CN104744223A - Liquid crystal compound containing tricyco[4. 4. 0. 0<3, 8>] decanyl difluoromethyl ether, preparation method and application - Google Patents
Liquid crystal compound containing tricyco[4. 4. 0. 0<3, 8>] decanyl difluoromethyl ether, preparation method and application Download PDFInfo
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Abstract
The invention relates to the field of liquid crystal materials, and particularly relates to a liquid crystal compound containing tricyco[4. 4. 0. 0<3, 8>] decanyl difluoromethyl ether, a preparation method and application. The liquid crystal compound has the general formula show in the description. A liquid crystal composition added with the compound provided by the invention is short in response time, moderate in deltan numerical value and high in charge retention rate, has a relatively low threshold voltage, and is broad in application prospect.
Description
Technical field
The present invention relates to liquid crystal material field, particularly one is containing three ring [4.4.0.0
3,8] liquid crystalline cpd of decyl and difluoro methyl ether, preparation method and application.
Background technology
At present, liquid crystal is used widely in field of information display, and the application simultaneously in optical communication also makes some progress (S.T.Wu, D.K.Yang.Reflective Liquid CrystalDisplays.Wiley, 2001).In recent years, the Application Areas of liquid crystalline cpd significantly widened kinds of displays part, electro-optical device, electronic component, sensor.For this reason, proposed many different structures, particularly in nematic liquid crystal field, nematic liquid crystal compound has obtained applying the most widely so far in flat-panel monitor.Especially in the system of tft active matrix.
Liquid crystal material requires to possess good chemistry and thermostability, the good stability to electric field and electromagnetic radiation, wider nematic temperature range, suitable specific refractory power, dielectric anisotropy, faster response speed and high voltage retention.
Along with the development of technique of display, higher requirement be it is also proposed to liquid crystal material, especially in quick response, reduce driving voltage, reduce the aspects such as power consumption.Therefore, the novel liquid crystal compound of the more improvement performances of exploitation is needed.
Summary of the invention
The object of this invention is to provide a kind of containing three ring [4.4.0.0
3,8] liquid crystalline cpd of decyl and difluoro methyl ether.
Another object of the present invention is to provide a kind of containing three ring [4.4.0.0
3,8] preparation method of liquid crystalline cpd of decyl and difluoro methyl ether.
Another object of the present invention is to provide a kind of containing three ring [4.4.0.0
3,8] application of liquid crystalline cpd of decyl and difluoro methyl ether.
For solving the problem, the present invention adopts following technical scheme:
A kind of containing three ring [4.4.0.0
3,8] liquid crystalline cpd of decyl and difluoro methyl ether, there is following formula:
In general formula I, the alkyl of C1 ~ C12 that R represents the alkyl of-H, C1 ~ C12 or alkoxyl group, one or more H atom is optionally substituted by halogen or alkoxyl group, one or more-CH
2-replaced by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-independently of one another and the alkyl of C1 ~ C12 that directly do not connect each other of O atom or alkoxyl group;
represent Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene independently of one another, Isosorbide-5-Nitrae-cyclohexylidene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms or Isosorbide-5-Nitrae-phenylene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms;
L
1, L
2, L
3and L
4represent H, F or Cl independently of one another;
X represents H, F, Cl, OCF
2h, OCF
3, CF
3, one in the alkyl of C1 ~ C6 or the alkoxyl group of C1 ~ C6;
M represents 0,1 or 2; N represents 0,1 or 2.
On this basis, the present invention has made preferred restriction to said structure, and preferably, R represents-H, C
1~ C
6alkyl, one or more-CH
2-independently of one another by-O-replace and Sauerstoffatom not be directly connected C
1~ C
6alkyl; More preferably, R represents-C
3h
7.
represent Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene or 1 ~ 2 hydrogen atom are replaced by fluorine atoms independently of one another;
L
1, L
2, L
3and L
4represent H or F independently of one another.
X represents H, F, OCF
2h, OCF
3or CH
3.
