CN117660019A - Liquid crystal compound with high birefringence, synthesis method, liquid crystal composition and application - Google Patents
Liquid crystal compound with high birefringence, synthesis method, liquid crystal composition and application Download PDFInfo
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- CN117660019A CN117660019A CN202211012117.2A CN202211012117A CN117660019A CN 117660019 A CN117660019 A CN 117660019A CN 202211012117 A CN202211012117 A CN 202211012117A CN 117660019 A CN117660019 A CN 117660019A
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- liquid crystal
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 138
- 150000001875 compounds Chemical class 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011737 fluorine Chemical group 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- -1 4-bromophenyl alcohol derivative Chemical class 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000000460 chlorine Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical group BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 claims description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- LFABNOYDEODDFX-UHFFFAOYSA-N bis(4-bromophenyl)methanone Chemical class C1=CC(Br)=CC=C1C(=O)C1=CC=C(Br)C=C1 LFABNOYDEODDFX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
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- 230000015572 biosynthetic process Effects 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KUVVJHBHRIXJKI-UHFFFAOYSA-N 3-fluoro-4-iodoaniline Chemical compound NC1=CC=C(I)C(F)=C1 KUVVJHBHRIXJKI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- STYJKBMRWQQJIS-UHFFFAOYSA-N 1-(4-bromophenyl)pentan-1-one Chemical compound CCCCC(=O)C1=CC=C(Br)C=C1 STYJKBMRWQQJIS-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- ZERQUOCILMRYJE-SNAWJCMRSA-N 1-bromo-4-[(e)-pent-1-enyl]benzene Chemical compound CCC\C=C\C1=CC=C(Br)C=C1 ZERQUOCILMRYJE-SNAWJCMRSA-N 0.000 description 2
- ODHFBTMYTBFTAQ-VOTSOKGWSA-N 1-ethynyl-4-[(E)-pent-1-enyl]benzene Chemical group CCC\C=C\c1ccc(C#C)cc1 ODHFBTMYTBFTAQ-VOTSOKGWSA-N 0.000 description 2
- VYMCYYVUEUCQIF-UHFFFAOYSA-N 1-phenyl-2-(2-phenylethynyl)benzene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1C1=CC=CC=C1 VYMCYYVUEUCQIF-UHFFFAOYSA-N 0.000 description 2
- DQTJNHXTFILGGG-UHFFFAOYSA-N 2,5-difluoro-4-iodoaniline Chemical group NC1=CC(F)=C(I)C=C1F DQTJNHXTFILGGG-UHFFFAOYSA-N 0.000 description 2
- DTBDAFLSBDGPEA-UHFFFAOYSA-N 3-Methylquinoline Natural products C1=CC=CC2=CC(C)=CN=C21 DTBDAFLSBDGPEA-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HOIDKJFWEVIJAT-UHFFFAOYSA-N 1-(4-bromophenyl)butan-1-one Chemical group CCCC(=O)C1=CC=C(Br)C=C1 HOIDKJFWEVIJAT-UHFFFAOYSA-N 0.000 description 1
- UOMOSYFPKGQIKI-UHFFFAOYSA-N 1-(4-bromophenyl)propan-1-one Chemical group CCC(=O)C1=CC=C(Br)C=C1 UOMOSYFPKGQIKI-UHFFFAOYSA-N 0.000 description 1
- CHXXMQJPYOKYSB-UHFFFAOYSA-N 3,5-difluoro-4-iodoaniline Chemical group NC1=CC(F)=C(I)C(F)=C1 CHXXMQJPYOKYSB-UHFFFAOYSA-N 0.000 description 1
- ONZHMGRKWJMTDE-UHFFFAOYSA-N 3-chloro-4-iodoaniline Chemical group NC1=CC=C(I)C(Cl)=C1 ONZHMGRKWJMTDE-UHFFFAOYSA-N 0.000 description 1
- UISBOJCPTKUBIC-UHFFFAOYSA-N 4-iodo-3-methylaniline Chemical group CC1=CC(N)=CC=C1I UISBOJCPTKUBIC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
-
- 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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- 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
- C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
- C09K19/0216—Super Birefringence Effect (S.B.E.); Electrically Controlled Birefringence (E.C.B.)
-
- 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
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
- C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
- C09K2019/181—Ph-C≡C-Ph
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
- C09K2019/188—Ph-C≡C-Ph-C≡C-Ph
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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
- C09K2219/11—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 High Frequency technical field
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a liquid crystal compound with high double refractive index, a synthesis method, a liquid crystal composition and application thereof, wherein the structural general formula of the liquid crystal compound is shown as formula I; the disclosed liquid crystal composition comprises one or more compounds shown as a general formula I; the liquid crystal compound and the composition thereof have the advantages of ultrahigh birefringence, lower viscosity and wide nematic phase temperature range, and can be used for preparing photoelectric devices and microwave devices.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal compound with a wide liquid crystal phase temperature range, a high birefringence and a low viscosity, a synthesis method thereof, a composition containing the liquid crystal compound and related applications.
