CN117625206A - Liquid crystal composition with low viscoelastic ratio, high dielectric adjustability and low dielectric loss and high-frequency component - Google Patents
Liquid crystal composition with low viscoelastic ratio, high dielectric adjustability and low dielectric loss and high-frequency component Download PDFInfo
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- CN117625206A CN117625206A CN202210986294.4A CN202210986294A CN117625206A CN 117625206 A CN117625206 A CN 117625206A CN 202210986294 A CN202210986294 A CN 202210986294A CN 117625206 A CN117625206 A CN 117625206A
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- Prior art keywords
- liquid crystal
- crystal composition
- substituted
- alkyl
- carbon atoms
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 131
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 23
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 18
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Chemical group 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 25
- 230000004044 response Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- -1 fluorine-substituted benzene rings Chemical group 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DQTJNHXTFILGGG-UHFFFAOYSA-N 2,5-difluoro-4-iodoaniline Chemical compound NC1=CC(F)=C(I)C=C1F DQTJNHXTFILGGG-UHFFFAOYSA-N 0.000 description 2
- YNOOQIUSYGWMSS-UHFFFAOYSA-N 2,5-difluoroaniline Chemical compound NC1=CC(F)=CC=C1F YNOOQIUSYGWMSS-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- APGNXGIUUTWIRE-UHFFFAOYSA-N 4-Pentylphenylacetylene Chemical group CCCCCC1=CC=C(C#C)C=C1 APGNXGIUUTWIRE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- NJBYFURDPJRBPH-UHFFFAOYSA-N 1-ethynyl-4-(4-pentylcyclohexyl)benzene Chemical group C1CC(CCCCC)CCC1C1=CC=C(C#C)C=C1 NJBYFURDPJRBPH-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- C09K19/06—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
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- 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
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- 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
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- 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
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P1/00—Auxiliary devices
- H01P1/18—Phase-shifters
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- 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
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/122—Ph-Ph
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- 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
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
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- 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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- 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
- C09K2019/183—Ph-Ph-C≡C-Ph
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- 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
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3013—Cy-Ph-Cy
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- 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
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
- C09K2019/3062—Cy-C≡C-Ph
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- C09K19/06—Non-steroidal liquid crystal compounds
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Abstract
The invention discloses a liquid crystal composition with low viscoelastic ratio, large dielectric adjustability and low dielectric loss and a high-frequency component, wherein the liquid crystal composition comprises one or more compounds shown in a structural formula I; wherein R is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms, alkenyl, alkenyloxy, fluorinated alkenyl or fluorinated alkenyloxy with 2-10 carbon atoms, cycloalkyl or alkyl substituted by cycloalkyl with 3-8 carbon atoms; z is Z 1 、Z 2 Is a single bond, -C≡C-, -CH=CH-, -CF=CF-, -CH 2 CH 2 The method comprises the steps of carrying out a first treatment on the surface of the Ring A and ring B are benzene rings or cyclohexane and cyclohexene, wherein hydrogen on the benzene rings can be substituted by fluorine, chlorine, methyl and ethyl; n=0, 1. The liquid crystal composition not only obtains larger dielectric tuning rate, extremely low dielectric loss, low rotational viscosity and larger elastic constant under high frequency, but also has the advantages of wider nematic phase working temperature range, larger low-frequency dielectric constant and the like.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal composition and a high-frequency component comprising the same, which are mainly applicable to the fields of filters, adjustable frequency selection surfaces, microwave phase shifters, microwave phased array antennas and the like.
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.
By utilizing the property that the effective dielectric constant of the liquid crystal material changes with the action of an external electric field or a magnetic field, novel high-frequency (1 GHz-100 GHz) components based on the liquid crystal material, such as a microwave phase shifter based on the liquid crystal material and the like, are developed.