M represent 0,1 or 2, n represent 0,1 or 2, and m+n≤3.
In some preferred embodiments, the compound of formula I is particularly preferably one or more of following compound:
In I1 ~ I18, R represents alkyl or the alkoxyl group of H, C1 ~ C6; Wherein, the H in alkyl or alkoxyl group can be optionally substituted by halogen, one or more-CH
2-can be replaced by-O-, but require that O atom does not directly connect each other.
As preferred forms of the present invention, the compound of formula I is selected from one or more of following compound:
Another object of the present invention is to provide described containing three ring [4.4.0.0
3,8] preparation method of liquid crystalline cpd of decyl and difluoro methyl ether, specifically comprise the steps:
Step 1):
generate with magnesium chips generation grignard reaction
Step 2):
with Br
2reaction generates
Step 3):
under the catalysis of cupric chloride lithium, generate
Step 4):
react with difluorodibromomethane and generate
Step 5):
the compound of general formula I is obtained by reacting through Williamson Synthesis,
In above-mentioned steps 1) to step 5) in, R in described structural formula,
l
1, L
2, L
3, L
4, X, m, n definition all identical with the definition in claim 1 general structure (I).
Synthetic route is as follows:
Concrete,
Step 1) in
(I-1) is 1:1 ~ 3 with the mol ratio of magnesium chips, and concrete steps are under nitrogen protection, will
(I-1) is dissolved in tetrahydrofuran (THF), gets
the 5%-10% of (I-1) and tetrahydrofuran (THF) mixing solutions and magnesium chips stir and cause grignard reaction, and backflow, drips remaining
the mixing solutions of (I-1) and tetrahydrofuran (THF), drips and finishes, back flow reaction 1h ~ 6h;
Step 2) be solvent with methylene dichloride, mol ratio is the Br of 1:1 ~ 3
21 ~ 3h is reacted at 0 ~ 5 DEG C, rear temperature control 0 ~ 5 DEG C dropping with triphenylphosphine
the mixing solutions of (I-3) and methylene dichloride (methylene dichloride with
volume mass ratio be 3 ~ 5:1, unit is mL/g), drip finish, temperature control-5 ~ 10 DEG C reaction 2 ~ 3h;
Step 3) be solvent with tetrahydrofuran (THF), mol ratio is 1 ~ 3:1
(I-2) with
(I-4) react under the catalysis of cupric chloride lithium, and feed way for add in reaction vessel
(I-2) are then drip under the condition of 10-20 DEG C in temperature
the mixing solutions of (I-4) and tetrahydrofuran (THF), drips and finishes, back flow reaction 3 ~ 6h or add in reaction vessel
then be drip under the condition of 40 ~ 50 degree in temperature
with the mixing solutions of tetrahydrofuran (THF), drip and finish, back flow reaction 3 ~ 6h;
Step 4): in molar ratio
(I-5): n-Buli:CF
2br
2=1:1 ~ 2:2 ~ 4, under nitrogen protection, will in low-temperature reactor
be dissolved in tetrahydrofuran (THF), open after stirring and be cooled to-75 DEG C ~-85 DEG C, start to drip n-Buli, dropwise the reaction of rear temperature control 2 ~ 4h, rear dropping CF
2br
2, dropwise, natural temperature reaction is to-30 DEG C ~-10 DEG C;
Step 5): make solvent with water, do consisting of phase-transferring agent with Tetrabutyl amonium bromide, adding mol ratio is 1:1 ~ 3
(I-6) with
(I-7), are warming up to backflow, reaction 5 ~ 10h.
Concrete, step 5) in molar ratio, Tetrabutyl amonium bromide is
5% ~ 10%.
Preferably, step 1) in
with the mixing solutions of tetrahydrofuran (THF) drip finish after, back flow reaction 1h ~ 3h.
Step 3) middle back flow reaction 4 ~ 5h;
Step 5) middle back flow reaction 6 ~ 7h.
