.6g (0.100mol) of 1, 4-cyclohexanediol was charged, dissolved in 120mL of tetrahydrofuran and a small amount of triethylamine (0.030mol), 3.6g (0.030mol) of valeryl chloride was added dropwise with vigorous stirring, the above materials were reacted at room temperature for 2 hours, then heated under reflux for 18 hours, 90mL of tetrahydrofuran was distilled off, cooled, the reaction solution was poured into 200mL of water, adjusted to pH 4 with dilute hydrochloric acid, and filtered. Washing the filter cake with ethanol for 2 times, and recrystallizing the filter cake with acetone to obtain 4- (valeryloxy) cyclohexanol.
(2) Preparation of small molecule liquid crystal 4- (allyloxy) benzoic acid 4- (valeryloxy) cyclohexyl ester (N): in a 250mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 10.0g (0.050mol) of 4- (valeryloxy) cyclohexanol was charged, dissolved in 120mL of tetrahydrofuran and a small amount of triethylamine (0.060mol), and 11.8g (0.060mol) of 4-allyloxybenzoyl chloride (prepared by the preparation method of example 1) was added dropwise under vigorous stirring, and after reacting the above materials at room temperature for 2 hours, the reaction was refluxed for 32 hours, and 90mL of tetrahydrofuran was distilled off. Cooling the residual liquid, pouring into 200mL of water, adjusting the pH value to 4 by using dilute hydrochloric acid, cooling, performing suction filtration, and recrystallizing by using ethanol to obtain the terminal group-containing ethylenic bond micromolecule liquid crystal 4- (allyloxy) benzoic acid 4- (valeryloxy) cyclohexyl.
A series of detections are carried out on the micromolecule liquid crystal N of the terminal group olefinic bond, and the infrared spectrum data are as follows: IR (KBr, cm)-1):2935,2850,1738,1709,1610，1599，1464,1273,1104,945。
The hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(CDCl3,δ,ppm):0.81-0.95(3H)；1.11-1.41(6H)；1.73-1.78(4H)；1.92-1.76(2H)；2.30-2.34(2H)；4.44-4.54(2H)；4.58-4.66(2H)；5.28-5.45(2H)；5.99-6.09(1H)；6.64-6.68(2H)；6.85-6.89(2H).
it can be seen that: the chemical shift value and the peak intensity in the nuclear magnetic spectrum are consistent with the chemical structure, and the prepared substance is 4- (allyloxy) benzoic acid 4- (valeryloxy) cyclohexyl by combining infrared spectrum information.
Step 2: preparation of bromopolysiloxane P2-Br
After 4- (allyloxy) benzoic acid 4- (valeryloxy) cyclohexyl ester (3.78g,10.5mmol), bromopropene (2.94g,24.5mmol) were dissolved in 32mL of toluene, it was poured into a 50mL three-necked flask, and after magnetically stirring and heating to 45.0 deg.C, polymethylhydrosiloxane (2.3g,1mmol) and 1.5mL of hexachloroplatinic acid catalyst hexachloroplatinic acid were added under nitrogen protection, and heated under nitrogen protection to reflux for 36 hours. And distilling 24mL of toluene from the reaction mixed solution, pouring 100mL of methanol into residual liquid, standing the precipitate overnight, pouring out the methanol, performing suction filtration, washing a filter cake with hot ethanol to remove unreacted monomers, and performing vacuum drying at room temperature to obtain 5.4g of bromopolysiloxane P2-Br.
The test analysis result of the brominated polysiloxane P2-Br is as follows:
the IR spectrum of P2-Br is shown in FIG. 10, and the IR spectrum data is: IR (KBr, cm)-1):2946,2929,2850,1740,1708,1607,1580,1511,1467,1381,1279,1170,1116,960。
The hydrogen nuclear magnetic spectrum of P2-Br is shown in FIG. 11, and the hydrogen nuclear magnetic spectrum data are as follows:
1H-NMR(CDCl3,δ,ppm):0.14(8.77H)；0.58-0.64(5.89H)；0.91-0.95(3.00H)；1.18-1.28(6.11H)；1.69-1.75(10.12H)；1.77-1.92(2.03H)；2.29-2.34(2.00H)；3.43-3.47(3.98H)；4.08-4.12(1.98H)；；4.78-4.93(2.02H)；6.79-6.81(2.01H)；7.01-7.03(2.01H).
as can be seen from fig. 11: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is brominated polysiloxane P2-Br by combining the infrared spectrum information.