In a microwave phase shifter, the dielectric tuning rate (also referred to as dielectric tunable) of the liquid crystal materialSex) determines the tuning capability of the microwave device. The dielectric tuning rate (tau) of the liquid crystal material is determined by the dielectric anisotropy (delta epsilon) of the liquid crystal material at high frequency and the dielectric constant (epsilon) of the liquid crystal material in the direction parallel to the molecules ∥ ) The determination is as follows:
τ＝Δε/ε ∥
dielectric loss of a liquid crystal material is an important factor affecting the insertion loss of its microwave device. In order to obtain a high performance liquid crystal microwave device, the dielectric loss of the liquid crystal material must be reduced. For liquid crystal materials, the loss tangent varies with the liquid crystal molecular orientation and the electric field orientation, i.e. the loss varies between the major and minor axes of the liquid crystal molecules, and when calculating the loss of the liquid crystal material, the maximum value of the loss, i.e. max (tan delta ∥ ,tanδ ⊥ ) As a loss of liquid crystal material.
In order to comprehensively evaluate the performance parameters of the liquid crystal material under microwaves, a quality factor (eta) parameter is introduced:
η＝τ/max(tanδ ∥ ,tanδ ⊥ )
liquid crystal materials for high frequency components are required to have a large dielectric tuning rate (τ), low loss (tan δ ∥ ,tanδ ⊥ ) High quality factor (eta).
With the rapid development of high, medium and low orbit satellite communication technologies, a rapid microwave beam switching speed is required for a communication-in-motion antenna for tracking a low orbit satellite. Therefore, high frequency components based on liquid crystals must also have a fast response capability. The response speed of the liquid crystal is mainly determined by the cell thickness (d) of the liquid crystal device and the rotational viscosity (gamma) of the liquid crystal material 1 ) And elastic constant (K) 11 ) The following is shown:
wherein: t is t on For on (powered) responseTime t off For off (power off) response time; v (V) th The threshold voltage of the liquid crystal is V, and the applied driving voltage is V; in the case where the cell thickness d is fixed, in order to improve the response speed of the liquid crystal device, it is necessary that the liquid crystal material has a low rotational viscosity (γ 1 ) Large elastic constant (K) 11 ) I.e. low viscosity-to-elastic constant ratio (gamma 1 /K 11 )。
To meet the requirement that high frequency components operate under electric field drive, it is also desirable that the liquid crystal material have a suitable dielectric constant at low frequencies, e.g., 1 KHz.
In order to meet the practical application, the liquid crystal material for high-frequency components is required to have a wider working temperature range, for example, -20 to +90 ℃, and the low-temperature working temperature of the existing liquid crystal material is required to be improved.
Existing commercial high-birefringence liquid crystal materials, e.g. in Molecular Crystals and Liquid Crystals,2011, 542 (1): 196/[718]-203/[725]Materials such as E7 and E44 containing cyanobiphenyl and terphenyl liquid crystals have low dielectric tuning rate (τ) and low dielectric loss (tan δ) at high frequencies as reported in the paper titled "Characterisation and Applications of Nematic Liquid Crystals in Microwave devices ∥ ,tanδ ⊥ ) A major disadvantage.
In patent CN103443245a liquid crystal medium comprising a tolane-based liquid crystal material is disclosed, for example, of the structure shown in the following formula:
although the compound has a high quality factor at high frequencies, its rotational viscosity (gamma 1 ) Up to 2100mpa·s, leading to a drawback of slow response speed. Moreover, the dielectric anisotropy value of the compound is small at low frequency, and is only 0.8.
In patent CN 103429704A, a fluorophenylalkyne liquid crystal compound:
although the compound has a large birefringence (Δn=0.35), the compound has good performance at high frequencies, but the compound has a rotational viscosity gamma 1 =1300 mpa·s, resulting in a slow response speed.
CN107955630A, CN105368465a discloses a liquid crystal composition having NCS groups at the molecular terminals and fluorine-substituted benzene rings as the molecular skeleton, and has a large dielectric constant and tuning rate at high frequencies, but a large dielectric loss value; in the disclosed embodiment thereof, the maximum dielectric loss tan delta ⊥ (19 GHz) is above 0.01; while the rotational viscosity is greater.
