CN110117277B - 一种负性液晶单体及制备方法 - Google Patents
一种负性液晶单体及制备方法 Download PDFInfo
- Publication number
- CN110117277B CN110117277B CN201910067759.4A CN201910067759A CN110117277B CN 110117277 B CN110117277 B CN 110117277B CN 201910067759 A CN201910067759 A CN 201910067759A CN 110117277 B CN110117277 B CN 110117277B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- monomer
- preparation
- reaction
- negative liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 49
- 239000000178 monomer Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 31
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- DNFDDDWPODPCHU-UHFFFAOYSA-N 2-bromo-6-fluorophenol Chemical compound OC1=C(F)C=CC=C1Br DNFDDDWPODPCHU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- AVGYMQGMWJDFLU-UHFFFAOYSA-N 1-bromo-3-fluoro-2-phenylmethoxybenzene Chemical compound FC1=CC=CC(Br)=C1OCC1=CC=CC=C1 AVGYMQGMWJDFLU-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VNXUIRXHRSJUNQ-UHFFFAOYSA-N bromoethane;triphenylphosphane Chemical compound CCBr.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VNXUIRXHRSJUNQ-UHFFFAOYSA-N 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- NVIGFYPVKZNNAZ-UHFFFAOYSA-N (4-butoxy-2,3-difluorophenyl)boronic acid Chemical compound CCCCOC1=CC=C(B(O)O)C(F)=C1F NVIGFYPVKZNNAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- ZECMXCUBDBPZEO-UHFFFAOYSA-N 1-ethenyl-4-(iodomethyl)cyclohexane Chemical compound ICC1CCC(C=C)CC1 ZECMXCUBDBPZEO-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- WNJSZOGOYJDJMP-UHFFFAOYSA-N ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 WNJSZOGOYJDJMP-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- -1 aryl boric acid Chemical compound 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/08—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing alicyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3411—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a three-membered ring
-
- 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于液晶化合物技术领域,具体公开了一种结构式(I)所示的负性液晶单体,此单体含有环氧乙烷和含氟二苯并呋喃类负介电各向异性液晶单体。该单体具有良好的负介电各向异性,其制备原料在液晶行业通用,适用于大规模生产。
