CN105131974A - Phenanthridone-structure heterocyclic polymerizable liquid crystal compound and preparation method thereof - Google Patents
Phenanthridone-structure heterocyclic polymerizable liquid crystal compound and preparation method thereof Download PDFInfo
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- CN105131974A CN105131974A CN201510451695.XA CN201510451695A CN105131974A CN 105131974 A CN105131974 A CN 105131974A CN 201510451695 A CN201510451695 A CN 201510451695A CN 105131974 A CN105131974 A CN 105131974A
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- 0 CC*(*C(C)(C)OC(C)(*C(C)(C)OC(C(*)=C)=O)C(C)C)[C@]1C=CC(O)=CC1 Chemical compound CC*(*C(C)(C)OC(C)(*C(C)(C)OC(C(*)=C)=O)C(C)C)[C@]1C=CC(O)=CC1 0.000 description 6
- FSZSDNXEHUQXSG-UHFFFAOYSA-O CN(C1=CCC(C(O)[OH2+])C=C1C1=C2CCCC1)C2=O Chemical compound CN(C1=CCC(C(O)[OH2+])C=C1C1=C2CCCC1)C2=O FSZSDNXEHUQXSG-UHFFFAOYSA-O 0.000 description 1
- BTERKECLGBVNMO-UHFFFAOYSA-O O=C1[NH2+]C2=CC=CCC=C2c2c1cccc2 Chemical compound O=C1[NH2+]C2=CC=CCC=C2c2c1cccc2 BTERKECLGBVNMO-UHFFFAOYSA-O 0.000 description 1
- UQJFJMGMOGWAFO-UHFFFAOYSA-O OC(c(cc1)cc(-c2c3cccc2)c1[NH2+]C3=O)=O Chemical compound OC(c(cc1)cc(-c2c3cccc2)c1[NH2+]C3=O)=O UQJFJMGMOGWAFO-UHFFFAOYSA-O 0.000 description 1
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Abstract
The invention provides a phenanthridone-structure heterocyclic polymerizable liquid crystal compound shown in a general formula I. The phenanthridone compound has a high refractive index, can be cured under the action of heating or ultraviolet and visible light, does not yellow easily, has good film forming ability after curing, can be widely used in the fields of panel display, flexible display and other optical films.
Description
Technical field
The present invention relates to a kind of polymerisable liquid crystal compound, the preparation method of polymerisable liquid crystal compound and the application in blooming thereof.
Background technology
Polymerisable liquid crystal compound, because the liquid fluidity of its uniqueness and crystal order, plays positive effect in the field such as lens pillar film (LenticularLens), retardation film (Retarder), patterned retardation film (PatternedRetarder) of particular optical film as bore hole 3D.
Phase shift films can realize the rotation of conversion between various polarization state, polarization plane, and the modulation of all kinds of polarized light, and at optical-fibre communications, photoelastic mechanics, optical precision measurement, and the field such as the optical compensation of flat pannel display has a wide range of applications.Particularly in the optical compensation of liquid-crystal display, play more and more important effect.Such as, for passive-matrix homeotropic liquid crystal display, when not added electric field, light oblique incidence, because incident light is by the existence of angle during liquid crystal layer, certain phase delay can be produced, now, phase shift films is adopted just can effectively to compensate the phase delay caused by oblique incidence, containment squint angle light leak, thus improve the viewing angle characteristic of liquid-crystal display, because high refractive index significantly can reduce thickness, be convenient to optical design, reduce film cost, so retardation film aspect, have great demand to high refractive index.In addition, for Color Liquid Crystal Display, being by realizing display to the modulation of RGB three primary colours, not only wanting accurate control lag amount, also having strict requirement to the dispersion of phase shift films, the dispersion of phase shift films has remarkably influenced to Color Liquid Crystal Display.
About the non-polymerisable liquid crystal of high refractive index, there is a lot of scientific efforts, as the people such as the Zhang Zhiyong (progress of high-birefringence liquid crystals compound, liquid crystal and display, 2014,29, the progress of high-birefringence liquid crystals chemical combination is reviewed 873-880), mention the liquid crystal of high birefringence rate, structure is as follows, wherein mainly comprises central group (mesogenic groups) and position, side group.Central group is formed primarily of ring texture, as phenyl ring, naphthalene nucleus or hexanaphthene etc., can introduce bridged group, ring can be introduced position, side group between ring texture.