Above-mentioned
n-Butyl Lithium, difluorodibromomethane, bromine etc. all can be obtained by itself known method synthesis in open commercial sources or document.
The present invention also provides a kind of liquid-crystal composition, wherein comprises the compound that mass percent is the general formula I of 1-50%, and preferred mass per-cent is the compound of the general formula I of 3-25%.
Liquid crystalline cpd of the present invention and liquid-crystal composition can be applicable in TN, IPS, FFS, ADS-TFT pattern.
Beneficial effect of the present invention is as follows: the liquid-crystal composition adding the compounds of this invention, and the time of response is short, Δ n numerical value is moderate, electric charge conservation rate is high, and has lower threshold voltage, has a extensive future.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Described starting material if no special instructions, all can obtain from open commercial sources.
" conventional aftertreatment " refers to, in aqueous, mixed solution methylene dichloride, ethyl acetate or toluene extract, separatory, washing, dry and vacuum rotary evaporator evaporation, then product underpressure distillation or recrystallization and/or chromatography purification.
Embodiment 1
The synthetic line preparing compound L C-01 is as follows:
1, the synthesis of compound 4
0.24 mole of Br is added successively in there-necked flask
2, 0.24 mole of triphenylphosphine, 0.2L methylene dichloride stirring and dissolving, after be cooled to 0 ~ 5 DEG C, temperature control 0 ~ 5 DEG C reaction 1h, rear temperature control 0 ~ 5 DEG C drips the compound 3 of 0.2 mole and the mixing solutions of 0.2L tetrahydrofuran (THF), drip and finish, temperature control stirring 2h, after add 0.4L water, stir 5 minutes, leave standstill 10 minutes, separatory, upper strata is aqueous phase, and lower floor is product phase.Washing that product is used mutually (0.4L × 3) three times, 20g anhydrous magnesium sulfate drying 1 hour.Filtration drying agent, with Rotary Evaporators except desolventizing, obtains 0.16 mole of light yellow liquid compound 4, GC:99.1%, yield: 80%.
2, the synthesis of compound 5
0.16 mole of magnesium chips is added in there-necked flask, 200ml tetrahydrofuran (THF), inflated with nitrogen displaced air three times, add the mixing solutions of 10ml by 0.16 mole compound 1 and 200ml tetrahydrofuran (THF), stir and cause grignard reaction, (total mol ratio of magnesium and compound 1 is 1:1 to the remaining compound of rear dropping 1, just the mixing solutions of compound 1 and tetrahydrofuran (THF) adds at twice, first add 5%-10% volume for causing, remainingly to add again) and the mixing solutions of tetrahydrofuran (THF), back flow reaction 1h, obtain Grignard reagent compound 2, after be cooled to 10-20 DEG C, add the cupric chloride lithium solution of 0.01 mole, the mixing solutions of temperature control 10-20 DEG C of dropping 0.16 mole compound 4 and 100ml tetrahydrofuran (THF), drip and finish, be warming up to back flow reaction 4h.
Aftertreatment: add 0.5L water in there-necked flask, 0.5L toluene, stirs 5 minutes, and leave standstill 10 minutes, separatory, upper strata is organic phase, and lower floor is aqueous phase.Organic phase (0.5L × 3) washing three times, anhydrous sodium sulfate drying, suction filtration, filtrate crosses silicagel column, 3 times of post height toluene rush post, concentrating under reduced pressure is spin-dried for solvent, adds 200ml ethanol, freezes case (-30 DEG C) 6h, suction filtration, dry to obtain 0.14 mole compound 5, GC:99%, yield: 86%.
3, the synthesis of compound 6
2L low-temperature reactor; nitrogen protection; add 0.14mol compound 5,0.3L THF wherein; open liquid nitrogen cooling extremely-75 DEG C ~-85 DEG C after stirring; start to drip 0.14moln-Buli (n-Butyl Lithium); process temperature control-75 DEG C ~-85 DEG C, dropwises the reaction of rear temperature control 1h, rear dropping 0.16molCF
2br
2, process temperature control-75 DEG C ~-85 DEG C, dropwises, and natural temperature reaction is to-30 DEG C of direct aftertreatments.