Background
Liquid crystal materials are widely used in electro-optical display devices, such as various liquid crystal televisions, desktop liquid crystal displays, mobile display terminals, and the like.
Applications other than display of liquid crystals are also important. By utilizing the birefringence characteristics of the liquid crystal, an optical phase modulation device based on the liquid crystal can be manufactured. The method is favorable for dielectric constant difference of liquid crystal at high frequency, and microwave and terahertz phase shifters, metamaterial holographic phased array antennas and the like based on liquid crystal materials are developed. In addition, liquid crystal materials also have great application potential in the field of laser communication, for example, liquid crystal-based wavelength selective switches have been used in 5G/6G optical communication.
The development of these new components requires liquid crystal materials with high birefringence, low viscosity and wide liquid crystal temperature range. The higher the birefringence of the liquid crystal material is, the more the phase modulation amount is increased; and the thickness of the liquid crystal device is reduced, so that the response speed of the liquid crystal is improved. The lower the viscosity of the liquid crystal is, the response time is advantageously shortened, and the response speed is improved.
Thus, for new component applications, new liquid crystal materials with birefringence (589 nm) greater than 0.4, and even greater than 0.5, are needed. The liquid crystal having an isothiocyanate group (NCS) at the molecular end has a large birefringence due to a large conjugated group. The literature (xiannyu, h., gauza, s.et al, high birefringence and large negative dielectric anisotropy phenyl-tolane liquid Crystals,2007,34 (12): 1473-1478) reports NCS liquid Crystals comprising a phenyldiphenylacetylene backbone, which have a high rotational viscosity, although their birefringence is close to 0.5.
Literature (Catanecu, C.O., S. -T.Wu, et al, tailored the physical properties of some high birefringence isothiocyanato-based liquid Crystals,2004,31 (4): 541-555) reports that NCS liquid crystal compounds containing olefinic end groups conjugated to benzene rings have higher birefringence, but a nematic liquid crystal phase temperature region is relatively narrow; and when the liquid crystal structure is applied to a microwave frequency band, the dielectric loss of the liquid crystal structure is found to be larger, and the liquid crystal structure needs to be further improved.
Disclosure of Invention
In view of the shortcomings or drawbacks of the prior art, the present invention provides, in one aspect, a liquid crystal compound having a high birefringence.
Therefore, the structure of the liquid crystal compound provided by the invention is shown as a general formula I:
wherein: r is selected from hydrogen, fluorine, chlorine or alkyl with 1-10 carbon atoms;
X 1 ～X 4 independently fluorine, chlorine, hydrogen or methyl; and when X 1 =hydrogen and X 3 When=hydrogen, X 2 And X 4 One or both of which are not fluorine atoms.
Optionally, the structure of the liquid crystal compound is shown in any one of the structures of the general formulas I-1 to I-5:
the invention also provides a synthesis method of the liquid crystal compound. The provided synthesis method comprises the following steps:
(1) Reducing the 4-bromophenyl ketone derivative into a 4-bromophenyl alcohol derivative in the presence of a reducing agent sodium borohydride or potassium borohydride;
(2) Reacting the 4-bromophenyl alcohol derivative with hydrochloric acid or hydrobromic acid to convert the halogen substituent;
(3) Reacting the halogen substituent with a base to eliminate a portion of hydrogen halide and obtain 4-bromobenzene substituted alkene;
(4) Reacting 4-bromobenzene substituted alkene with an ethynylation reagent under palladium catalysis to obtain phenylacetylene derivatives; the ethynylation reagent is selected from trimethylsilyl acetylene or 2-methylbutynyl alcohol;
(5) Under the action of alkali, the phenylacetylene derivative eliminates trimethylsilyl or acetone to obtain phenylacetylene intermediate;
(6) Coupling the phenylacetylene intermediate with iodized or brominated aniline under palladium catalysis to obtain a diphenylacetylene intermediate;
(7) The reaction of the diphenylacetylene intermediate with thiophosgene gives the liquid crystal compound of claim 1.
The synthetic reaction equation is shown as follows:
the synthesis method has the advantages of low-cost and easily available raw materials, mild reaction conditions and good selectivity.
The invention also provides a liquid crystal composition. To this end, a liquid crystal composition is provided comprising a first component comprising one or more liquid crystal compounds selected from those of formula I.
Optionally, the first component comprises one or more liquid crystal compounds selected from the group consisting of liquid crystal compounds represented by any of the structures of formulas I-1 to I-5.
Further, the liquid crystal composition further comprises a second component, wherein the second component comprises one or more liquid crystal compounds of the structural general formula II:
wherein: r is R 2 Selected from alkyl groups having 1 to 10 carbon atoms; x is X 8 And X 9 Independently fluorine or hydrogen.