Description
技术领域
本发明属于液晶化合物技术领域,具体地说,涉及一种负性液晶单体及制备方法。
背景技术
近十几年液晶显示技术得到了迅速的发展,液晶显示产品在人们普通生活得到了快速普及。新型液晶显示方式主要有光学补偿弯曲模式(OCB)、共面转变液晶显示(IPS)、垂直取向模式(VA)、轴对称微结构液晶显示(ASM)、多畴扭曲液晶显示等。各种显示方式液晶盒的设计不同、驱动方式不同,液晶分子指向矢和玻璃基板方向不同,光学补偿弯曲模式(OCB)、共面转变液晶显示(IPS)液晶分子指向矢和玻璃基板方向是平行的,而垂直取向模式(VA)、轴对称微结构液晶显示(ASM)在无电场状态下液晶分子指向矢和玻璃基板方向垂直。平行排列方式的IPS,液晶的介电各向异性(Δε)既可以是正的,也可以是负的。
垂直取向模式(VA)所有液晶分子在零场时和玻璃基板方向垂直,与垂直入射光线平行。当偏振片正交时,会显示良好的暗态,所以该类器件有良好的对比度,用到液晶的介电各向异性(Δε)必须是负的。液晶的光学各向异性(Δη)、液晶盒的厚度(d)、入射光的波长(λ)几乎影响不到对比度。垂直取向模式(VA)的响应时间比扭曲型器件要短得多,约为一半左右。在外加电压影响下,VA器件主要产生的是液晶分子的弯曲形变,ECB产生的是液晶分子的展曲形变,而扭曲显示产生的是液晶分子的扭曲形变,其响应时间也分别与弯曲、展曲、扭曲弹性常数成反比,由于大部分的液晶在通常的情况下液晶的弯曲弹性常数大于展曲弹性常数,展曲弹性常数又大于扭曲弹性常数,这也是VA器件响应时间较快的原因。
为了能使显示器件的性能更加接近理想化,人们一直在致力于研究新的液晶化合物,这得以使液晶化合物及显示器件的性能仍在不断的向前发展。近几年,侧位含氟,含氰等多种负性材料在液晶混合物中得到了大量应用。但液晶材料领域的研发仍远未完成,为了改进液晶显示器元件的性能,不断尝试以研发能够优化这种显示器的新化合物。
有鉴于此特提出本发明。
发明内容
本发明要解决的技术问题在于克服现有技术的不足,提供一种含有环氧乙烷和含氟二苯并呋喃类负介电各向异性液晶化合物。该化合物有良好的负介电各向异性,其制备原料在液晶行业通用,适用于大规模生产。
为解决上述技术问题,本发明第一目的提供一种负性液晶单体其结构式如式(I)所示:
其中,R1、R2各自独立为H、Cl、F、-OCF3、-OCF2H、C1-C10的烷基或烷氧基、C1-C10的氟代直链烷基、C2-C10的直链烯基或烯氧基、C2-C10的氟代直链烯烃基、C1-C15的烷基酰氧基或芳基酰氧基、含烷基取代基或氟取代基的芳烃基、含有或无取代基的环丙基或环丁基或环戊基或环己环、其它含取代基的含氧或氮的五元或六元杂环基;
n1为0或1;
Z1、Z2各自独立为单键、—CH2—、—(CH2)2—、—(CH2)4—、—CH2O—、—CF2O—、—CH2=CH2—、—OCH2—或—OCF2—;
环A为1,4-亚苯基、1,4-亚环己基、1~4个氢原子被氟取代的1,4-亚苯基、
进一步的,R1、R2各自独立为H或C1-C10的烷基或烷氧基。
进一步的,Z1、Z2各自独立为单键、—CH2—、—CH2O—或—OCH2—;环A为1,4-亚苯基火1,4-亚环己基。
进一步的,所述单体的结构为以下式(Ia)~式(Ic)中的任意一种:
进一步的,所述单体的结构为以下式(Id)~式(If)中的任意一种:
进一步的,所述单体的结构式为式(Ig)~式(Ik)中的任意一种:
其中R为C1-C4的直链烷基或者烷氧基。
本发明第二目的提供一种液晶组合物,所述液晶组合物包括上述所述液晶单体的一种或多种。
本发明第三目的提供一种上述液晶单体或液晶组合物在制备液晶显示材料或电光学显示材料中的应用。
本发明的第四目的在于提供一种上述液晶单体的制备方法,所述制备方法为式(II)所示的稀类单体与间氯过氧苯甲酸发生反应制得,反应方程式为:
反应方程式中的M-CPBA表示间氯过氧苯甲酸。
进一步的,将式(II)所示的稀类单体降温至-2~2℃后加入间氯过氧苯甲酸,然后在0~10℃下反应2~4h,在室温下反应4~6h,再经过滤、洗涤、干燥制得式(I)所示单体。
所述的含烯键类单体制备技术为液晶行业内通用成熟路线和工艺条件。烯类单体可由液晶行业通用制备技术先制备式(III)所示的醛,然后witttig反应制备烯类单体,反应方程式如下:
采用上述技术方案后,本发明与现有技术相比具有以下有益效果:该化合物单体具有良好的负介电各向异性,其制备原料在液晶行业通用,适用于大规模生产。
附图说明
图1为实施例1的产物T-1的质谱分析图;
图2为实施例2的产物T-2的质谱分析图;