Aftertreatment: the mixing solutions (PH<5) dripping the dense HCl+0.5L water of 140g to reaction solution, stir 0.5h, separatory, aqueous phase (0.5L × 2) methylbenzene extraction twice, merge organic phase and be washed to neutrality (2L/ time, about 2 times), organic phase anhydrous sodium sulfate drying, suction filtration, filtrate crosses silicon gel column, 3 times of post height toluene rinse pillars, merged post liquid to concentrate, obtain 0.14mol compound 6, GC content 70% (main peak), yield 100%.
4, the synthesis of compound 8
The reaction unit of 2L there-necked flask, adds 0.5L water, 0.007mol Tetrabutyl amonium bromide, 0.14mol compound 6,0.14mol compound 7, is warming up to backflow under stirring, backflow 6h, controls GC (raw material) <2% in rear sampling, start aftertreatment.
Aftertreatment: add toluene 1L in reaction solution, stir, separatory, aqueous phase (0.5L × 2) methylbenzene extraction twice, merge organic phase (0.5L × 2) washing 2 times, organic phase anhydrous sodium sulfate drying, suction filtration, filtrate crosses silicon gel column, 3 times of post height toluene rinse pillars, cross post liquid concentrating under reduced pressure, 500ml ethanol 80 DEG C is put in refrigerator-freezer recrystallization (freezing 3h), rear suction filtration after dissolving, and dries to obtain 0.05mol compound 8 (LC-01), GC content 99%, yield: 50%.
GC-MS:562 (molecular ion peak), 495 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.5-6.2(m,8H)，1.8-0.8(m,21H)。
Embodiment 2
The synthetic line preparing compd B YLC-02 is as follows:
1, the synthesis of compound 4
The Br of 0.08 mole is added successively in there-necked flask
2, 0.24 mole of triphenylphosphine, 0.2L methylene dichloride stirring and dissolving, after be cooled to 0 ~ 5 DEG C, temperature control 0 ~ 5 DEG C reaction 3h, rear temperature control 0 ~ 5 DEG C drips the compound 3 of 0.0.08 mole and the mixing solutions of 0.3L tetrahydrofuran (THF), drip and finish, temperature control stirring 3h, after add 0.4L water, stir 5 minutes, leave standstill 10 minutes, separatory, upper strata is aqueous phase, and lower floor is product phase.Washing that product is used mutually (0.4L × 3) three times, 20g anhydrous magnesium sulfate drying 1 hour.Filtration drying agent, with Rotary Evaporators except desolventizing, obtains 0.164 mole of light yellow liquid compound 4, GC:99.5%, yield: 82%.
2, the synthesis of compound 5
0.48 mole of magnesium chips is added in there-necked flask, 200ml tetrahydrofuran (THF), inflated with nitrogen displaced air three times, add the mixing solutions of 20ml by 0.16 mole compound 1 and 200ml tetrahydrofuran (THF), stir and cause grignard reaction, the remaining compound 1 of rear dropping and tetrahydrofuran (THF) mixing solutions, back flow reaction 3h, obtain Grignard reagent compound 2, after be cooled to 10-20 DEG C, add the cupric chloride lithium solution of 0.01 mole, the temperature control 10-20 DEG C of mixing solutions dripping 0.05 mole compound 4 and 100ml tetrahydrofuran (THF), drip and finish, be warming up to back flow reaction 5h.
Aftertreatment: add 0.5L water in there-necked flask, 0.5L toluene, stirs 5 minutes, and leave standstill 10 minutes, separatory, upper strata is organic phase, and lower floor is aqueous phase.Organic phase (0.5L × 3) washing three times, anhydrous sodium sulfate drying, suction filtration, filtrate crosses silicagel column, 3 times of post height toluene rush post, concentrating under reduced pressure is spin-dried for solvent, adds 200ml ethanol, freezes case (-30 DEG C) 6h, suction filtration, dry to obtain 0.13 mole compound 5, GC:98%, yield: 80%.