Further, the liquid crystal composition further comprises a third component, wherein the third component comprises one or more liquid crystal compounds of the structural general formula II:
wherein:
R 1 is alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorinated alkyl with 2-10 carbon atoms, fluorinated alkenyl with 2-10 carbon atoms or cycloalkyl with 2-10 carbon atoms; x is X 5 、X 6 And X 7 Independently fluorine, chlorine, hydrogen, methyl or ethyl;
k. m, n and p are independently 0 or 1;
ring A is benzene ring, cyclohexane or cyclohexene; when R is 1 Is alkenyl or fluorinated alkenyl, and ring A is a benzene ring, wherein at least one ethylene (-CH) is spaced between the olefinic bond and the benzene ring 2 -)。
Optionally, the mass ratio of the first component is 1-100%, the mass ratio of the second component is 0-90%, and the mass ratio of the third component is 0-90%.
Preferably, the liquid crystal composition has a birefringence of greater than 0.40 at 25 ℃ and 589 nm.
Preferably, the liquid crystal composition has a rotational viscosity of less than 500 mPa-s at 25 ℃.
Preferably, dielectric anisotropy delta epsilon of the liquid crystal composition at high frequency 19GHz is more than or equal to 1.4; the adjustability is more than or equal to 0.34.
The liquid crystal composition has extremely high birefringence, wide nematic liquid crystal temperature range, low rotational viscosity, large dielectric tuning rate at high frequency and low dielectric loss. The liquid crystal composition of the invention can be used for preparing optical elements. Is particularly suitable for preparing microwave components. The method is mainly applicable to the fields of optical devices, microwave phase shifters, microwave phased array antennas, laser phase modulation, laser phased arrays, laser communication and the like.
Detailed Description
Unless specifically stated otherwise, scientific and technical terms herein have been understood based on the knowledge of one of ordinary skill in the relevant art.
In a preferred embodiment of the invention, the liquid crystal composition comprises one or more compounds selected from the group consisting of the compounds of the general structural formula I, one or more compounds selected from the group consisting of the compounds of the general structural formula II. In another preferred embodiment of the invention, the liquid crystal composition comprises one or more compounds of the general structural formula (I), one or more compounds of the general structural formula (II) and one or more compounds of the general structural formula (III).
The liquid crystal composition according to the invention comprises 1% to 100%, preferably 10% to 90%, more preferably 20% to 80% of the compound of formula I, based on the total amount of the mixture. The liquid crystal composition of the present invention comprises 0 to 90%, preferably 10 to 70%, particularly preferably 20 to 60% by weight of the total amount of the mixture of the compound of the general structural formula II. The liquid-crystal compositions according to the invention also comprise from 0 to 90%, preferably from 10 to 70%, particularly preferably from 20 to 60%, by weight, based on the total amount of the mixture, of compounds of the general structural formula III. Those skilled in the art can optimize the selection of specific combinations and ratios within the scope of the disclosure.
The liquid crystal composition according to the present invention may further comprise 0.001% to 1% of an additive such as a hindered phenol-based antioxidant, an amine-based light stabilizer, etc. Wherein the hindered phenolic antioxidant is preferably selected from the following structures:
wherein: r is R 3 Is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
The hindered amine light stabilizer is preferably selected from the following structures:
the preferable addition amount of the hindered phenol antioxidant and the amine light receiving stabilizer is 0.01 to 0.5%, and more preferably 0.02 to 0.2%.
The liquid crystal composition of the invention can also contain one or more chiral additives, and the content is 0.01% -1%; preferably 0.1 to 0.5%. The chiral additive is preferably selected from the following structures:
wherein R is 4 Is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
The liquid crystal composition according to the present invention is composed of a plurality of compounds, preferably 3 to 20 compounds, more preferably 5 to 18 compounds. These compounds can be mixed in a conventional manner: weighing various compounds according to a preset mass ratio, heating and raising the temperature, and simultaneously, carrying out homogeneous mixing by adopting a magnetic stirring mode or an ultrasonic stirring mode and the like until all components are completely dissolved; and filtering to obtain the final product. The liquid crystal compositions may also be prepared in other conventional ways, for example using so-called premixes, or using so-called "multi-bottle" systems in which the ingredients themselves are ready-to-use mixtures.
The performance of liquid crystal at high frequency is tested by a test method reported in literature: penirschke, A. (2004) Cavity perturbation method for characterization of liquid crystals up to GHz.Microwave Conference,2004.34th European.
Liquid crystal is poured into Polytetrafluoroethylene (PTFE) or fused quartz capillaries, and the capillaries filled with liquid crystal are inserted into the middle of the resonance chamber. The input signal source is then applied and the result of the output signal is recorded with a vector network analyzer. The change in the resonance frequency and Q factor between the capillary filled with liquid crystal and the blank capillary was measured, and the dielectric constant and loss tangent were calculated. The permittivity components perpendicular and parallel to the liquid crystal directors are obtained by the orientation of the liquid crystal in a magnetic field, the direction of which is set accordingly, and then rotated by 90 ° accordingly.