图3为实施例2的产物T-2的核磁氢谱图;
图4为实施例3的产物T-2的质谱分析图;
图5为实施例3的产物T-2的核磁氢谱图;
图6为实施例4的产物T-2的质谱分析图;
图7为实施例4的产物T-2的核磁氢谱图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对实施例中的技术方案进行清楚、完整地描述,以下实施例用于说明本发明,但不用来限制本发明的范围。
本实施例中以通用中间体Z为基础,分别按照合成路线一至三来合成本发明的单体。反应结束后的后处理一般是水洗、提取、合并有机相后干燥、减压下蒸除溶剂,以及重结晶,柱层析,本领域的技术人员都能按照下面的描述来实现本发明。
合成路线一:
n1为0,z1和z2均为单键,步骤为:
(1)中间体Z在惰性气体保护下与催化剂反应生成酮类中间体Z-1;
(2)中间体Z-1在催化剂和惰性气体条件下发生Witting反应,生成稀类中间体Z-2;
反应方程式为:
合成路线二:
n1为1,环A为1,4-亚环己基,z1为—CH2O—、z2为单键,步骤为:
(1)中间体Z和硼酸三甲酯在惰性气体和催化剂条件下生成芳基硼酸中间体Z-3;
(2)中间体Z-3与双氧水发生氧化反应,生成酚类中间体Z-4;
反应方程式为:
合成路线三:
n1为1,环A为1,4-亚环己基,z1为单键、z2为单键,步骤为:
(2)中间体Z-6在酸性条件下反应,生成中间体Z-7;
(3)中间体Z-7在氢气条件下发生加成反应,生成中间体Z-8;
(4)中间体Z-8与甲酸反应,生成酮类中间体Z-9;
(5)中间体Z-9在催化剂和惰性气体条件下发生Witting反应,生成稀类中间体Z-10;
(6)中间体Z-10在酸性条件下反应,生成酮类中间体Z-11;
(7)中间体Z-11在催化剂和惰性气体条件下发生Witting反应,生成稀类中间体Z-12;
反应方程式如下:
(1)
(2)
实施例1:
步骤1:中间体A-3的制备:
在1L反瓶内投入95.5g 2-氟-6-溴苯酚,103g碳酸钾,300ml DMF(N,N-二甲基甲酰胺),升温到60℃,滴加65g苄氯,然后60-70℃保温12小时。降至室温加入600ml水,用500ml甲苯提取,后续水洗干燥蒸馏处理后,得到138g 3-氟-2-苄氧基溴苯。
在2L反应瓶内投入138g 3-氟-2-苄氧基溴苯,126g 4-丁氧基-2,3-二氟苯硼酸,69g碳酸钾,150ml乙醇,300ml水。氮气保护下,加入0.2g催化剂pd-132,然后加热回流8小时。降至室温下,甲苯提取,经过后处理得到黄色液体(中间体A-1)174g;
在1L高压釜内投入174g中间体A-1,8g 5%钯炭,400ml无水乙醇,氢气压力保持0.5Mpa,温度30-40℃,反应8小时后,反应完毕,过滤去除钯炭,蒸干溶剂得131g黄色固体(中间体A-2)。加入100ml石油醚打浆抽滤,得到103g白色固体,纯度97.6%;
在1L反应瓶内投入103g中间体A-2,96g碳酸钾,600ml DMF,氮气保护下,加热到140-150℃保温过夜。反应完毕后,降至室温,加水稀释使用甲苯提取。经过后处理之后得到87g红色固体。经过石油醚过硅胶柱脱色,再用乙醇结晶提纯得到79g白色固体(中间体A-3),纯度99.6%,熔点68.3℃。
步骤2:
在500ml反应瓶内加入中间体(A-3)27.6g,四甲基乙二胺12g,四氢呋喃200ml,氮气保护下,降温到-78℃,滴加丁基锂(2.5mol/L)45ml,加完-70~-80℃保温1小时,然后滴加15g硼酸三甲酯。加完逐渐升至室温搅拌5小时。酸性水解后,加入乙酸乙酯提取,水洗等后处理后,得到白色固体。经过1倍甲苯和2倍石油醚打浆纯化之后得到白色固体(中间体B-1)25.9g,纯度96.5%;
在反应瓶内加入白色固体(中间体B-1)25.9g,100ml四氢呋喃,搅拌下控温0℃左右,滴加20%双氧水27g。加完室温搅拌过夜。料液经过提取,还原水洗处理,蒸干溶剂得到浅黄色固体(中间体B-2)21g,纯度97.3%。
步骤(3)
向15克中间体B-2中加入13.8克碳酸钾,100毫升DMF,升温到70℃搅拌30分钟,然后滴加4-乙烯基环己基甲基碘17.5克。然后70-80℃反应6小时。降至室温经过处理提纯得到产物乙烯(B-3),使用乙醇结晶提纯得到12.1克乙烯产物(B-3),纯度99.5%;
将乙烯(B-3)12.1克加入100毫升二氯甲烷,搅拌降温到0℃,分批加入间氯过氧苯甲酸(折纯)10.3克,控温0-10℃搅拌2小时,室温搅拌5小时。反应完毕,过滤。滤液用100毫升饱和亚硫酸钠溶液洗涤一次,然后再100毫升水洗一次。分液后,加入无水硫酸钠干燥,过硅胶柱,蒸干溶剂,得到白色固体。经过甲苯和乙醇混合溶剂提纯后得到单体(T-1),纯度99.5%,熔点149℃。质谱分析图如图1所示,分析产物为目标产物。