3, the synthesis of compound 6
2L low-temperature reactor; nitrogen protection; add 0.13mol compound 5,0.3L THF wherein; open liquid nitrogen cooling extremely-75 DEG C ~-85 DEG C after stirring; start to drip 0.26moln-Buli (n-Butyl Lithium); process temperature control-75 DEG C ~-85 DEG C, dropwise rear temperature control reaction 4h, rear dropping 0.15mol massfraction is the CF of 51%
2br
2with the mixing solutions of tetrahydrofuran (THF), process temperature control-75 DEG C ~-85 DEG C, dropwises, and natural temperature reaction is to-10 DEG C of direct aftertreatments.
Aftertreatment: the mixing solutions (PH<5) dripping the dense HCl+0.5L water of 120g to reaction solution, stir 0.5h, separatory, aqueous phase (0.5L × 2) methylbenzene extraction twice, merge organic phase and be washed to neutrality (2L/ time, about 2 times), organic phase anhydrous sodium sulfate drying, suction filtration, filtrate crosses silicon gel column, 3 times of post height toluene rinse pillars, merged post liquid to concentrate, obtain 0.13mol compound 6, GC content 66% (main peak), yield 100%.
3, the synthesis of compound 8
The reaction unit of 2L there-necked flask, adds 0.4L water, 0.013mol Tetrabutyl amonium bromide, 0.13mol compound 6,0.39mol compound 7, is warming up to backflow under stirring, backflow 7h, controls GC (raw material) <2% in rear sampling, start aftertreatment.
Aftertreatment: add toluene 1L in reaction solution, stir, separatory, aqueous phase (0.5L × 2) methylbenzene extraction twice, merge organic phase (0.5L × 2) washing 2 times, organic phase anhydrous sodium sulfate drying, suction filtration, filtrate crosses silicon gel column, 3 times of post height toluene rinse pillars, cross post liquid concentrating under reduced pressure, 300ml ethanol 80 DEG C is put in refrigerator-freezer recrystallization (freezing 3h), rear suction filtration after dissolving, and dries to obtain 0.038mol compound 8 (LC-02), GC content 99%, yield: 44%.
GC-MS:674 (molecular ion peak), 513 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.0-6.5(m,10H)，1.8-0.9(m,21H)。
Embodiment 3
With
replace
compound L C-07 can be obtained according to the method for embodiment 1:
After testing, GC content 99.8%, etherificate yield 40%.
GC-MS:656 (molecular ion peak), 589 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.0-6.5(m,11H)，1.8-0.9(m,21H)。
Following compound can be synthesized equally by the method for embodiment 1 ~ embodiment 3:
GC-MS:580 (molecular ion peak), 513 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.2-6.2(m,7H)，1.8-0.8(m,21H)。
GC-MS:544 (molecular ion peak), 495 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.4-6.1(m,9H)，1.8-0.8(m,21H)。
GC-MS:562 (molecular ion peak), 513 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.2-6.4(m,8H)，1.8-0.8(m,21H)。
GC-MS:544 (molecular ion peak), 477 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.4-6.2(m,9H)，1.8-0.8(m,21H)。
GC-MS:562 (molecular ion peak), 495 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.5-6.2(m,8H)，1.8-0.8(m,21H)。
GC-MS:674 (molecular ion peak), 607 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.4-6.2(m,10H)，1.8-0.9(m,21H)。
GC-MS:638 (molecular ion peak), 589 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.4-6.5(m,12H)，1.8-0.9(m,21H)。
GC-MS:656 (molecular ion peak), 607 (losing 3,4,5-trifluoromethoxy phenoxy base);
1H-NMR(300MHz,CDCl
3)：7.4-6.4(m,11H)，1.8-0.9(m,21H)。
GC-MS:656 (molecular ion peak), 495 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.4-6.5(m,10H)，1.8-0.9(m,21H)。
GC-MS:638 (molecular ion peak), 495 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.4-6.8(m,10H)，1.8-0.9(m,21H)。
GC-MS:656 (molecular ion peak), 513 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.0-6.5(m,10H)，1.8-0.9(m,21H)。
GC-MS:674 (molecular ion peak), 419 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.6-6.5(m,10H)，1.7-0.9(m,21H)。
GC-MS:656 (molecular ion peak), 401 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.6-6.8(m,11H)，1.8-0.8(m,21H)。
GC-MS:704 (molecular ion peak), 589 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.5-6.4(m,12H)，1.7-0.9(m,21H)。
GC-MS:722 (molecular ion peak), 607 (fractures of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3)：7.4-6.3(m,11H)，1.8-0.9(m,21H)。
Embodiment 4:
The liquid crystalline cpd used in following composition is all provided by Beijing Bayi Space LCD Materials Technology Co., Ltd..Except specified otherwise, in embodiment, the content of each component all represents mass percent.