The preferred liquid crystal composition of the invention preferably has high-frequency dielectric anisotropy delta epsilon of more than or equal to 1.4; the adjustability is more than or equal to 0.35. The dielectric constant of the liquid crystal composition is more than or equal to 10.0 at low frequency of 1KHz, and more preferably more than or equal to 12.0.
The liquid crystal composition according to the present invention is very suitable for preparing a microwave component, and can operate in UHF-band (0.3-1 GHz), L-band (1-2 GHz), S-band (2-4 GHz), C-band (4-8 GHz), X-band (8-12 GHz), ku-band (12-18 GHz), K-band (18-27 GHz), ka-band (27-40 GHz), V-band (50-75 GHz), W-band (75-110 GHz) and at most 1 THz. The construction of metamaterial phased array antennas according to the present application is known to the expert.
An optical element according to the present application, for example, a laser phase modulation element operating at 1550nm, a wavelength selective switch, or the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples, and it is apparent that the described examples are only some of the examples of the present invention, but not all of the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention will be described in further detail with reference to specific examples.
And testing physical properties and photoelectric properties of the mixed liquid crystal. The invention relates to a detailed test method for physical properties and photoelectric properties, which comprises the following steps:
(1) Clearing point (Tni):
polarized light heat stage method: the liquid crystal sample was coated on a glass slide and placed in an orthogonal polarized light microhotplate, and the heating rate was set to 2 ℃/min. And observing the temperature of the liquid crystal sample from a bright state to black in a polarizing microscope, namely, a clear point.
Or differential scanning calorimetry: the temperature rising rate was set at 2℃per minute under a nitrogen atmosphere.
(2) Low temperature storage temperature (LTS): about 1mL of the mixed liquid crystal was put into a transparent glass bottle (abbreviated as "in bottle") or into a 5 μm antiparallel box (abbreviated as "in cell") and placed in a low temperature refrigerator. The temperature is set at-20 ℃,30 ℃ below zero and 40 ℃ below zero, and the temperature is respectively stored for 120 hours, 500 hours and 1000 hours, and whether crystal precipitation or smectic phase exists or not is observed. If no crystal is precipitated at-30 ℃, the LTS is less than or equal to-30 ℃.
(3) Birefringence (Δn): the Abbe refractometer is adopted, a light source 589nm is adopted under the constant temperature condition of 25 ℃, and the ordinary light (n o ) And extraordinary ray (n e ) Is of the order of (1), birefringence Δn=n e －n o 。
(4) Dielectric constant (Δε): under the constant temperature condition of 25 ℃, an LCR table is adopted for testing. Delta epsilon=epsilon ∥ -ε ⊥ I.e. the dielectric constant in the direction of the long axis of the molecule (. Epsilon.) ∥ ) Dielectric constant (ε) in the short axis direction of molecules ⊥ ) Is a difference in (c).
(5) Spring constant (K) 11 ，K 33 ): under the constant temperature condition of 25 ℃, K is obtained by testing a liquid crystal capacitance-voltage (C-V) curve and fitting 11 And K 33 。
(6) Rotational viscosity (. Gamma.) 1 ): under the constant temperature condition of 25 ℃, the transient current value Ip of the deflection of liquid crystal molecules along with the movement of an electric field is tested by applying voltage to a liquid crystal test box, and the rotational viscosity gamma is calculated 1 。
The designations and descriptions herein are given in tables 1-3 below:
TABLE 1 physical parameters
Table 2 Structure abbreviations
Table 3 abbreviations for example
Liquid crystal phase transition temperature: c represents the melting point, S represents the smectic phase, N represents the nematic phase, and Iso represents the liquid state.