And step 3: preparation of 1-butylimidazolium Bromide Ionic liquid Crystal Polymer P2
8.82g (24.5mmol) of bromopolysiloxane P2-Br is dissolved in 50ml of toluene to obtain solution I; 3.04g (24.5mmol) of 1-butylimidazole was dissolved in 50ml of toluene to obtain a solution II. Mixing the two under stirring, heating and refluxing for 1 hour by using a microwave reactor; and (3) after the reaction is finished, carrying out reduced pressure distillation to remove the toluene solvent to prepare a crude product of the target product, adding the crude product into acetone, separating out, filtering and drying to obtain the liquid crystal polymer P2 containing the 1-butylimidazolium bromide salt ions.
The test analysis result of the 1-butylimidazolium bromide ionic liquid crystal polymer P2 is as follows:
the infrared spectrum of P2 is shown in FIG. 12, and the data outside the infrared spectrum are: IR (KBr, cm)-1):3108,2932,2868,1737,1705,1609,1579,1510,1465,1420,1381,1277,1229,1171,1103,1078,1011,926。
The hydrogen nuclear magnetic spectrum of P2 is shown in FIG. 13, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(DMSO-d6,δ,ppm):0.14(4.55H)；0.58-0.64(3.04H)；0.87-0.95(4.57H)；1.14-1.44(5.10H)；1.62-1.80(3.05H)；1.90-2.04(5.07H)；2.29-2.35(1.02H)；3.34-3.39(1.00H)；3.46-3.51(0.99H)；4.01-4.12(3.04H)；4.40-4.50(0.50H)；4.70-4.86(0.50H)；4.98-4.99(0.99H)；5.29-5.31(1.01H)；6.81-6.88(0.96H)；7.03-7.05(1.01H)；8.92(1.00H).
as can be seen from fig. 13: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is 1-butylimidazolium bromide ionic liquid crystal polymer P2 according to the infrared spectrum information.
A representative photograph of P2 is shown in FIG. 14, from which it can be seen that: the material has liquid crystal texture of smectic phase and nematic phase during the temperature rising process.
And 4, step 4: measurement of the electronic switching Performance of the P2 film
A P2 thin film with the thickness of 0.5mm, 2WLED lamp beads and a 3V dry battery pack are connected into a series circuit by leads, and the P2 thin film is placed on a temperature control hot table. The lamp beads are not bright at room temperature, the conductivity of the ionic liquid crystal polymer film is increased along with the increase of the temperature of the ionic liquid crystal polymer film, when the ionic liquid crystal polymer film is heated to 71 ℃, the lamp beads display weak bright light and twinkle, and when the ionic liquid crystal polymer film is continuously heated to 75 ℃, the lamp beads are full bright. Thus, the critical temperature at which the P1 film exhibits electronic switching performance is 71 ℃.
Example 3
A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, in particular to a quaternary ammonium salt ionic liquid crystal polymer P3 containing 1-hexyl imidazole group, the chemical structural formula of which is as follows:
the preparation and test methods were as follows:
step 1: preparation of Small molecule liquid Crystal O
(1) Preparation of hydroxyl-containing intermediate hexanoic acid 4 '-hydroxy- [1,1' -bis (cyclohexyl) ] -4-alcohol ester: 19.8g (0.100mol) of 4,4' -dihydroxybicyclohexane was charged in a 250mL three-necked flask equipped with a stirrer, a condenser and a thermometer, dissolved in 160mL of tetrahydrofuran and a small amount of triethylamine (0.030mol), 3.9g (0.030mol) of hexanoyl chloride was added dropwise with vigorous stirring, the above materials were reacted at room temperature for 2 hours, then heated under reflux for 18 hours, 120mL of tetrahydrofuran was distilled off, cooled, the reaction solution was poured into 200mL of water, adjusted to pH 4 with dilute hydrochloric acid, and filtered. Washing the filter cake with ethanol for 2 times, and recrystallizing the filter cake with acetone to obtain hexanoic acid 4 '-hydroxy- [1,1' -bis (cyclohexyl) ] -4-alcohol ester.