CN110499163A, US2019292458A1 discloses liquid crystal compositions based on a molecular terminal NCS group and a molecular skeleton fluorine substituted benzene ring, in the disclosed embodiments, the maximum dielectric loss tan delta ⊥ (19 GHz) is more than or equal to 0.083; while the rotational viscosity is greater.
It can be found in the prior art that there is a discrepancy between the performance parameters of the liquid crystal materials used in microwaves. Some liquid crystals having low dielectric loss, their rotational viscosity and their rotational viscosity/elastic constant ratio (gamma 1 /K 11 ) Often too large to meet the requirements of a quick response. On the other hand, an increase in dielectric tunability also tends to result in an increase in rotational viscosity, further resulting in a decrease in response speed.
Disclosure of Invention
In order to overcome the defects or shortcomings of the prior art, the invention provides a liquid crystal composition with low viscoelastic ratio, large dielectric adjustability and low dielectric loss.
For this purpose, the liquid crystal composition provided by the invention comprises one or more compounds selected from the compounds shown in the structural general formula I:
wherein:
r is alkyl with 1-10 carbon atoms, alkyl with fluorine substituted hydrogen, alkoxy or alkoxy with fluorine substituted hydrogen; alkenyl having 2 to 10 carbon atoms, alkenyl in which hydrogen is substituted by fluorine, alkenyloxy, or alkenyloxy in which hydrogen is substituted by fluorine; or cycloalkyl having 3 to 8 carbon atoms, cycloalkyl having hydrogen substituted by fluorine, alkyl having cycloalkyl substituted by hydrogen, or alkyl having cycloalkyl substituted by hydrogen substituted by fluorine;
Z 1 is a single bond, -C≡C-, -CH=CH-, -CF=CF-, or-CH 2 CH 2 ；
Z 2 Is a single bond, -C≡C-, -CH=CH-, -CF=CF-, or-CH 2 CH 2 ；
Ring A is benzene ring, cyclohexane, cyclohexene or benzene ring with hydrogen substituted by fluorine, chlorine, methyl or/and ethyl; n=0 or 1;
ring B is a benzene ring, cyclohexane, cyclohexene or a benzene ring in which hydrogen is substituted by fluorine, chlorine, methyl or/and ethyl.
Optionally, the liquid crystal composition of the present invention comprises one or more compounds selected from the group consisting of compounds represented by structural formulas I-1 to I-8:
further, the liquid crystal composition of the invention further comprises one or more compounds selected from the group consisting of the structural formula II:
wherein: r is R 2 Is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group, a fluorinated alkenyl group or a fluorinated alkenyloxy group; or is halogen; or NCS;
R 3 is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group, a fluorinated alkenyl group or a fluorinated alkenyloxy group; or is halogen; or NCS;
ring C is a benzene ring, cyclohexane, cyclohexene or a benzene ring in which a hydrogen atom is substituted by a fluorine atom;
ring D is a benzene ring, cyclohexane, cyclohexene or a benzene ring in which a hydrogen atom is substituted with a fluorine atom.
Alternatively, the compound of formula II is selected from compounds of formula II-A, II-B or II-C:
further, the liquid crystal composition of the invention further comprises one or more compounds selected from the group consisting of the general structural formula III:
wherein:
R 1 is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group, a fluorinated alkenyl group or a fluorinated alkenyloxy group;
X 4 is H or F; x is X 5 Is H or F; x is X 6 Is H or F;
k is 0 or 1; m is 0 or 1; r is 0 or 1;
ring E is a benzene ring, cyclohexane or cyclohexene.
Alternatively, the mass ratio of the compound shown in the structural general formula I is 50% -100%, the mass ratio of the compound shown in the structural general formula II is 0% -40%, and the mass ratio of the compound shown in the structural general formula III is 0% -50%.
Further, the liquid crystal composition has a high frequency 19GHz vertical dielectric loss value tan delta ⊥ Less than or equal to 0.010, a quality factor eta of more than or equal to 30, rotational viscosity of less than or equal to 300 mPa.s and elastic constant K 11 ≥12pN。
The liquid crystal composition not only obtains larger dielectric tuning rate, extremely low dielectric loss, low rotational viscosity and larger elastic constant under high frequency, but also has the advantages of wider nematic phase working temperature range, larger low-frequency dielectric constant and the like. The liquid crystal composition of the invention can be used for preparing photoelectric display devices and high-frequency components.