Example 1:
this example is the synthesis of 2-fluoro-4-isothiocyanato-1- ((4- (E-1-n-pentenyl) phenyl) ethynyl) benzene
The synthetic route and method are as follows:
step one:
24.1g of 4-pentanoyl-1-bromobenzene and 100mL of ethanol are added into a reaction vessel, and 1.51g of sodium borohydride is slowly added in batches under the stirring of 0-10 ℃; naturally heating to room temperature for reaction for 2h, and evaporating ethanol under reduced pressure;
step two:
slowly adding 100mL of 10% hydrochloric acid into the product obtained in the step one, stirring at room temperature for reaction for 2 hours, separating an oil layer, washing with water to be neutral, and drying to obtain oily liquid;
step three:
adding the product obtained in the step two, 100mL of absolute ethyl alcohol and 11.2g of potassium hydroxide into a reaction container, heating and refluxing for reaction for 2 hours, steaming out ethanol, slowly adding 200mL of water and 100mL of petroleum ether into the product, separating out an organic layer, washing with water to be neutral, drying, and removing the solvent completely to obtain 20.2g of E-4-pentenyl-1-bromobenzene with the yield of 90%;
step four:
under the protection of nitrogen, adding 11.3g of E-4-pentenyl-1-bromobenzene, 100mL of triethylamine and catalyst (0.35 g of bis (triphenylphosphine) palladium chloride, 0.29g of cuprous iodide and 0.39g of triphenylphosphine) into a reaction vessel, heating to 50 ℃, dropwise adding 50mL of triethylamine solution dissolved with 9.8g of trimethylsilylacetylene, continuing to react for 4h after dropwise adding, cooling to room temperature, filtering, decompressing and evaporating the filtrate to remove the triethylamine, passing the product through a silica gel column, eluting with petroleum ether, and obtaining 10.9g of oily liquid;
step five:
under the protection of nitrogen, adding 10.9g of the product obtained in the previous step, 50mL of ethanol and 1.4g of potassium carbonate into a reaction vessel, stirring at room temperature for reaction for 4 hours, evaporating ethanol under reduced pressure, adding 50mL of petroleum ether and 50mL of water, separating an organic layer, washing with water to be neutral, and concentrating to obtain 7.6g of (E) -4-pentenyl phenylacetylene;
step six:
under the protection of nitrogen, adding 7.1g of 3-fluoro-4-iodoaniline, 100mL of triethylamine (reaction solvent), 0.21g of bis (triphenylphosphine) palladium chloride, 0.17g of cuprous iodide and 0.24g of triphenylphosphine into a reaction vessel, heating to 40-50 ℃, dropwise adding 50mL of triethylamine solution in which 5.1g of (E) -4-pentenyl phenylacetylene is dissolved, continuing to react for 4 hours after dropwise adding, cooling to room temperature, filtering, decompressing and steaming the filtrate to remove triethylamine, adding 100mL of toluene, adding 100mL of saturated ammonium chloride aqueous solution, washing, separating out an organic layer, concentrating and steaming to remove toluene, and recrystallizing a product by petroleum ether to obtain brown solid 6.7g;
step seven:
6.7g of the reaction product of the last step, 100mL of acetone and 10mL of water are added into a reaction vessel, 3.7g of thiophosgene is slowly added dropwise at room temperature, stirring is continued for 2h after the addition, the acetone is distilled off, 100mL of toluene is added, the water is washed to be neutral, the toluene is distilled off under reduced pressure, and the product is subjected to a silica gel column and eluted by petroleum ether. The crude product was recrystallized from n-heptane 2 times to give 5.8g of white solid with a liquid chromatography purity of 99.9%.
And (3) structural identification:
1 H NMR(500MHz,CDCl 3 )δ(ppm):0.958(t,J＝7.5Hz,3H),1.467～1.540(m,2H),2.203(q,J＝7.5Hz,2H),6.254～6.312(m,1H),6.371(d,J＝16Hz,1H),6.974(dd,J 1 ＝16Hz,J 2 ＝8Hz,2H),7.323(d,J＝8.5Hz,2H),7.443～7.474(m,3H).
13 C NMR(125MHz,CDCl 3 )δ(ppm):13.8,22.5,35.2,82.1,96.8,111.6,113.1,113.3,120.5,121.8,125.9,129.3,131.9,132.7,134.0,138.2,138.6,162.5(d,J＝250Hz).
MS m/z(RI,％):321.1(M + ，100)，292.1(20)，234.1(61)，233.1(80).
the phase transition temperature was measured by DSC: c82.4n141.7iso.
The monomer liquid crystal was added to the base formula HOST at a ratio of 15%, and tested at 25℃to give a birefringence Δn=0.535, rotational viscosity γ 1 ＝220mPa·s。
Example 2:
this example is the synthesis of 2-chloro-4-isothiocyanato- ((4-E- (1-pentenyl) phenyl) ethynyl) benzene
The same procedure as in example 1 was followed except that 3-fluoro-4-iodoaniline as the starting material in step five was replaced with 3-chloro-4-iodoaniline; synthesis gave 3VPTP (Cl-3) S.
And (3) structural identification:
1 H NMR(500MHz,CDCl 3 )δ(ppm):0.958(t,J＝7.5Hz,3H),1.467～1.537(m,2H),2.202(q,J＝7.5Hz,2H),6.254～6.312(m,1H),6.371(d,J＝16Hz,1H),7.071(dd,J 1 ＝8Hz,J 2 ＝2Hz,1H),7.278(d,J＝2Hz,1H),7.324(d,J＝8.5Hz,2H),7.426～7.449(m,3H).
13 C NMR(125MHz,CDCl 3 )δ(ppm):13.8,22.5,35.2,85.7,96.8,120.5,122.5,124.0,125.9,126.4,129.3,131.6,132.0,132.7,133.7,136.7,138.3,138.7.
MS m/z(RI,％):339.2(38)，337.2(M + 100.0), 308.1 (29), 273.1 (37), 215.1 (72), phase transition temperature by DSC: c47.6n113.5iso.