In the present invention, each performance test parameter shorthand is as follows:
△ n is optical anisotropy, n
ofor specific refractory power (589nm, 20 DEG C);
V
10for threshold voltage, be the character voltage (V, 20 DEG C) when transmitance changes 10%, V
90for saturation voltage, be character voltage when transmitance changes 90% (V, 20 DEG C); Liquid crystal comprehensive parameter tester EOT-5016.The polaroid that setting polarizing axis is orthogonal, is attached to testing cassete (4.0 μm) top and bottom being marked with liquid crystal by polaroid.To liquid crystal cell making alive, the voltage when light is reduced to 10% transmitance from the original state of full impregnated is saturation voltage.Light source is halogen light, and the square wave of liquid crystal cell 64HZ drives.
Cp is the clearing point (DEG C) of liquid-crystal composition;
τ
onfor until time when reaching transmitance 90%, τ
offfor until reach time when transmitance 10% is cut off, τ is τ
on+ τ
off(time of response) (ms).
VHR is electric charge conservation rate (%): injected by mixed liquid crystal in liquid crystal cell, put into thermostat container, after temperature DEG C is stablized, enters test procedure, manually gets and a little obtain electric charge conservation rate numerical value.Measuring voltage is 5V, and power-up time is 5ms, Holding Time is 500ms.
Get the liquid crystalline cpd of following parts by weight and prepare liquid-crystal composition, the performance perameter of concrete proportioning and the liquid-crystal composition of gained is by shown in following table.
The application of liquid crystalline cpd of the present invention in IPS, FFS, ADS-TFT pattern, result is as following table:
Table 1.1 adds the weight percent of each component in the liquid-crystal composition 1 of the compounds of this invention
The performance perameter of table 1.2 liquid-crystal composition 1
| Performance perameter | Parameter value |
| △n | 0.101 |
| Δε | +9.6 |
| V 10 | 1.11 |
| η | 11 |
| Cp | 112 |
| τ | 10 |
| VHR | 99％ |
Table 2.1 adds the weight percent of each component in the liquid-crystal composition 2 of the compounds of this invention
The performance perameter of table 2.2 liquid-crystal composition 2
| Performance perameter | Parameter value |
| △n | 0.112 |
| Δε | +10.1 |
| V 10 | 1.05 |
| η | 16 |
| Cp | 120 |
| τ | 8 |
| VHR | 99％ |
Table 3.1 does not add the weight percent of each component of liquid-crystal composition 3 of the compounds of this invention
The performance perameter of table 3.2 liquid-crystal composition 3
| Performance perameter | Parameter value |
| △n | 0.098 |
| Δε | +9.3 |
| V 10 | 1.15 |
| η | 21 |
| Cp | 100 |
| τ | 15 |
| VHR | 97％ |
Table 4.1 does not add the weight percent of liquid-crystal composition 4 component of the compounds of this invention
Table 4.2 liquid-crystal composition 4 performance perameter
| Performance perameter | Parameter value |
| △n | 0.096 |
| Δε | +9.0 |
| V 10 | 1.20 |
| η | 23 |
| Cp | 96 |
| τ | 16 |
| VHR | 96％ |
Compared do not added the liquid-crystal composition 3 (table 3.1) of the compounds of this invention and the performance perameter of liquid-crystal composition 4 (table 4.1) from the liquid-crystal composition 1 (table 1.1), the liquid-crystal composition 2 (table 2.1) that add the compounds of this invention, the liquid-crystal composition time of response adding the compounds of this invention is shorter, Δ n numerical value is moderate, electric charge conservation rate is higher, and there is lower threshold voltage, be particularly useful for the TFT display mode of fast-response.The add-on of the compound of general structure of the present invention (I) is advisable with 1-50%, more preferably 3-25%.