Detailed Description
Unless specifically stated otherwise, scientific and technical terms herein have been understood based on knowledge within the ordinary skill of the relevant art.
In a preferred embodiment of the invention, the liquid crystal composition comprises one or more compounds of the general structural formula (I). In another preferred embodiment of the invention, the liquid crystal composition comprises one or more compounds of the general structural formula (I) and one or more compounds of the general structural formula (II). In a further 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 preferably comprises 50 to 100%, preferably 60 to 95%, more preferably 70 to 90% of the compound of formula I, based on the total amount of the mixture; and 0 to 40%, preferably 5 to 30%, particularly preferably 10 to 20%, by weight, based on the total amount of the mixture, of compounds of the general structural formula II. The liquid-crystal compositions according to the invention may also comprise from 0 to 50%, preferably from 5 to 40%, particularly preferably from 10 to 30%, based on the total amount of the mixture, of compounds of the general structural formula III. In particular, the skilled artisan can make optimization selections based on the disclosure of the present invention.
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 and still more preferably 7 to 15 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 preparation method of the compound shown in the general formula I comprises the following steps:
(1) Reacting 2, 5-difluoroaniline with a halogenating reagent to obtain 4-halogen substituted-2, 5-difluoroaniline;
(2) 4-halogen substituted-2, 5-difluoroaniline and aryl boric acid derivatives or derivatives containing terminal alkynyl are subjected to coupling reaction under the catalysis of transition metal to obtain biphenyl amine intermediates or alkynyl aniline intermediates;
(3) And (3) carrying out phosgenation reaction on the biphenylamine intermediate or the alkynyl aniline intermediate to obtain the isothiocyanate liquid crystal compound.
Wherein the halogenating agent in step (1) is selected from iodine, bromine or N-bromosuccinimide. The transition metal catalyst in the step (2) is selected from palladium or nickel-containing complexes.
Preparation of compounds of general formula i example 1: the synthesis of 2, 5-difluoro-1-isothiocyanate-4- ((4-n-amyl) ethynyl) benzene is carried out by the following specific method:
(1) Adding 12.9g of 2, 5-difluoroaniline, 100mL of dichloromethane and 8.4g of sodium bicarbonate into a reaction vessel, stirring at room temperature, adding 25.4g of iodine in batches, stirring for reaction overnight, separating an organic layer, washing with sodium bisulphite in a water-soluble manner, and washing with water to be neutral; concentrating to remove the solvent, and recrystallizing the obtained product with petroleum ether to obtain 19g of 2, 5-difluoro-4-iodoaniline;
(2) Under the protection of nitrogen, adding 12.8g of 2, 5-difluoro-4-iodoaniline, 100mL of triethylamine, 0.35g of diphenylphosphine palladium chloride, 0.29g of cuprous iodide and 0.39g of triphenylphosphine into a reactor, heating to 50 ℃, dropwise adding 30mL of triethylamine solution dissolved with 8.6g of 4-pentylphenyl acetylene, carrying out heat preservation reaction for 4 hours after the dropwise addition, cooling to room temperature, filtering, concentrating the filtrate to dryness, adding 100mL of toluene, washing with water, drying, removing the toluene under reduced pressure, adding petroleum ether, and recrystallizing to obtain 12.6g of brown solid;
(3) Adding 12.6g of brown solid obtained in the previous step, 100mL of chloroform and 25mL of water into a reaction vessel, cooling to below 5 ℃, slowly dropwise adding 7.2g of thiophosgene, heating to reflux for 2h after the dropwise adding is finished, cooling to room temperature, separating liquid, washing an organic layer with sodium bicarbonate aqueous solution, washing with water to be neutral, removing a solvent by reduced pressure distillation, purifying the obtained product by a silica gel column, eluting with n-heptane, recrystallizing the product with the n-heptane to obtain 10.9g of white solid with the gas chromatography purity of 99.9 percent.