The monomer liquid crystal is added into the basic formula HOST according to the proportion of 15 percent, and the mixture is prepared byThe birefringence delta n=0.502 and the rotational viscosity gamma are obtained by testing at 25 DEG C 1 ＝328mPa·s。
Example 3:
this example is the synthesis of 2-methyl-4-isothiocyanato- ((4-E- (1-pentenyl) phenyl) ethynyl) benzene
The same procedure as in example 1 was followed except that 3-fluoro-4-iodoaniline as the starting material in step five was replaced with 3-methyl-4-iodoaniline; synthesizing to obtain 3VPTP (M-3) S.
And (3) structural identification:
1 H NMR(500MHz,CDCl 3 )δ(ppm):0.957(t,J＝7.5Hz,3H),1.465～1.538(m,2H),2.200(q,J＝7.5Hz,2H),2.469(s,3H),6.240～6.299(m,1H),6.367(d,J＝16Hz,1H),7.003(dd,J 1 ＝8Hz,J 2 ＝2Hz,1H),7.072(s,1H),7.314(d,J＝8Hz,1H),7.324(d,J＝8.5Hz,2H),7.418～7.441(m,3H).
13 C NMR(125MHz,CDCl 3 )δ(ppm):13.8,22.5,35.2,82.1,96.8,111.6(d,J＝15Hz),113.2(d,J＝24Hz),120.5,121.8,125.9,129.3,131.9,132.1(d,J＝11Hz),132.7,134.0,138.2,138.6,162.5(d,J＝250Hz).
MS m/z(RI,％):317.2(M + ，100.0)，288.1(16)，230.2(25)，215.1(37).
the phase transition temperature was measured by DSC: c85.9n110.4iso.
The monomer liquid crystal is added into a basic formula HOST according to the proportion of 15 percent, and the birefringence delta n=0.518 and the rotational viscosity gamma are obtained by testing at 25 DEG C 1 ＝345mPa·s。
Example 4:
this example is the synthesis of 2, 5-difluoro-4-isothiocyanate group- ((4-E- (1-butenyl) phenyl) ethynyl) benzene
By the same method as in example 1, 4-pentanoyl-1-bromobenzene in step 1 was replaced with 4-butyryl-1-bromobenzene, and 3-fluoro-4-iodoaniline as the starting material in step five was replaced with 2, 5-difluoro-4-iodoaniline; synthesizing to obtain 2VPTXS.
And (3) structural identification:
1 H NMR(500MHz,CDCl 3 )δ(ppm):1.002(t,J＝7Hz,3H),2.119～2.173(m,2H),6.189～6.274(m,2H),6.672(dd,J 1 ＝8.5Hz,J 2 ＝6Hz,1H),7.122(dd,1H,J 1 ＝9.5Hz,J 2 ＝6.5Hz),7.210(d,J＝8.5Hz,2H),7.339(d,J＝8Hz,2H).
13 C NMR(125MHz,CDCl 3 )δ(ppm):13.5,26.2,81.4,97.5,111.8(dd,J 1 ＝18.5Hz,J 2 ＝8.5Hz),113.0(d,J＝26Hz),119.3,119.6(dd,J 1 ＝22Hz,J 2 ＝2.4Hz),120.1,121.0(dd,J 1 ＝16Hz,J 2 ＝11Hz),126.0,128.2,132.0,134.5,138.9,143.6,154.6(d,J＝250Hz),158.3(d,J＝250Hz).
MS m/z(RI,％):325.1(M + ，10.0)，310.1(18)，251.2(38)，251.2(54).
the phase transition temperature was measured by DSC: c86.8 N123.6 Iso.
The monomer liquid crystal is added into a basic formula HOST according to the proportion of 15 percent, and the birefringence delta n=0.528 and the rotational viscosity gamma are obtained by testing at 25 DEG C 1 ＝192mPa·s。
Example 5:
this example is the synthesis of 2, 5-difluoro-4-isothiocyanate group- ((4-E- (1-butenyl) phenyl) ethynyl) benzene
The same procedure as in example 1 was followed except that 3-fluoro-4-iodoaniline as the starting material in step five was replaced with 2, 5-difluoro-4-iodoaniline; synthesizing to obtain the 3VPTXS.
And (3) structural identification:
1 H NMR(500MHz,CDCl 3 )δ(ppm):0.945(t,3H,J＝7.5Hz),1.363～1.425(m,2H),1.617～1.663(m,2H),2.652(t,2H,J＝8Hz),6.189～6.274(m,2H),6.672(dd,J 1 ＝8.5Hz,J 2 ＝6Hz,1H),7.122(dd,1H,J 1 ＝9.5Hz,J 2 ＝6.5Hz),7.210(d,J＝8.5Hz,2H),7.339(d,J＝8Hz,2H).
13 C NMR(125MHz,CDCl 3 )δ(ppm):13.8,22.4,35.2,81.3,97.5,111.8(dd,J 1 ＝19Hz,J 2 ＝9Hz),113.1(d,J＝26Hz),119.6(d,J＝23Hz),120.1,121.0(dd,J 1 ＝19Hz,J 2 ＝9Hz),126.0,129.3,132.0,132.9,138.9,143.6,154.7(d,J＝250Hz),158.3(d,J＝250Hz).
