CN100348693C - Tetracycloester liquid crystal compounds - Google Patents
Tetracycloester liquid crystal compounds Download PDFInfo
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- CN100348693C CN100348693C CNB2005101027591A CN200510102759A CN100348693C CN 100348693 C CN100348693 C CN 100348693C CN B2005101027591 A CNB2005101027591 A CN B2005101027591A CN 200510102759 A CN200510102759 A CN 200510102759A CN 100348693 C CN100348693 C CN 100348693C
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Abstract
The present invention discloses a tetracycloester liquid crystal compound, which belongs to liquid crystal materials. In order to solve the problems of high viscosity and poor intermiscibility of the tetracycloester liquid crystal compound, a flexible ethylene bridge bond is inserted into a main chain of the tetracycloester liquid crystal compound, and the structural formula of the tetracycloester liquid crystal compound is disclosed in drawings. The tetracycloester liquid crystal compound of the present invention is mainly used for liquid crystal display.
Description
Technical field
The present invention is a kind of Tetracycloester liquid crystal compounds, belongs to liquid crystal material, is mainly used in liquid-crystal display.
Background technology
Liquid-crystal display has panelized, advantage such as low in energy consumption, in light weight, radiationless, in the field of information display development rapidly.Liquid-crystal display utilizes the optical anisotropy of liquid crystal material and the characteristic of dielectric anisotropy to realize Presentation Function.According to the display format classification, twisted-nematic formula (TN), supertwist are arranged to row formula (STN), dynamic scattering mode (DSP) etc.The used liquid crystal material of liquid-crystal display generally is-40 ℃～80 ℃ and has nematic phase in the environment for use temperature range; Simultaneously must tool with the chemical stability of height, lower viscosity, and physics of liquid crystals character such as the degree of birefringence of suitable purposes, dielectric anisotropy, resistivity.With a kind of liquid crystalline cpd is to satisfy whole working conditionss, must mix 10～20 kinds of liquid crystalline cpds and form mixed liquid crystal.Usually in order to improve the upper limit use temperature of liquid crystal compound, need in some liquid crystal compounds, add a certain proportion of liquid crystalline cpd with high clearing point.
Show and form by multiple small molecules organic compound that these micromolecular primary structure features are rodlike molecule structures with liquid crystal material.Many types have now been developed into, for example various biphenyl nitriles, ester class, cyclohexyl (connection) benzene class, oxygen heterocyclic ring benzene class, pyrimidine lopps, diphenyl acetylene class, ethylene bridged bond class and alkene end group class and various fluorine-containing phenyl ring classes etc.Ester liquid crystal has the advantages that phase transition temperature interval is wide, the dielectric anisotropy value big, be easy to prepare, and shows being used widely of field at twisted nematic (TN), super-twist nematic (STN).
As everyone knows,,, can significantly improve the clearing point of liquid crystal material, but along with the number of rings purpose increases, viscosity increases sharply also as three rings, Fourth Ring etc. along with the increase of six-ring number in the liquid crystal molecule skeleton.Reported the ester liquid crystal of following structural formula among the open JP5865251 of Japanese Patent:
It is wide that above-mentioned liquid crystalline cpd has the liquid crystal phase region, the characteristics that clearing point is high (＞300 ℃).But this compounds viscosity height is poor with the intermiscibility of other liquid crystalline cpd, adds to easily to cause partial crystallization in the prescription.
Summary of the invention
Purpose of the present invention is exactly in order to overcome the deficiency in the background technology, designs a kind ofly not only to have high clearing point but also have low viscous liquid crystalline cpd.
Design of the present invention: for the real above-mentioned purpose of seeing, between the main chain phenyl ring of liquid crystalline cpd and hexanaphthene, insert tool respectively, make molecule have flexibility, reduced the viscosity of compound, and improve and the intermiscibility of other liquid crystal with flexible ethylene bridged bond.
The present invention is a kind of Tetracycloester liquid crystal compounds, and its characteristics are to have symmetric ethylene bridged bond, and its structural formula is as follows:
R wherein
1, R
2The expression carbon number is 1～10 straight chained alkyl; Ring A is phenyl ring or hexanaphthene.