Wherein, SL and SR is respectively the left side and the right group, RL and RR is respectively the left side and the right cyclic group, and M is bridged group.
The people such as He Jun (Molecular design and simulation of quick high birefringence rate nematic liquid crystal calculates, liquid crystal and display, 2009,24,15-21) provide a whole set of and utilize Semi-empirical quantum algorithm, can be obtained the Δ n of liquid crystal material by analog calculation.
The high refractive index resins in non-liquid crystal field, normal employing adds mineral compound and improves specific refractory power containing fluorene group or sulfur atom-containing.But mineral compound can produce detrimentally affect to liquid crystal in liquid crystal, during sulfur atom-containing synthesis, peculiar smell is very large, is unfavorable for suitability for industrialized production.
Conventional polymerisable liquid crystal, specific refractory power is about 0.15.Existing high refractive index polymerizable liquid crystal, many containing acetylene bond and cyano group, easily cause xanthochromia and viscosity too high.Therefore, a kind of polymerisable liquid crystal not containing acetylene bond and cyano group newly of special needs, meets the demand of blooming.
Summary of the invention
Goal of the invention: goal of the invention of the present invention is the many deficiencies in order to overcome prior art, provides a kind of high refractive index polymerizable liquid crystalline cpd containing heterocycle.Another object of the present invention is to provide a kind of preparation method of the polymerisable liquid crystal compound containing heterocycle.Another object of the present invention is to provide a kind of purposes of the polymerisable liquid crystal compound containing heterocycle.
Technical scheme: in order to reach foregoing invention object, the invention provides a kind of heterocycle polymerisable liquid crystal compound, this liquid crystalline cpd has formula I phenanthridone structure:
Wherein,
R
1for hydrogen or carbonatoms are the alkyl of 1-6, or can by methyl monosubstituted or polysubstituted aromatic hydrocarbon;
R
2for hydrogen or methyl;
X is singly-bound or carbonyl;
Z is-COO-or-OCO-;
M is 0 or 1;
N is the integer of 1 to 11.
In some embodiments of the present invention, the compound of described formula I is selected from the group of the composition of compound shown in formula I-1:
Wherein,
R
1for hydrogen or carbonatoms are the alkyl of 1-6;
R
2for hydrogen or methyl;
X is singly-bound or carbonyl;
M is 0 or 1;
N is the integer of 1 to 11.
In some embodiments of the present invention, the compound of described formula I is selected from the group be made up of compound shown in formula I-2:
Wherein,
R
2for hydrogen or methyl;
N is the integer of 1 to 11.
In certain preferred embodiments of the present invention, the compound of described formula I-1 is selected from the group be made up of compound shown in formula I-1-1 to I-1-6:
and
In certain preferred embodiments of the present invention, the compound of described formula I-2 is selected from the group be made up of compound shown in formula I-2-1 to I-2-4:
and
Formula I-1 synthetic route is as follows:
Wherein, R
1for hydrogen or carbonatoms are the alkyl of 1-6; R
2for hydrogen or methyl; X is singly-bound or carbonyl; M is 0 or 1; N is the integer of 1 to 11.
A and B of certain mol proportion is joined in reaction vessel, add corresponding stopper (as Resorcinol) simultaneously, catalyzer (as tosic acid) and solvent (as benzene and substituted benzene solvent thereof), back flow reaction can obtain crude product I-1, passed through post to purify, the product I-1 refined can be obtained.
Formula I-2-in-1 one-tenth route is as follows:
Wherein, R
2for hydrogen or methyl; N is the integer of 1 to 11.
C and D of certain mol proportion is joined in reaction vessel, add corresponding stopper (as Resorcinol) simultaneously, catalyzer (as tosic acid) and solvent (as benzene and substituted benzene solvent thereof), back flow reaction can obtain crude product I-2, passed through post to purify, the product I-2 refined can be obtained.
Present invention also offers a kind of above-mentioned application of compound in flat pannel display, Flexible Displays and function blooming field with formula I.
Embodiment
Below with reference to specific embodiments, the present invention is described.It should be noted that, the following examples are example of the present invention, are only used for the present invention is described, and are not used for limiting the present invention.
What in the present invention, parent liquid crystal was chosen is the commodity liquid crystal being numbered TS023-102 that Jiangsu Hecheng Display Technology Co., Ltd. produces.By the compound of gained with 20% part by weight be dissolved in parent, utilize Abbe refractometer to its n
oand n
emeasure, and calculate △ n, then according to the ratio of composition in parent, according to the degree of birefringence △ n (25 DEG C, 589nm) of the extrapolated polymerizable liquid crystal compound of linear relationship.Wherein n
oand n
eneed to regulate eyepiece angle, both differ 90 °, △ n=n
e-n
o.