MS m/z(RI,％):339.1(M + ，100)，310.1(32)，252.1(58)，251.1(78).
the phase transition temperature was measured by DSC: c82.0 N130.3 Iso.
The monomer liquid crystal is added into a basic formula HOST according to the proportion of 15 percent, and the birefringence delta n=0.520 and the rotational viscosity gamma are obtained by testing at 25 DEG C 1 ＝214mPa·s。
Example 6:
this example is the synthesis of 2, 6-difluoro-4-isothiocyanate group- ((4-E- (1-propenyl) phenyl) ethynyl) benzene
The same procedure used in example 1 was repeated except that 4-pentanoyl-1-bromobenzene in step 1 was replaced with 4-propionyl-1-bromobenzene and 3-fluoro-4-iodoaniline as the starting material in step five was replaced with 3, 5-difluoro-4-iodoaniline; synthesis gave 1VPTUiS.
And (3) structural identification:
1 H NMR(500MHz,CDCl 3 )δ(ppm):1.898(d,J＝3Hz,3H),6.262～6.332(m,1H),6.388(d,J＝16Hz,1H),6.800(d,J＝7Hz,2H),7.307(d,J＝8Hz,2H),7.476(d,J＝8Hz,2H).
13 C NMR(125MHz,CDCl 3 )δ(ppm):18.6,75.7,101.1,102.3(t,J＝21Hz),109.3,109.5,120.2,125.8,127.6,130.5,132.0,132.2(t,J＝14Hz),138.9,139.9,162.8,(d,J＝254Hz).
MS m/z(RI,％):311.2(M + ，100)，252.2(12)，251.2(20).
the phase transition temperature was measured by DSC: and C111.7N 159.9 Iso.
The monomer liquid crystal is added into a basic formula HOST according to the proportion of 10 percent, and the birefringence delta n=0.569 and the rotational viscosity gamma are obtained by testing at 25 DEG C 1 ＝152mPa·s。
Example 7:
the mass ratio of each monomer and the property data of the liquid crystal composition of this example are shown in Table 4.
TABLE 4 example 7 liquid crystal compositions and Properties
Example 8:
the mass ratio of each monomer and the property data of the liquid crystal composition of this example are shown in Table 5.
TABLE 5 example 8 liquid crystal compositions and Properties
Example 9:
the mass ratio of each monomer and the performance data of the liquid crystal composition of this example are shown in Table 6.
TABLE 6 example 9 liquid crystal compositions and Properties
Comparative example 1:
isothiocyanate-type Liquid crystal compounds having a conjugated olefin chain with a benzene ring are reported in publication journal Liquid Crystals,2004,31 (4): 541-555. The typical molecular structure is shown below:
compared with the embodiment 1 of the invention, each benzene ring has one fluorine substituent, and the difference is that the substitution positions of fluorine are different; the liquid crystal phase transition temperature and the birefringence are tested, and the comparison data are shown in the following table 7:
TABLE 7
The table shows that after the fluorine substitution position of the liquid crystal compound is changed, the liquid crystal clearing point is obviously raised, and the nematic phase temperature zone is enlarged; the birefringence is also significantly improved.
Comparative example 2:
isothiocyanate-type Liquid crystal compounds having a conjugated olefin chain with a benzene ring are reported in publication journal Liquid Crystals,2004,31 (4): 541-555. The typical molecular structure is shown below:
compared with the embodiment 5 of the invention, two fluorine substituents are arranged on the benzene ring, and the difference is that the substitution positions of fluorine are different; the liquid crystal phase transition temperature and the birefringence are tested, and the comparison data are shown in the following table 8:
TABLE 8
| Project | Monomer liquid crystal | Liquid crystal phase transition temperature (DEG C) | Nematic thermal region (. Degree. C.) | Birefringence (Deltan) |
| Comparative example 2 | 3VPTUS | C63.3 N 108.0 Iso | 44.7 | 0.501 |
| Example 5 | 3VPTXS | C82.0 N 130.3 Iso | 48.3 | 0.520 |
The table shows that after the fluorine substitution position of the liquid crystal compound is changed, the liquid crystal clearing point is obviously raised, and the nematic phase temperature zone is enlarged; the birefringence is obviously improved.
Comparative example 2 liquid crystal compound 3VPTUS and example 5 liquid crystal compound 3VPTXS were prepared according to 15:85 and M0 to obtain liquid crystal compositions M1 and M2.
Liquid crystal composition M0: is composed of a monomer liquid crystal compound shown in the following Table 9.
TABLE 9
| Monomer liquid crystal | Mass ratio/% |
| 2CPUS | 25 |
| 3CPUS | 25 |
| 5CPUS | 25 |
| 3CCV | 25 |
M0 to M2 were poured into a polytetrafluoroethylene tube, respectively, and the dielectric constant and loss tangent at 19GHz were measured by cavity perturbation at 25℃and the quality factor was calculated, and the results are shown in Table 10 below.