Except the composition that test example exemplifies, the liquid-crystal composition adding other compound provided by the invention composition also can obtain optical property excellent equally.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. one kind contains three ring [4.4.0.0
3,8] liquid crystalline cpd of decyl and difluoro methyl ether, it is characterized in that there is following formula:
In general formula I: the alkyl of C1 ~ C12 that R represents the alkyl of-H, C1 ~ C12 or alkoxyl group, one or more H atom is optionally substituted by halogen or alkoxyl group, one or more-CH
2-replaced by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-independently of one another and the alkyl of C1 ~ C12 that directly do not connect each other of O atom or alkoxyl group;
represent Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene independently of one another, Isosorbide-5-Nitrae-cyclohexylidene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms or Isosorbide-5-Nitrae-phenylene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms;
L
1, L
2, L
3and L
4represent H, F or Cl independently of one another;
X represents H, F, Cl, OCF
2h, OCF
3, CF
3, one in the alkyl of C1 ~ C6 or the alkoxyl group of C1 ~ C6;
M represents 0,1 or 2; N represents 0,1 or 2.
2. liquid crystalline cpd according to claim 1, is characterized in that, R represents-H, C
1~ C
6alkyl, one or more-CH
2-independently of one another by-O-replace and Sauerstoffatom not be directly connected C
1~ C
6alkyl;
represent Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene or 1 ~ 2 hydrogen atom are replaced by fluorine atoms independently of one another;
L
1, L
2, L
3and L
4represent H or F independently of one another;
X represents H, F, OCF
2h, OCF
3or CH
3;
M represent 0,1 or 2, n represent 0,1 or 2, and m+n≤3.
3. liquid crystalline cpd according to claim 1 and 2, is characterized in that, the compound of formula I is selected from one or more of following compound:
In I1 ~ I18, R represents the alkyl of H, C1 ~ C6, one or more CH
2group is replaced by-O-and the alkyl of C1 ~ C6 that is not directly connected each other of Sauerstoffatom independently of one another.
4. contain three ring [4.4.0.0 described in any one of claim 1-3
3,8] preparation method of liquid crystalline cpd of decyl and difluoro methyl ether, it is characterized in that,
Step 1):
generate with magnesium generation grignard reaction
Step 2):
with Br
2reaction generates
Step 3):
with
under the catalysis of cupric chloride lithium, generate
Step 4):
react with difluorodibromomethane and generate
Step 5):
with
the compound of general formula I is obtained by reacting through Williamson Synthesis,
In above-mentioned steps 1) to step 5) in, R in described structural formula,
l
1, L
2, L
3, L
4, X, m, n definition all identical with the definition in claim 1 general formula I.