(2) Preparing a small-molecule liquid crystal 4- (allyloxy) benzoic acid 4'- (hexanoyloxy) - [1,1' -bis (cyclohexane) ] -4-alcohol ester (O): in a 250mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 14.8g (0.050mol) of 4 '-hydroxy- [1,1' -bis (cyclohexyl) ] -4-ol hexanoate was charged, dissolved in 160mL of tetrahydrofuran and a small amount of triethylamine (0.060mol), and 11.8g (0.060mol) of 4-allyloxybenzoyl chloride (prepared by the preparation method of example 1) was added dropwise under vigorous stirring, and after reacting the above materials at room temperature for 2 hours, the reaction was refluxed for 32 hours, and 120mL of tetrahydrofuran was distilled off. And (3) cooling the residual liquid, pouring the residual liquid into 200mL of water, adjusting the pH value to 5 by using dilute hydrochloric acid, cooling, performing suction filtration, and recrystallizing by using ethanol to obtain the terminal group-containing ethylenic bond micromolecule liquid crystal O.
A series of detections are carried out on the terminal group-containing ethylenic bond micromolecule liquid crystal O, and the infrared spectrum data are as follows: IR (KBr, cm)-1):2942,2852,1737,1708,1609,1598，1466,1271,1113,942。
The hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(CDCl3,δ,ppm):0.88-1.53(17H)；1.65-1.94(10H)；2.38-2.51(2H)；4.42-4.71(4H)；5.31-5.45(2H)；5.98-6.05(1H)；6.71-6.86(2H)；6.89-6.95(2H).
the chemical shift value and the peak intensity of the nuclear magnetic spectrum are consistent with the chemical structure, and the infrared spectrum information is combined to confirm that the prepared substance is 4- (allyloxy) benzoic acid 4'- (hexanoyloxy) - [1,1' -di (cyclohexane) ] -4-alcohol ester.
Step 2: preparation of bromopolysiloxane P3-Br
After 4- (allyloxy) benzoic acid 4'- (hexanoyloxy) - [1,1' -bis (cyclohexane) ] -4-alcohol ester (2.87g,6.3mmol), bromopropene (2.24g,18.7mmol) were dissolved in 32mL of toluene, it was poured into a 50mL three-necked flask, and after magnetic stirring and heating to 45.0 deg.C, polymethylhydrosiloxane (1.7g,1mmol) and 1.5mL of hexachloroplatinic acid catalyst hexachloroplatinic acid were added under nitrogen protection, and the reaction was heated under reflux for 36 hours under nitrogen protection. And distilling 24mL of toluene from the reaction mixed solution, pouring 100mL of methanol into residual liquid, standing the precipitate overnight, pouring out the methanol, performing suction filtration, washing a filter cake with hot ethanol to remove unreacted monomers, and performing vacuum drying at room temperature to obtain 7.9g of bromopolysiloxane P3-Br.
The test analysis result of the brominated polysiloxane P3-Br is as follows:
the IR spectrum of P2-Br is shown in FIG. 15, and the IR spectrum data is: IR (KBr, cm)-1):2932,2867,2850,1738,1711,1605,1509,1466,1368,1270,1119,1065,1048,846,770。
The hydrogen nuclear magnetic spectrum of P3-Br is shown in FIG. 16, and the hydrogen nuclear magnetic spectrum data are as follows:
1H-NMR(CDCl3,δ,ppm):0.14(5.97H)；0.60-0.62(3.97H)；0.88-0.90(1.46H)；1.04-1.32(7.08H)；1.64-1.83(8.00H)；1.92-1.96(0.98H)；2.31-2.33(0.98H)；3.45-3.47(2.91H)；4.10-4.12(0.99H)；4.50-4.53(0.47H)；4.72-4.77(0.50H)；6.81-6.83(0.93H)；7.03-7.05(1.00H).
as can be seen from fig. 16: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is brominated polysiloxane P3-Br by combining the infrared spectrum information.