The synthetic route of the method is as follows:
the product structure identification data are as follows:
1 H NMR(500MHz,CDCl 3 )δ(ppm):0.887(t,3H,J＝7Hz),1.265～1.339(m,4H),1.575～1.635(m,2H),2.604(t,2H,J＝7.5Hz),6.868(dd,1H,J 1 ＝8.5Hz,J 2 ＝6Hz),7.159(d,2H,J＝8.5Hz),7.229(dd,1H,J 1 ＝9.5Hz,J 2 ＝6.5Hz),7.429(d,2H,J＝8Hz)。
13 C NMR(125MHz,CDCl 3 )δ(ppm):14.0,22.6,30.9,31.5,36.0,80.5,97.5,111.9(dd,J 1 ＝18.5Hz,J 2 ＝8.5Hz),113.0(d,J＝26Hz),119.3,119.7(dd,J 1 ＝22Hz,J 2 ＝2.4Hz),120.9(dd,J 1 ＝16Hz,J 2 ＝11Hz),128.7,131.7,143.6,144.3,154.6(d,J＝250Hz),158.3(d,J＝250Hz).
MS m/z(RI,％):341.1(M + ,100),284.1(92)。
DSC：C 51.5N(44.9)I。
according to DSC test data, the liquid crystal compound is a single-phase liquid crystal, and a nematic phase appears when the temperature is reduced to 44.9 ℃.
Preparation of compounds of general formula i example 2: the synthesis of 2, 5-difluoro-1-isothiocyanate-4- ((4- (4-n-pentylcyclohexyl) phenyl) ethynyl) benzene is carried out by the following specific method:
preparation example 1 was replaced with 4- (4-n-pentylcyclohexyl) phenylacetylene, and the same synthesis as in preparation example 1 was repeated except for using 4-pentylphenylacetylene to obtain 2, 5-difluoro-1-isothiocyanate-4- ((4- (4-n-pentylcyclohexyl) phenyl) ethynyl) benzene.
The structural identification data are as follows:
1 H NMR(500MHz,CDCl 3 )δ(ppm):0.896(t,3H,J＝7.5Hz),1.002～1.084(m,2H),1.197～1.352(m,9H),1.391～1.474(m,2H),1.864～1.885(m,4H),2.474(t,3H,J＝12Hz),6.898(dd,1H,J 1 ＝8.5Hz,J 2 ＝6.5Hz),7.198(d,2H,J＝8Hz),7.252(dd,1H,J 1 ＝9.5Hz,J 2 ＝6.0Hz),7.447(d,2H,J＝8.5Hz).
13 C NMR(125MHz,CDCl 3 )δ(ppm)：14.1,22.7,26.7,32.2,33.5,34.1,37.3,37.4,44.7,80.4,97.5,112.0(dd,J 1 ＝19Hz,J 2 ＝10Hz),113.1(d,J＝26Hz),119.3,119.7(dd,J 1 ＝22Hz,J 2 ＝4.5Hz),120.9(dd,J 1 ＝21Hz,J 2 ＝14Hz),127.1,131.8,143.5,149.5,154.7(d,J＝252.5Hz),158.3(d,J＝265Hz).
MS m/z(RI,％):423.2(M + ,100.0),310.1(11.6),297.1(39.3),284.1(25.1),252.1(13.1).
DSC：C 61.5N 236.3I。
according to DSC test data, the nematic phase temperature range of the liquid crystal compound reaches 174.8 ℃.
Other specific compounds of formula I can be prepared by selecting the corresponding starting materials based on the disclosure of the preparation method described above.
Compared with the high-frequency liquid crystal composition based on isothiocyanato disclosed in the present literature, the compound with the structural general formula I is characterized in that two fluorine atom substituents are arranged at the 2, 5-positions of a benzene ring connected with-NCS. The compound with the structural general formula I not only has extremely reduced dielectric loss and larger dielectric anisotropy, but also has the excellent characteristics of low viscosity, larger elastic constant and wider liquid crystal phase area.