实施例2
实施例3
步骤(1)中间体A-3的制法与实施例1相同。
步骤(2)
反应器内加入25g中间体A-3,加入120ml干燥四氢呋喃,加入10g四甲基乙二胺。氮气保护下降温到-70~-80℃,滴加0.1mol丁基锂(约2.5mol/L),保温1小时。-70~-80℃滴加12g中间体C-1和50ml四氢呋喃溶液。加完,逐步恢复室温搅拌2小时。经过盐酸酸化,甲苯提取处理,得到300ml甲苯料液;
反应器中加入甲苯料液(中间体C-2),加入5g对甲基苯磺酸,乙二醇50ml,搅拌下回流分水反应4小时。反应完毕。经过水洗中和处理,蒸干甲苯得到中间体(C-3)。经过4倍乙醇结晶提纯得到24克中间体(C-3),纯度95.3%;
将24克中间体(C-3)加入150ml甲苯,1.5克5%钯炭,30-40℃,常压下搅拌加氢10小时。反应完毕,过滤回收钯炭得到产物(C-4)溶液;
将产物(C-4)溶液加入300毫升85%甲酸,60℃搅拌6小时。分液水洗中和。蒸干甲苯得到中间体C-5,经过异丙醇结晶提纯得到15g中间体C-5纯度98.3%。
步骤(3)
将21.6g氯甲醚三苯基膦盐中加入120ml四氢呋喃,氮气保护下降温到0℃,然后加入6.5g叔丁醇钾,保温30分钟。然后滴加15g中间体C-5和50ml四氢呋喃配置溶液,控温0-10℃。加完室温搅拌过夜。经过加水稀释,石油醚提取,过硅胶柱提纯,蒸干溶剂,2倍乙醇结晶提纯得到13g烯醚(C-6);
将13g烯醚(C-6)加入100ml四氢呋喃,20ml水,20克30%盐酸,加热回流3小时。室温下加入二氯甲烷提取,分液水洗中和处理,蒸干溶剂。加入130ml甲醇降温到0-10℃,加入15g氢氧化钾搅拌2小时。加水200毫升。加入200毫升二氯甲烷,提取水洗干燥处理,蒸干溶剂得到9.5g反式醛(C-7);
将14.2g溴乙烷三苯基膦盐中加入100ml四氢呋喃,氮气保护下降温到0℃,然后加入4.5g叔丁醇钾,保温30分钟。然后滴加9.5g反式醛(C-7)和50ml四氢呋喃配置溶液,控温0-10℃。加完室温搅拌过夜。经过加水稀释,石油醚提取,过硅胶柱提纯,蒸干溶剂,得到浅黄色固体,经过乙醇结晶提纯得到白色晶体(C-8)8.2g,纯度98.4%;
将白色晶体(C-8)4.2g克加入80ml二氯甲烷,搅拌降温到0℃,分批加入间氯过氧苯甲酸(折纯)5.6克,控温0-10℃搅拌2小时,室温5小时。反应完毕,过滤。滤液用50毫升饱和亚硫酸钠溶液洗涤一次,然后再50毫升水洗一次。分液后,加入无水硫酸钠干燥,过硅胶柱,蒸干溶剂,得到白色固体。使用4倍石油醚和1倍甲苯结晶提纯2次,得到3.5g白色晶体环氧乙烷(T-3),纯度99.55%,熔点135.9℃。质谱分析图如图4所示,核磁氢谱如图5所示,分析产物为目标产物。
实施例4
步骤(1)
步骤(2)
在500ml反应瓶内加入中间体(A-4)26.6g,四甲基乙二胺12g,四氢呋喃200ml,氮气保护下,降温到-78℃,滴加丁基锂(2.5mol/L)45ml,加完-70~-80℃保温1小时,然后滴加11g DMF。加完逐渐升至室温搅拌5小时。酸性水解后,加入乙酸乙酯提取,水洗等后处理后,得到黄色固体。经过1倍甲苯和3倍乙醇打浆纯化之后得到白色固体(中间体A-5)20.5g;
在500ml反应瓶内投入32g溴乙烷三苯基膦盐,120ml四氢呋喃。氮气保护下降温到0℃,加入10.3g叔丁醇钾,然后0℃保温30分钟。0℃,滴加20.5g中间体A-5和40ml四氢呋喃配置得溶液。加完,逐渐升至室温搅拌过夜。经过加水稀释、正庚烷提取、过硅胶柱纯化,蒸干溶剂,得到中间体A-6,进一步乙醇结晶提纯得到白色晶体10g(烯键顺反混合物);
将10克中间体A-6加入100毫升二氯甲烷,搅拌降温到0℃,分批加入间氯过氧苯甲酸(折纯)13.6克,控温0-10℃搅拌2小时,室温搅拌过夜。反应完毕,过滤。滤液用50毫升饱和亚硫酸钠溶液洗涤一次,然后再50毫升水洗一次。分液后,加入无水硫酸钠干燥,过硅胶柱,蒸干溶剂,得到白色固体。经过甲苯和乙醇混合溶剂纯化后,得到4.3g白色晶体(T-4),纯度99.5%。质谱分析图如图6所示和核磁氢谱如图7所示,分析产物为目标产物。
以上所述仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专利的技术人员在不脱离本发明技术方案范围内,当可利用上述提示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明方案的范围内。
Claims (1)
将烯类单体降温至-2~2℃后加入间氯过氧苯甲酸,然后在0~10℃下反应2~4h,在室温下反应4~6h,再经过滤、洗涤、干燥制得式(Ig)~式(Ik)所示单体;