And step 3: preparation of 1-hexyl imidazolium Bromide Ionic liquid Crystal Polymer P3
6.81g (18.7mmol) of bromopolysiloxane P3-Br was dissolved in 50ml of toluene to obtain solution I; 4.00g (26.3mmol) of 1-hexylimidazole was dissolved in 50ml of toluene to obtain a solution II. Mixing the two under stirring, heating and refluxing for 1 hour by using a microwave reactor; and (3) after the reaction is finished, carrying out reduced pressure distillation to remove the toluene solvent to prepare a crude product of the target product, adding the crude product into acetone, separating out, filtering and drying to obtain the liquid crystal polymer P3 containing 1-hexyl imidazolium bromide salt ions.
The test analysis result of the 1-hexyl imidazolium bromide ionic liquid crystal polymer P3 is as follows:
the infrared spectrum data of P3 is shown in FIG. 17, and the infrared spectrum data is: IR (KBr, cm)-1):3106,2932,2867,2850,1738,1707,1610,1508,1465,1380,1269,1228,1170,1106,1076,1029,906,842,769。
The hydrogen nuclear magnetic spectrum of P3 is shown in FIG. 18, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(DMSO-d6,δ,ppm):0.16(4.10H)；0.61-0.65(2.71H)；0.90-0.92(4.04H)；1.04-1.07(0.71H)；1.23-1.36(8.93H)；1.65-2.11(9.61H)；2.33-2.35(0.68H)；3.26-3.28(0.66H)；3.49-3.53(0.34H)；3.72-3.76(1.00H)；3.76-3.94(0.35H)；4.05-4.14(2.66H)；4.80-4.98(2.31H)；6.83-6.85(0.66H)；7.05-7.07(0.67H)；8.94(1.00H).
as can be seen from fig. 18: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is the 1-hexyl imidazole bromide salt ion liquid crystal polymer P3 according to the infrared spectrum information.
A representative photograph of P3 is shown in FIG. 19, from which it can be seen that: the material has liquid crystal texture of smectic phase and nematic phase during the temperature rising process.
And 4, step 4: measurement of the electronic switching Performance of the P3 film
A P3 thin film with the thickness of 0.5mm, a 2W LED lamp bead and a 3V dry battery pack are connected into a series circuit through a lead, and the P3 thin film is placed on a temperature control hot table. The lamp beads are not bright at room temperature, the conductivity of the ionic liquid crystal polymer film is increased along with the increase of the temperature of the ionic liquid crystal polymer film, when the ionic liquid crystal polymer film is heated to 61 ℃, the lamp beads display weak bright light and twinkle, and when the ionic liquid crystal polymer film is continuously heated to 64 ℃, the lamp beads are full bright. Thus, the critical temperature at which the P3 film exhibits electronic switching performance is 61 ℃.
Example 4
A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, in particular to a quaternary ammonium salt ionic liquid crystal polymer P4 containing 1-methylimidazole group, the chemical structural formula of which is as follows:
the preparation method is the same as that in example 1, except that hydroquinone is used as a raw material in the step (3) to replace biphenol, octanoyl chloride is used to replace heptanoyl chloride, and the other steps are the same as those in example 1.
The result of the test analysis of the ionic liquid crystal polymer P4 is as follows:
the infrared spectrum data of P4 is shown in FIG. 20, and the infrared spectrum data is: IR (KBr, cm)-1):3142,2926,2865,1728,1696,1606,1579,1510,1462,1427,1370,1304,1262,1169,1106,1018,998,948,929,849,769。
The hydrogen nuclear magnetic spectrum of P4 is shown in FIG. 21, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(DMSO-d6,δ,ppm):0.06(3.58H)；0.52-0.55(2.41H)；0.0.81-0.82(1.16H)；1.17-1.25(2.05H)；1.58-1.59(0.78H)；1.90-1.93(2.40H)；2.48-2.49(0.38H)；3.11-3.19(1.19H)；3.22-3.26(0.40H)；3.28-3.39(0.40H)；3.50-3.65(2.35H)；3.95-4.04(0.78H)；4.77-4.87(2.00H)；7.00-7.01(0.40H)；7.21-7.22(0.80H)；8.02-8.03(0.40H)；8.84(1.00H).
as can be seen from fig. 21: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is the 1-methylimidazolium bromide ionic liquid crystal polymer P4 according to the infrared spectrum information.