Another characteristics of the present invention are that structural formula is as follows:
The 3rd characteristics of the present invention are that structural formula is as follows:
The 4th characteristics of the present invention are that structural formula is as follows:
The 5th characteristics of the present invention are that structural formula is as follows:
The preparation of the compound that the present invention relates to is adopted 4-substituted benzoic acid and sulfur oxychloride to reflux and is prepared the 4-substituted benzoyl chloride, again with 4-fortified phenol or 4-substituted cyclohexyl alcohol under organic bases (pyridine) catalysis, back flow reaction preparation in inert solvent such as benzene,toluene,xylene etc.
The compound that the present invention relates to adopts following method synthetic:
4-[2-(trans-the 4-alkyl-cyclohexyl) ethyl wherein] benzoate anion prepares according to method described in the document US 4558151; 4-[2-(trans-alkyl-cyclohexyl) ethyl] phenol is according to the described methods preparation of document US 4439015.
The liquid crystalline cpd of the present invention's design has the good advantage of high clearing point, low viscosity and intermiscibility.
Embodiment
1, invention is implemented with reference to following structural formula:
In the 500mL there-necked flask, add 0.05mol 4-[2-(trans-4-propyl group cyclohexyl) ethyl] phenylformic acid, 50mL sulfur oxychloride, back flow reaction 8 hours.Steam and remove excessive sulfur oxychloride, get 4-[2-(trans-4-propyl group cyclohexyl) ethyl] Benzoyl chloride.
Add 100mL toluene, 4-[2-(trans-the propyl group cyclohexyl) ethyl] phenol 0.05mol, pyridine 3mL, back flow reaction 4 hours.The cooling after washing is to neutrality, dried over mgso.Remove toluene under reduced pressure, obtain light yellow solid.Ethyl alcohol recrystallization gets white crystal 17g, liquid chromatography purity 99.5%, yield 68%.
Structure is identified: MS:502 (M
+, 16)
IR (wave number, cm
-1): 1715 (s)
H
1NMR(δ)：0.96(t，6H)；1.33～1.58(m，36H)；2.55(t，4H)；7.10(d，2H)；7.19(d，2H)；7.27(d，2H)；8.09(d，2H)。
Transformation temperature: fusing point: 137.7 ℃; Clearing point: 236.2 ℃
2, the present invention implements with reference to following structural formula:
The preparation method is with embodiment 1, with 4-[2-(trans-the amyl group cyclohexyl) ethyl] alternative 4-[2-(trans-the amyl group cyclohexyl) ethyl of phenol] phenol.React white crystal 16g, liquid chromatography purity 99.4%, yield 61%.
MS：530(M
+，12)
IR (wave number, cm
-1): 1715 (s)
NMR(δ)：0.96(t，6H)；1.33～1.58(m，40H)；2.55(t，4H)；7.10(d，2H)；7.19(d，2H)；7.27(d，2H)；8.09(d，2H)；
Transformation temperature: fusing point: 92.2 ℃; Smectic phase height: 112.8 ℃; Clearing point: 224.0 ℃.
3, the present invention implements with reference to following structural formula:
With 0.5mol 4-[2-(trans-the propyl group cyclohexyl) ethyl] phenol joins in the autoclave, 10% palladium/carbon catalyst 10g, catalytic hydrogenation is 8 hours under 120 ℃, 6mPa, obtains 4-[2-(trans-4-propyl group cyclohexyl) ethyl] suitable, the anti-configuration mixture of hexalin.Ethyl alcohol recrystallization obtains trans-4-[2-(trans-4-propyl group cyclohexyl) ethyl] hexalin 29.5g, yield 24%.
With trans-4-[2-(trans-4-propyl group cyclohexyl) ethyl] 4-[2-(trans-the propyl group cyclohexyl) ethyl in the bad hexanol alternate embodiment 1] phenol, prepare 4-[2-(trans-4-propyl group cyclohexyl) ethyl] phenylformic acid is trans-4-[2-(trans-4-propyl group cyclohexyl) ethyl] hexamethylene alcohol ester 16.5g, liquid chromatography purity 99.4%, yield 65%.
MS：508(M
+，24)
IR (wave number, cm
-1): 1725 (s)
NMR(δ)：0.96(t，6H)；1.25～1.86(m，45H)；2.55(t，3H)；3.91(m，1H)；7.23(d，2H)；7.94(d，2H)
Transformation temperature: fusing point: 96.7 ℃; Clearing point: 223.4 ℃.
4, the present invention implements with reference to following structural formula:
The preparation method is with embodiment 3, react white crystal 18.5g, liquid chromatography purity 99.5%, yield 69%.