Table 10
| Composition and method for producing the same | Liquid crystal compound | ε ⊥ | ε ∥ | Δε | tanδ ⊥ | tanδ ∥ | η |
| M0 | - | 2.361 | 2.989 | 0.628 | 0.0106 | 0.0049 | 19.82 |
| M1 | 3VPTUS | 2.515 | 3.294 | 0.779 | 0.0116 | 0.0052 | 20.38 |
| M2 | 3VPTXS | 2.513 | 3.295 | 0.782 | 0.0108 | 0.0051 | 21.97 |
It can be seen that the compound of example 5 of the present invention has a higher activity at 19GHz than the compound of comparative example 2Low dielectric loss value tan delta ⊥ And a larger dielectric anisotropy value Δε, while the quality factor significantly increases η.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (13)
1. A liquid crystal compound with high birefringence, which is characterized in that the structure of the liquid crystal compound is shown as a general formula I:
wherein: r is selected from hydrogen, fluorine, chlorine or alkyl with 1-10 carbon atoms;
X 1 ～X 4 independently fluorine, chlorine, hydrogen or methyl; and when X 1 =hydrogen and X 3 When=hydrogen, X 2 And X 4 One or both of which are not fluorine atoms.
2. The liquid crystal compound according to claim 1, wherein the structure of the liquid crystal compound is represented by any one of the general formulae i-1 to i-5:
3. the method for synthesizing a liquid crystal compound according to claim 1, comprising:
(1) Reducing the 4-bromophenyl ketone derivative into a 4-bromophenyl alcohol derivative in the presence of a reducing agent sodium borohydride or potassium borohydride;
(2) Reacting the 4-bromophenyl alcohol derivative with hydrochloric acid or hydrobromic acid to convert the halogen substituent;
(3) Reacting the halogen substituent with a base to eliminate a portion of hydrogen halide and obtain 4-bromobenzene substituted alkene;
(4) Reacting 4-bromobenzene substituted alkene with an ethynylation reagent under palladium catalysis to obtain phenylacetylene derivatives; the ethynylation reagent is selected from trimethylsilyl acetylene or 2-methylbutynyl alcohol;
(5) Under the action of alkali, the phenylacetylene derivative eliminates trimethylsilyl or acetone to obtain phenylacetylene intermediate;
(6) Coupling the phenylacetylene intermediate with iodized or brominated aniline under palladium catalysis to obtain a diphenylacetylene intermediate;
(7) The reaction of the diphenylacetylene intermediate with thiophosgene gives the liquid crystal compound of claim 1.
4. A liquid crystal composition comprising a first component comprising one or more liquid crystal compounds selected from the group consisting of claim 1.
5. The liquid crystal composition according to claim 4, wherein the first component comprises one or more liquid crystal compounds selected from the group consisting of claim 2.
6. The liquid crystal composition of claim 4, further comprising a second component comprising one or more liquid crystal compounds of formula ii:
wherein: r is R 2 Selected from alkyl groups having 1 to 10 carbon atoms; x is X 8 And X 9 Independently fluorine or hydrogen.
7. The liquid crystal composition of claim 6, further comprising a third component comprising one or more liquid crystal compounds of formula ii:
wherein:
R 1 is alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorinated alkyl with 1-10 carbon atoms, fluorinated alkenyl with 2-10 carbon atoms or cycloalkyl with 3-10 carbon atoms; x is X 5 、X 6 And X 7 Independently fluorine, chlorine, hydrogen, methyl or ethyl;
k. m, n and p are independently 0 or 1;
ring A is benzene ring, cyclohexane or cyclohexene; when R is 1 Is alkenyl or fluorinated alkenyl, and when ring A is a benzene ring, R 1 At least one ethylene group is spaced between the olefinic bond and the benzene ring.
8. The liquid crystal composition according to claim 4, 6 or 7, wherein the first component is 1 to 100% by mass, the second component is 0 to 90% by mass, and the third component is 0 to 90% by mass.
9. The liquid crystal composition of claim 4, 6 or 7, wherein the liquid crystal composition has a birefringence of greater than 0.40 at 25 ℃ and 589 nm.
10. The liquid crystal composition according to claim 4, 6 or 7, characterized in that the liquid crystal composition has a rotational viscosity of less than 500 mPa-s at 25 ℃.
11. The liquid crystal composition according to claim 4, 6 or 7, wherein the liquid crystal composition has dielectric anisotropy Δε of 1.4 or more at a high frequency of 19 GHz; the adjustability is more than or equal to 0.34.
12. Use of a liquid crystal composition according to claim 4, 6 or 7 for the preparation of an optical element.
13. Use of a liquid crystal composition according to claim 4, 6 or 7 for the preparation of a microwave assembly.
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