A representative photograph of P4 is shown in FIG. 22, from which it can be seen that: the material has liquid crystal texture of smectic phase and nematic phase during the temperature rising process.
A P4 thin film with the thickness of 0.5mm, a 2W LED lamp bead and a 3V dry battery pack are connected into a series circuit through a lead, and the P4 thin film is placed on a temperature control hot table. At room temperature, the lamp beads are not bright, the conductivity of the ionic liquid crystal polymer film is increased along with the increase of the temperature of the ionic liquid crystal polymer film, when the ionic liquid crystal polymer film is heated to 82 ℃, the lamp beads display weak bright light and twinkle, and when the ionic liquid crystal polymer film is continuously heated to 84 ℃, the lamp beads are full bright. Thus, the critical temperature at which the P4 film exhibits electronic switching performance is 82 ℃.
Example 5
A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, in particular to a quaternary ammonium salt ionic liquid crystal polymer P5 containing 1-trimethylsilylimidazole group, the chemical structural formula of which is as follows:
the preparation method is the same as that of example 2, except that trimethyl silylimidazole is used instead of 1-butylimidazole in step 3.
The result of the test analysis of the ionic liquid crystal polymer P5 is as follows:
the infrared spectrum data of P5 is shown in FIG. 23, and the infrared spectrum data is: IR (KBr, cm)-1):3114,2924,2857,1728,1606,1500,1459,1421,1381,1262,1234,1212,1166,1108,1081,1028,1004,919,844,798,760。
The hydrogen nuclear magnetic spectrum of P5 is shown in FIG. 24, and the hydrogen nuclear magnetic spectrum data is as follows:
1H-NMR(DMSO-d6,δ,ppm):0.14-0.21(13.55H)；0.6-0.68(2.96H)；0.0.93-0.0.95(1.48H)；1.16-1.28(3.02H)；1.75-1.78(3.00H)；1.98-2.00(3.02H)；2.31-2.33(1.01H)；3.20-3.23(0.49H)；3.47-3.59(1.01H)；3.96-3.97(0.50H)；4.10-4.12(1.00H)；4.49-4.62(1.01H)；4.88-4.89(0.43H)；5.12-5.15(1.46H)；6.81-6.83(0.98H)；7.03-7.05(0.99H)；8.92(1.00H).
as can be seen from fig. 24: the chemical shift value and the peak intensity in the nuclear magnetic spectrum accord with the chemical structure, and the prepared substance is 1-trimethylsilylimidazolium bromide ion liquid crystal polymer P5 according to the infrared spectrum information.
A representative photograph of P5 is shown in FIG. 25, from which it can be seen that: the material has liquid crystal texture of smectic phase and nematic phase during the temperature rising process.
A P5 thin film with the thickness of 0.5mm, a 2W LED lamp bead and a 3V dry battery pack are connected into a series circuit through a lead, and the P5 thin film is placed on a temperature control hot table. The lamp beads are not bright at room temperature, the conductivity of the ionic liquid crystal polymer film is increased along with the increase of the temperature of the ionic liquid crystal polymer film, when the ionic liquid crystal polymer film is heated to 66 ℃, the lamp beads display weak bright light and twinkle, and when the ionic liquid crystal polymer film is continuously heated to 66 ℃, the lamp beads are full bright. Thus, the critical temperature at which the P5 film exhibits electronic switching performance is 66 ℃.
Claims (10)
1. A quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance is characterized in that the structural general formula of the quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance is as follows:
in the formula: b is cyclohexane
Phenyl radical
Dicyclohexyl alkyl
Or biphenyl
One of (1);
x and y are mole fractions in 1 mole of polymethylhydrosiloxane, 0< x <1, 0< y <1, and x + y is 1;
alkyl- (CH)2)mCH3Wherein m is an integer, and m is 1-9;
r is C1-C6 alkyl or 1-trimethylsilyl;
polysiloxane backbone based on average molecular weight Mn1,700-3,200 polymethylhydrosiloxane;
n is the number of silicon-hydrogen bonds in polymethylhydrosiloxane molecules, n is an integer, and n is 25-53; the number average molecular weight range of the quaternary ammonium salt ionic liquid crystal polymer with the temperature control electronic switch performance is 0.5-5 ten thousand.