MS：536(M
+，22)，
IR (wave number, cm
-1): 1725 (s)
NMR(δ)：0.96(t，6H)；1.25～1.86(m，49H)；2.55(t，3H)；3.91(m，1H)；7.23(d，2H)；7.94(d，2H)
Transformation temperature: fusing point: 89.5 ℃; Clearing point: 218.5 ℃.
Comparative Examples:
In order further to illustrate the characteristic of The compounds of this invention, in the prescription A that following liquid crystalline cpd is formed, massfraction %
Prescription A
Adding 5% compound of the present invention (1) and compound (2) respectively opposes than test with known compound (3).
Measure clearing point, viscosity, and be placed in the refrigerator-freezer-20 ℃ and preserve and observed its partial crystallization point in 3 days, the result as shown in Table 1:
| Sequence number | Clearing point ℃ | Preserved 3 days for-20 ℃ | Viscosity (mPs) |
| Prescription A | 54 | Do not see partial crystallization | 28 |
| Prescription A+ (1) | 62 | Do not see partial crystallization | 29 |
| Prescription A+ (2) | 61 | Do not see partial crystallization | 29 |
| Prescription A+ (3) | 63 | Partial crystallization | 32 |
As can be seen from the table, compound 1,2 can play the effect that improves the prescription clearing point among a small amount of the present invention of interpolation in prescription, preserve at-20 ℃ and partial crystallization did not take place in 3 days, and partial crystallization takes place the compound 3 of structural similitude, has limited the application of compound 3.After adding compound 1,2, the viscosity of prescription slightly increases, and the dispensing viscosity that adds compound 3 then significantly increases.Contrast above data as can be seen, liquid crystalline cpd tool of the present invention with high clearing point, simultaneously have low viscosity, with the good advantage of other liquid crystalline cpd intermiscibility.
Claims (5)
1, a kind of Tetracycloester liquid crystal compounds is characterized in that having symmetric ethylene bridged bond, and its structural formula is as follows:
R wherein
1, R
2The expression carbon number is 1～10 straight chained alkyl, and ring A is phenyl ring or hexanaphthene.
2,, it is characterized in that structural formula is as follows according to the described liquid crystalline cpd of claim 1:
3,, it is characterized in that structural formula is as follows according to the described liquid crystalline cpd of claim 1:
4,, it is characterized in that structural formula is as follows according to the described liquid crystalline cpd of claim 1:
5, liquid crystalline cpd according to claim 1 is characterized in that structural formula is as follows:
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|---|---|---|---|
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| CNB2005101027591A CN100348693C (en) | 2005-09-14 | 2005-09-14 | Tetracycloester liquid crystal compounds |
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| CN100348693C true CN100348693C (en) | 2007-11-14 |
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| CN108865176B (en) * | 2018-07-02 | 2020-12-01 | 西安彩晶光电科技股份有限公司 | Liquid crystal composition and photoelectric element |
| CN108929704B (en) * | 2018-07-02 | 2020-08-11 | 西安彩晶光电科技股份有限公司 | Liquid crystal composition and photoelectric element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111671A (en) * | 1994-03-29 | 1995-11-15 | 智索公司 | Liquid crystal compound and liquid crystal combinated material |
| CN1188134A (en) * | 1996-11-22 | 1998-07-22 | 智索股份有限公司 | Polyhaloalkyl ether derivatives as well as liquid crystal compositions and liquid crystal display elements containing them |
-
2005
- 2005-09-14 CN CNB2005101027591A patent/CN100348693C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111671A (en) * | 1994-03-29 | 1995-11-15 | 智索公司 | Liquid crystal compound and liquid crystal combinated material |
| CN1188134A (en) * | 1996-11-22 | 1998-07-22 | 智索股份有限公司 | Polyhaloalkyl ether derivatives as well as liquid crystal compositions and liquid crystal display elements containing them |
Non-Patent Citations (1)
| Title |
|---|
| C2桥键类液晶的合成进展 陈新兵 等.合成化学，第11卷第1期 2003 * |
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Effective date of registration: 20100108 Address after: No. 9, Sinosteel Road, Jingwei Industrial Park, Xi'an economic and Technological Development Zone, Shaanxi Patentee after: Xi'an Caijing Opto-Electrical Science & Technology Co., Ltd. Address before: No. eight, No. 168 East Road, Yanta District, Shaanxi, Xi'an Patentee before: Xi'an Inst. of Modern Chemistry |