5. according to claim 4 containing three ring [4.4.0.0
3,8] preparation method of liquid crystalline cpd of decyl and difluoro methyl ether, it is characterized in that,
Step 1) in
be 1:1 ~ 3 with the mol ratio of magnesium chips, under nitrogen protection, will
be dissolved in tetrahydrofuran (THF), get
stir with the 5%-10% of tetrahydrofuran (THF) mixing solutions and magnesium chips and cause grignard reaction, backflow, drips remaining
with the mixing solutions of tetrahydrofuran (THF), drip and finish, back flow reaction 1h ~ 6h;
Step 2) be reaction solvent with methylene dichloride, mol ratio is the Br of 1:1 ~ 3
21 ~ 3h is reacted at 0 ~ 5 DEG C, rear temperature control 0 ~ 5 DEG C dropping with triphenylphosphine
with the mixing solutions of methylene dichloride, drip and finish, temperature control-5 ~ 10 DEG C reaction 2 ~ 3h;
Step 3) be reaction solvent with tetrahydrofuran (THF), mol ratio is 1 ~ 3:1's
with
react under the catalysis of cupric chloride lithium, feed way for add in reaction vessel
then be drip under the condition of 10-20 DEG C in temperature
with the mixing solutions of tetrahydrofuran (THF) or add in reaction vessel
then be drip under the condition of 40 ~ 50 degree in temperature
with the mixing solutions of tetrahydrofuran (THF), drip and finish, back flow reaction 3 ~ 6h;
Step 4) in molar ratio
n-Buli:CF
2br
2=1:1 ~ 2:2 ~ 4, under nitrogen protection, will in low-temperature reactor
be dissolved in tetrahydrofuran (THF), open after stirring and be cooled to-75 DEG C ~-85 DEG C, start to drip n-Buli, dropwise the reaction of rear temperature control 2 ~ 4h, rear dropping CF
2br
2, dropwise, natural temperature reaction is to-30 DEG C ~-10 DEG C;
Step 5): make solvent with water, do consisting of phase-transferring agent with Tetrabutyl amonium bromide, adding mol ratio is 1:1 ~ 3
with
be warming up to backflow, reaction 5 ~ 10h.
6. the preparation method of liquid crystalline cpd according to claim 5, is characterized in that, step 1) in
with the mixing solutions of tetrahydrofuran (THF) drip finish after, back flow reaction 1h ~ 3h.
7. the preparation method of liquid crystalline cpd according to claim 5, is characterized in that, step 3) middle back flow reaction 4 ~ 5h; Step 5) middle back flow reaction 6 ~ 7h.
8. comprise described in any one of claim 1-3 containing three ring [4.4.0.0
3,8] liquid-crystal composition of liquid crystalline cpd of decyl and difluoro methyl ether.
9. liquid-crystal composition according to claim 8, is characterized in that, containing three ring [4.4.0.0
3,8] mass percentage of liquid crystalline cpd of decyl and difluoro methyl ether is 1 ~ 50%, is preferably 3 ~ 25%.
10. the liquid crystalline cpd described in any one of claim 1-3 or the application of the liquid-crystal composition described in claim 8 or 9 in TN, IPS, FFS, ADS-TFT mode LCD device.
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|---|---|---|---|---|
| CN102618296A (en) * | 2012-02-17 | 2012-08-01 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method thereof |
| CN103204832A (en) * | 2013-04-01 | 2013-07-17 | 北京八亿时空液晶科技股份有限公司 | Compound containing tetrahydrofuran, preparation method and application |
| CN103254908A (en) * | 2013-05-07 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Positive dielectric liquid crystal mixture containing (3,3,0) bicycle-octane monomer |
| CN103467251A (en) * | 2012-09-24 | 2013-12-25 | 石家庄诚志永华显示材料有限公司 | Adamantane derivative and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618296A (en) * | 2012-02-17 | 2012-08-01 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method thereof |
| CN103467251A (en) * | 2012-09-24 | 2013-12-25 | 石家庄诚志永华显示材料有限公司 | Adamantane derivative and preparation method and application thereof |
| CN103204832A (en) * | 2013-04-01 | 2013-07-17 | 北京八亿时空液晶科技股份有限公司 | Compound containing tetrahydrofuran, preparation method and application |
| CN103254908A (en) * | 2013-05-07 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Positive dielectric liquid crystal mixture containing (3,3,0) bicycle-octane monomer |
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