所述负性液晶单体的结构式为式(Ig)~式(Ik)中的任意一种:
其中,R1为H或者—CH3,R或R2为C1-C4的直链烷基或者烷氧基,Z1为单键或—CH2O—,Z2为单键,环A为1,4-亚环己基,n1为0或1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910067759.4A CN110117277B (zh) | 2019-01-24 | 2019-01-24 | 一种负性液晶单体及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910067759.4A CN110117277B (zh) | 2019-01-24 | 2019-01-24 | 一种负性液晶单体及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110117277A CN110117277A (zh) | 2019-08-13 |
CN110117277B true CN110117277B (zh) | 2022-12-30 |
Family
ID=67520262
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910067759.4A Active CN110117277B (zh) | 2019-01-24 | 2019-01-24 | 一种负性液晶单体及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110117277B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110577833B (zh) * | 2019-08-15 | 2021-03-23 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
CN113528150B (zh) * | 2020-04-16 | 2023-03-14 | 河北迈尔斯通电子材料有限公司 | 一种含氟负性液晶化合物及其制备方法 |
CN112175629B (zh) * | 2020-09-14 | 2023-03-24 | 北京八亿时空液晶科技股份有限公司 | 一种含三联苯的快速响应液晶组合物及其应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106883865A (zh) * | 2015-12-15 | 2017-06-23 | 北京八亿时空液晶科技股份有限公司 | 一种含有苯并呋喃的负介电各向异性液晶组合物及其应用 |
CN107267156A (zh) * | 2016-04-07 | 2017-10-20 | 北京八亿时空液晶科技股份有限公司 | 一种液晶组合物及其应用 |
CN107794057A (zh) * | 2017-10-31 | 2018-03-13 | 晶美晟光电材料(南京)有限公司 | 负性液晶化合物、液晶混合物及其应用 |
CN108034433A (zh) * | 2017-11-17 | 2018-05-15 | 晶美晟光电材料(南京)有限公司 | 一种负型液晶混合物及其应用 |
CN108865178A (zh) * | 2018-08-13 | 2018-11-23 | 晶美晟光电材料(南京)有限公司 | 一种具有高介电常数的液晶组合物及其应用 |
CN109181711A (zh) * | 2018-08-20 | 2019-01-11 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
-
2019
- 2019-01-24 CN CN201910067759.4A patent/CN110117277B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106883865A (zh) * | 2015-12-15 | 2017-06-23 | 北京八亿时空液晶科技股份有限公司 | 一种含有苯并呋喃的负介电各向异性液晶组合物及其应用 |
CN107267156A (zh) * | 2016-04-07 | 2017-10-20 | 北京八亿时空液晶科技股份有限公司 | 一种液晶组合物及其应用 |
CN107794057A (zh) * | 2017-10-31 | 2018-03-13 | 晶美晟光电材料(南京)有限公司 | 负性液晶化合物、液晶混合物及其应用 |
CN108034433A (zh) * | 2017-11-17 | 2018-05-15 | 晶美晟光电材料(南京)有限公司 | 一种负型液晶混合物及其应用 |