2. The quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switching performance according to claim 1, wherein the alkyl group of C1-C6 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl or n-hexyl.
3. The quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switching performance according to claim 1, wherein the quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switching performance is an ionic liquid crystal polymer which is formed by grafting liquid crystal units on a polysiloxane main chain, and also grafting cations and bromide anions of imidazole units, and solid, smectic phase liquid crystal, nematic phase liquid crystal and liquid are sequentially generated along with the increase of temperature, wherein the quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switching performance has textures of smectic phase and nematic phase.
4. The preparation method of the quaternary ammonium salt ionic liquid crystal polymer with the temperature-controlled electronic switching performance as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
step 1: preparation of small molecule liquid crystal with terminal olefinic bond
The micromolecular liquid crystal with terminal group olefinic bond is prepared by allyloxybenzoyl chloride and monophenol intermediates through esterification reaction; or prepared by esterification reaction of allyloxybenzoyl chloride and hydroxyl-containing intermediate;
step 2: preparation of bromopolysiloxanes
The bromopolysiloxane is prepared by carrying out graft polymerization on micromolecular liquid crystal with terminal olefinic bond, bromopropylene and polymethylhydrosiloxane by adopting a platinum catalyst; wherein, the adding proportion of bromopropylene and micromolecular liquid crystal with terminal group olefinic bond is determined according to the proportion of x and y in the quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance; and the sum of the number of moles of bromopropylene and the number of moles of terminal ethylenic small molecular liquid crystals is equal to the number of moles of Si-H bonds in the polymethylhydrosiloxane;
and step 3: preparation of quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance
Taking bromopolysiloxane and 1-alkyl imidazole as raw materials, taking toluene as a solvent, and obtaining the following components in molar ratio: bromine element in brominated polysiloxane: 1-alkylimidazole ═ 1: (1-1.2) weighing raw materials, mixing the raw materials in a toluene solvent, carrying out microwave heating reflux reaction for 0.5-1 h, and carrying out reduced pressure distillation to remove the toluene solvent after the reaction is finished to obtain a crude product of the quaternary ammonium salt ionic liquid crystal polymer;
and adding acetone into the crude product of the quaternary ammonium salt ionic liquid crystal polymer, separating out, and filtering to obtain the quaternary ammonium salt ionic liquid crystal polymer with the temperature control electronic switch performance.
5. The method for preparing quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switch performance according to claim 4, wherein in the step 1, allyloxybenzoyl chloride is prepared by reacting allyloxybenzoic acid with thionyl chloride; the method specifically comprises the following steps:
the method comprises the following steps: preparation of allyloxybenzoic acids
(1) Molar ratio, p-hydroxybenzoic acid: potassium hydroxide: potassium iodide ═ 1: (2-3): (0.05-0.1) weighing raw materials, fully dissolving the raw materials in an ethanol-water mixed solvent, and dropwise adding bromopropylene with stirring, wherein the molar amount of the bromopropylene is equal to that of the p-hydroxybenzoic acid; after the dropwise addition is finished, uniformly stirring, and heating for reflux reaction for 16-32 hours;
(2) after the reflux reaction is finished, carrying out impurity removal post-treatment on the reaction liquid, carrying out solid-liquid separation, and recrystallizing a solid phase by using ethanol to obtain allyloxy benzoic acid;
step two: preparation of allyloxybenzoyl chloride
Dripping thionyl chloride into allyloxy benzoic acid at room temperature, wherein the molar ratio of the allyloxy benzoic acid: thionyl chloride is 1: (3-5); and after the dropwise addition is finished, stirring at room temperature for reaction for 2-3 h, then heating to 60-66 ℃ for reaction for 5-8 h, and after the reaction is finished, carrying out reduced pressure distillation to remove excessive thionyl chloride to obtain a yellow transparent liquid, namely allyloxybenzoyl chloride, and sealing for later use.