The molecular structure of the structural general formula II is composed of 2 rings, has the characteristics of low viscosity, low melting point and low dielectric loss, can further improve the low-temperature compatibility of the liquid crystal composition, greatly reduces the viscosity of the liquid crystal composition, and simultaneously reduces the dielectric loss.
The preferred specific structure of the components of formula II is as follows:
the general formula II-A is more preferably a specific compound of the formula:
the general formula II-B is further preferably a compound of the following structure:
the general formulae II to C are further preferably compounds of the following structure:
the preferred specific structure of the compound of the general structural formula III in the composition of the invention is as follows:
the compound with the structural general formula III in the composition has a wider liquid crystal phase range, lower viscosity and larger dielectric constant, particularly has larger dielectric constant at low frequency of 1KHz, and can play a role in adjusting the liquid crystal phase range and the dielectric constant of the composition at low frequency.
In a further embodiment, the liquid crystal composition according to the present invention may further comprise 0.001 to 1% of an additive selected from the group consisting of hindered phenol antioxidants and/or hindered amine light stabilizers. Wherein the hindered phenolic antioxidant is preferably selected from the following structures:
wherein R' is an alkyl group or an alkoxy group having 1 to 9 carbon atoms.
The hindered amine light stabilizer is preferably selected from the following structures:
the preferred mass percentage of the hindered phenol antioxidant and the amine light receiving stabilizer in the liquid crystal composition is 0.01-0.5%, and more preferably 0.02-0.2%.
In still further embodiments, the liquid crystal composition of the present invention may further comprise one or more chiral additives in an amount of 0.01% to 1%; preferably 0.1 to 0.5%. The chiral additive is preferably selected from the following structures:
wherein R' is: alkyl or alkoxy having 1 to 9 carbon atoms.
The tuning rate tau of the liquid crystal composition is more than or equal to 0.25, and more preferably more than or equal to 0.28; preferred liquid crystal materials have a vertical dielectric loss tan delta ⊥ Less than or equal to 0.010, more preferably tan delta ⊥ Less than or equal to 0.009; the quality factor eta is more than or equal to 30, preferably eta is more than or equal to 40. The preferred liquid crystal composition of the present invention has a nematic phase temperature range of 0 to 90℃or more, and more preferably has a nematic phase temperature range of-10 to 100℃or more; preferred rotational viscosity gamma of liquid crystal composition 1 Less than or equal to 300 mPas, more preferably less than or equal to 280 mPas; elastic constant K of preferred liquid crystal composition 11 More preferably at least 12pN, more preferably K 11 Not less than 14pN; preferred liquid crystal composition gamma 1 /K 11 Less than or equal to 18, more preferably gamma of the liquid crystal composition 1 /K 11 And is less than or equal to 17. The preferred liquid crystal composition has a dielectric constant of 6.0 or more, more preferably 7.0 or more at low frequencies of 1 KHz.
The liquid crystal composition according to the present invention is suitable for the preparation of high frequency components, such as microwave components, more particularly phase shifters which can be tuned by an externally applied magnetic or electric field. These phase shifters may operate in the UHF-band (0.3-1 GHz), the L-band (1-2 GHz), the S-band (2-4 GHz), the C-band (4-8 GHz), the X-band (8-12 GHz), the Ku-band (12-18 GHz), the K-band (18-27 GHz), the Ka-band (27-40 GHz), the V-band (50-75 GHz), the W-band (75-110 GHz) and at most 1 THz. The construction of phase shifters according to the present application is known to the expert. Typically a loaded line shifter, inverted microstrip line, fin line (Finline) shifter, preferably Antipodal (Antipodal) fin line shifter, slotted shifter, microstrip line shifter or coplanar waveguide (CPW) shifter is used. These components may implement a reconstructed antenna array.