CN108865178A (zh) * | 2018-08-13 | 2018-11-23 | 晶美晟光电材料(南京)有限公司 | 一种具有高介电常数的液晶组合物及其应用 |
CN109181711A (zh) * | 2018-08-20 | 2019-01-11 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN110117277A (zh) | 2019-08-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110117277B (zh) | 一种负性液晶单体及制备方法 | |
CN110577833B (zh) | 一种负性液晶化合物及其制备方法 | |
CN109181711B (zh) | 一种负性液晶化合物及其制备方法 | |
CN107298980B (zh) | 一种负性液晶化合物及其制备方法 | |
KR20150086177A (ko) | 2,3-디플루오로페닐 기를 함유하는 음성 액정 화합물, 및 그의 제조 방법 및 용도 | |
CN111344277B (zh) | 聚合性化合物以及使用其的液晶组合物及液晶显示元件 | |
CN107779202B (zh) | 一种负性液晶化合物的制备方法 | |
US20150252261A1 (en) | Cycloheptane derivative and preparation method and use thereof | |
TW201122085A (en) | Polymerizable liquid crystal compounds having oxiranyl group, polymerizable liquid crystal composition and polymers | |
JP5604809B2 (ja) | フルオロベンゼン誘導体及びこの化合物を含有する液晶組成物 | |
WO2007142236A1 (ja) | 水酸基を有する3-エチルオキセタン化合物及びその製法 | |
CN113913193B (zh) | 具有负介电各向异性的液晶化合物、液晶组合物、液晶显示器件 | |
CN117466849B (zh) | 一种含异硫氰基的液晶单体化合物及其制备方法 | |
CN110437846B (zh) | 含炔键的氟取代苯并噁唑液晶化合物及其制备方法 | |
CN113355105A (zh) | 一种含有二苯并噻吩并含氧杂环类液晶化合物及其应用 | |
US3736293A (en) | Polyethers containing repeating perchloroaromatic units | |
CN111484410B (zh) | 添加剂及其应用 | |
CN112745236A (zh) | 含有四苯基乙烯-三苯胺结构的二胺单体、制备方法及其在制备无色聚酰亚胺中的应用 | |
CN113736475B (zh) | 一种新型液晶化合物及其制备方法与应用 | |
CN111662212A (zh) | 一种液晶中间体及其制备方法 | |
CN113528150B (zh) | 一种含氟负性液晶化合物及其制备方法 | |
CN113684036B (zh) | 一种二苯并噻吩砜液晶化合物及其制备方法和应用 | |
CN112980458A (zh) | 一种含桥环烷烃液晶化合物及其制备方法与应用 | |
KR20240051455A (ko) | 위상차 필름의 액정 화합물 제조용 단량체 제조방법 및 이를 이용한 위상차 필름용 액정 화합물 제조방법 | |
CN111349447A (zh) | 一种含有二氟甲氧基桥键的液晶化合物、制备方法及应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A Negative Liquid Crystal Monomer and Its Preparation Method Granted publication date: 20221230 Pledgee: Bank of China Limited Xingtang Branch Pledgor: HEBEI MILESTONE ELECTRONIC MATERIAL Co.,Ltd. Registration number: Y2024130000005 |
|
PE01 | Entry into force of the registration of the contract for pledge of patent right |