6. The preparation method of the quaternary ammonium salt ionic liquid crystal polymer with the temperature-controlled electronic switch performance as claimed in claim 4, wherein the monophenol intermediate is prepared by the following preparation method:
according to the functional group of B in the prepared quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, selecting a dihydric phenol compound, and dissolving the dihydric phenol compound and triethylamine in tetrahydrofuran to obtain a mixed solution; adding fatty acyl chloride into the mixed solution while stirring, reacting at room temperature for 2-3 h after the addition is finished, heating and refluxing for 16-32 h, removing impurities after the reflux reaction is finished, carrying out solid-liquid separation, and recrystallizing a solid phase by using acetone to obtain a monophenol intermediate, wherein the molar ratio of the fatty acyl chloride to the dihydric phenol compound to the triethylamine is 1: 3-5: 1;
the hydroxyl-containing intermediate is prepared by the following preparation method:
according to the functional group of B in the prepared quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance, dihydroxy alcohol compounds are selected, and the dihydroxy alcohol compounds and triethylamine are dissolved in tetrahydrofuran to obtain mixed liquor; dropwise adding fatty acyl chloride into the mixed solution with stirring, reacting at room temperature for 2-3 h after dropwise adding is completed, heating and performing reflux reaction for 16-32 h, removing impurities after the reflux reaction is completed, and recrystallizing a solid phase with acetone to obtain a monophenol intermediate; wherein the molar ratio of the fatty acyl chloride to the dihydroxy alcohol compound to the triethylamine is 1: 3-5: 1.
7. The method for preparing quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switching performance according to claim 6, wherein the dihydric phenol compound or the dihydric alcohol compound is one of 1, 4-cyclohexanediol, hydroquinone, 4 '-dihydroxydicyclohexyl and 4,4' -dihydroxybiphenyl;
the fatty acyl chloride is one of acetyl chloride, propionyl chloride, butyryl chloride, valeryl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride or decanoyl chloride;
and removing impurities, namely distilling a product after the reflux reaction to remove 1/2-4/5 volume of tetrahydrofuran, cooling residual liquid, mixing the residual liquid with 5 times of water, adding dilute hydrochloric acid to adjust the pH value to 3-5, carrying out solid-liquid separation, washing a filter cake for at least 2 times by using solid-phase ethanol, and recrystallizing by using acetone.
8. The preparation method of the quaternary ammonium salt ionic liquid crystal polymer with the temperature-controlled electronic switch performance as claimed in claim 4, wherein the small molecular liquid crystal with the terminal group ethylenic bond is prepared by the following preparation method, and the specific steps are as follows:
the monophenol intermediate or the hydroxyl group-containing intermediate as a raw material and triethylamine were dissolved in tetrahydrofuran, and allyloxybenzoyl chloride was added dropwise with stirring, wherein the molar ratio of allyloxybenzoyl chloride: monophenol intermediate or hydroxyl group-containing intermediate: triethylamine (1-1.5): 1: 1;
and after the dropwise addition is finished, reacting at room temperature for 2-3 h, heating and refluxing for 16-32 h, removing impurities after the refluxing reaction is finished, carrying out solid-liquid separation, and recrystallizing a solid phase by using ethanol to obtain the micromolecule liquid crystal with terminal olefinic bonds.
9. The method for preparing quaternary ammonium salt ionic liquid crystal polymer with temperature-controlled electronic switch performance according to claim 4, wherein in the step 2, the method for preparing brominated polysiloxane specifically comprises the following steps: under the protection of nitrogen, dissolving micromolecular liquid crystal of end group olefinic bond, bromopropylene and polymethylhydrosiloxane by using toluene, wherein the dosage of the toluene is controlled by taking the complete dissolution of the bromopropylene and the micromolecular liquid crystal of end group olefinic bond as a standard to obtain a mixed solution;
adding a platinum catalyst into the mixed solution, carrying out reflux reaction for 35-40 h under the protection of nitrogen, carrying out reduced pressure distillation to remove a toluene solvent of 3/4, mixing the residual liquid with methanol, separating out a precipitate, carrying out solid-liquid separation, washing a filter cake with ethanol, and drying to obtain bromopolysiloxane; wherein, the addition amount of the platinum catalyst is 0.01-1 percent of the mass of the polymethylhydrosiloxane.
10. A temperature-controlled electronic switch, characterized by being made of the quaternary ammonium salt ionic liquid crystal polymer with the temperature-controlled electronic switch performance as claimed in any one of claims 1 to 3.
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