The liquid crystal composition herein has properties (dielectric constant, dielectric loss) at high frequencies using literature (Penirschke, a. (2004). Cavity perturbation method for characterization of liquid crystals up to GHz).Microwave Conference,2004.34th EuropeanTest methods reported: liquid crystal was introduced into Polytetrafluoroethylene (PTFE) or fused silica capillaries, and the filled capillaries were introduced into the middle of the chamber having a resonance frequency of 19 GHz. 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 alignment of the liquid crystal in a magnetic field, the direction of the magnetic field is set accordingly, and then rotated by 90 ° accordingly.
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 physical properties and the photoelectric properties of the mixed liquid crystal in the following examples were tested, and the detailed test method of the physical properties and the photoelectric properties related to the invention is as follows:
(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 placed in a transparent glass bottle 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 code numbers and descriptions are given in tables 1-3 below:
TABLE 1 physical parameters
| (Code) | Description of the invention | Unit (B) |
| T ni | Clearing point | ℃ |
| LTS | Low temperature storage temperature | ℃ |
| ε ⊥ | Dielectric constant perpendicular to director | |
| ε ∥ | Dielectric constant parallel to director | |
| Δε | Dielectric anisotropy | |
| tanδ ⊥ | Dielectric loss tangent perpendicular to director | |
| tanδ ∥ | Dielectric loss tangent perpendicular to director | |
| Δn | Birefringence index | |
| γ 1 | Rotational viscosity | mPa·s |
| K 11 | Elastic constant of splay | pN |
| K 33 | Flexural spring constant | pN |
| τ | Dielectric tuning rate | |
| η | Quality factor |
TABLE 2 abbreviations for building blocks herein
Table 3 Structure abbreviations exemplify
Example 1:
table 4 example 1 composition and properties
The monomeric liquid crystal component in example 1 is selected from liquid crystal compounds of the general structural formula I. The test performance shows that the liquid crystal display device has a wider liquid crystal phase temperature region, a larger dielectric tuning rate, lower dielectric loss, low rotational viscosity and a larger elastic constant. The liquid crystal composition of example 1 had a low rotational viscosity/elastic constant ratio (γ 1 /K 11 ) Has favorable response speed.
Example 2:
table 5 example 2 composition and properties
The monomer liquid crystal component in example 2 is selected from liquid crystal compounds represented by structural formulas I, II and III. The test performance shows that the liquid crystal display device has a wider liquid crystal phase temperature region, a larger dielectric tuning rate, lower dielectric loss, extremely low rotational viscosity and a larger elastic constant. The liquid crystal composition of example 2 had an extremely low rotational viscosity/elastic constant ratio (γ 1 /K 11 ) Has very favorable response speed.
Example 3:
TABLE 6 example 3 compositions and Properties
The monomeric liquid crystal component in example 3 is selected from liquid crystal compounds of general structural formulae I, II. The test performance shows that the liquid crystal display device has a wider liquid crystal phase temperature region, a larger dielectric tuning rate, extremely low dielectric loss, low rotational viscosity and a large elastic constant. The liquid crystal composition of example 3 had an extremely low rotational viscosity/elastic constant ratio (γ 1 /K 11 ) Has favorable response speed.
Comparative example 1:
this comparative example differs from example 1 above in that the corresponding monomer liquid crystal was replaced with a prior known 2, 6-difluoro-substituted NCS monomer liquid crystal, and the performance test data thereof are shown in Table 7 below.
TABLE 7
Example 1 compared with comparative example 1, the clear point of the liquid crystal was 24℃higher, the birefringence increased, the rotational viscosity decreased, the elastic constant increased, and the viscoelastic ratio (. Gamma.) 1 /K 11 ) Greatly reduces; the high-frequency dielectric anisotropy value at 19GHz is also obviously increased, and the dielectric loss is greatly reduced; the dielectric tuning rate of the liquid crystal is increased, and the quality factor is greatly increased.
Comparative example 2:
a liquid crystal composition for high frequency components, the components of which are selected from 2, 6-difluoro-substituted isothiocyanato liquid crystal compounds, is disclosed in US2019292458 A1. In its example N4, the following compositions and performance parameters of table 8 are disclosed:
TABLE 8
The liquid crystal component in comparative example 2 was an isothiocyanato liquid crystal compound substituted with 2, 6-difluoro entirely. Compared with the embodiments 1-3 of the invention, the dielectric loss of the comparative example 2 is large, and the quality factor is low; at the same time, the rotational viscosity is high, the rotational viscosity/elastic constant (gamma 1 /K 11 ) Much higher than the embodiments of the present invention.
Claims (10)
1. A liquid crystal composition having a low viscoelastic ratio, high dielectric tunability and low dielectric loss, comprising one or more compounds selected from the group consisting of compounds of formula i:
wherein:
r is alkyl with 1-10 carbon atoms, alkyl with fluorine substituted hydrogen, alkoxy or alkoxy with fluorine substituted hydrogen; alkenyl having 2 to 10 carbon atoms, alkenyl in which hydrogen is substituted by fluorine, alkenyloxy, or alkenyloxy in which hydrogen is substituted by fluorine; or cycloalkyl having 3 to 8 carbon atoms, cycloalkyl having hydrogen substituted by fluorine, alkyl having cycloalkyl substituted by hydrogen, or alkyl having cycloalkyl substituted by hydrogen substituted by fluorine;
Z 1 is a single bond, -C≡C-, -CH=CH-, -CF=CF-, or-CH 2 CH 2 ；
Z 2 Is a single bond, -C≡C-, -CH=CH-, -CF=CF-, or-CH 2 CH 2 ；
Ring A is benzene ring, cyclohexane, cyclohexene or benzene ring with hydrogen substituted by fluorine, chlorine, methyl or/and ethyl; n=0 or 1;
ring B is a benzene ring, cyclohexane, cyclohexene or a benzene ring in which hydrogen is substituted by fluorine, chlorine, methyl or/and ethyl.
2. The liquid crystal composition according to claim 1, comprising one or more compounds selected from the group consisting of compounds represented by structural formulae I-1 to I-8:
3. the liquid crystal composition according to claim 1, further comprising one or more compounds selected from the group consisting of structural formula ii:
wherein: r is R 2 Is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group, a fluorinated alkenyl group or a fluorinated alkenyloxy group; or is halogen; or NCS;
R 3 is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group, a fluorinated alkenyl group or a fluorinated alkenyloxy group; or is halogen; or NCS;
ring C is a benzene ring, cyclohexane, cyclohexene or a benzene ring in which a hydrogen atom is substituted by a fluorine atom;
ring D is a benzene ring, cyclohexane, cyclohexene or a benzene ring in which a hydrogen atom is substituted with a fluorine atom.
4. A liquid crystal composition according to claim 3, wherein the compound of formula ii is selected from compounds of formulae ii-a, ii-B or ii-C:
5. a liquid crystal composition according to claim 1 or 3, further comprising one or more compounds selected from the group consisting of compounds of the general structural formula iii:
wherein:
R 1 is alkyl, alkoxy or fluorinated alkyl with 1-10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group, a fluorinated alkenyl group or a fluorinated alkenyloxy group;
X 4 is H or F; x is X 5 Is H or F; x is X 6 Is H or F;
k is 0 or 1; m is 0 or 1; r is 0 or 1;
ring E is a benzene ring, cyclohexane or cyclohexene.
6. The liquid crystal composition according to claim 1, wherein the mass ratio of the compound represented by the general structural formula I is 50% to 100%, the mass ratio of the compound represented by the general structural formula II is 0% to 40%, and the mass ratio of the compound represented by the general structural formula III is 0% to 50%.
7. The liquid crystal composition according to claim 1, wherein the liquid crystal composition has a high frequency 19GHz vertical dielectric loss value tan delta ⊥ Less than or equal to 0.010, a quality factor eta of more than or equal to 30, rotational viscosity of less than or equal to 300 mPa.s and elastic constant K 11 ≥12pN。
8. Use of the liquid crystal composition according to claim 1 for the preparation of electro-optical and display devices.
9. Use of the liquid crystal composition according to claim 1 for the preparation of high frequency components.
10. A high frequency component, characterized in that it is produced using the liquid crystal composition according to any one of claims 1 to 7.
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