Embodiment 1
The compd A 1 of 1.1mmol and the compound B-11 of 1mmol are joined in 50mL eggplant-shape bottle, adds the Resorcinol of 0.1mmol, the tosic acid of 1mmol, 20mL toluene solution, 115 DEG C of back flow reaction 4 hours.Product, through extraction into ethyl acetate, is crossed post and is obtained 0.22 gram of faint yellow Compound I-1-1.
1HNMR(CHCl
3)δ：8.58(1H),8.50(1H),8.31(1H),8.15(1H),8.09(2H),7.80(1H),7.68(1H),7.56(1H),7.47(2H),6.36(1H),6.12(1H),5.97(1H),4.26(2H),4.09(2H),3.89(3H),1.80(2H),1.65(2H).
Record the Δ n=0.25 of Compound I-1-1.
Embodiment 2
The compd A 1 of 1.1mmol and the compd B 2 of 1mmol are joined in 50mL eggplant-shape bottle, adds the Resorcinol of 0.1mmol, the tosic acid of 1mmol, 20mL toluene solution, 115 DEG C of back flow reaction 4 hours.Product, through extraction into ethyl acetate, is crossed post and is obtained 0.31 gram of faint yellow Compound I-1-5.
1HNMR(CHCl
3)δ：8.58(1H),8.49(1H),8.39(1H),8.15(1H),7.90(2H),7.79(1H),7.68(1H),7.55(1H),7.47(2H),6.38(1H),6.30(1H),4.17(2H),4.09(2H),3.89(3H),2.01(3H),1.77(2H),1.67(2H),1.48(2H),1.38(2H)。
Record the Δ n=0.26 of Compound I-1-5.
Embodiment 3
The compd A 2 of 1.1mmol and the compd B 3 of 1mmol are joined in 50mL eggplant-shape bottle, adds the Resorcinol of 0.1mmol, the tosic acid of 1mmol, 20mL toluene solution, 115 DEG C of back flow reaction 4 hours.Product, through extraction into ethyl acetate, is crossed post and is obtained 0.32 gram of faint yellow Compound I-1-6.
1HNMR(CHCl
3)δ：8.52(2H),8.28(1H),8.10(1H),7.93(2H),7.81(1H),7.71(1H),7.52(1H),7.45(2H),6.33(1H),6.05(2H),4.74(1H),4.23(2H),4.09(1H),3.92(2H),1.65(4H),1.46(4H),1.22(3H)。
Record the Δ n=0.25 of Compound I-1-6.
Embodiment 4
The compd B 4 of the compound A-13 of 1mmol and 1.1mmol is joined in 50mL eggplant-shape bottle, adds the Resorcinol of 0.1mmol, the tosic acid of 1mmol, 20mL toluene solution, 115 DEG C of back flow reaction 4 hours.Product, through extraction into ethyl acetate, is crossed post and is obtained 0.29 gram of faint yellow Compound I-2-1.
1HNMR(CHCl
3)δ：8.49(1H),8.25(1H),8.00(3H)7.68(1H),7.51(1H),7.27(1H),7.14(2H),7.09(1H),7.04(3H),6.36(1H),6.00(2H),4.10(4H),2.22(6H),1.92(2H),1.70(2H)。
Record the Δ n=0.25 of Compound I-2-1.
Embodiment 5
By the I-1-1 that above-described embodiment 1 to 4 prepares, I-1-5, I-1-6 and I-2-1 polymerisable liquid crystal compound, after solidification, obtained blooming solar radiation 10 days, does not turn yellow.Film no pin-hole defect after solidification and color fringe, good film-forming property.
Above experimental result shows, the heterocycle polymerisable liquid crystal compound containing phenanthridone structure provided by the invention has high degree of birefringence, and Δ n is greater than 0.25.And experimental result shows, polymerisable liquid crystal compound provided by the invention is inhibited from yellowing, long service life, obtained film no pin-hole defect and color fringe, good film-forming property, can meet the various requirement of blooming, compared to the prior art achieves extraordinary technique effect.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a heterocycle polymerisable liquid crystal compound, this liquid crystalline cpd has the phenanthridone structure of formula I:
Wherein,
R
1for hydrogen, carbonatoms are the alkyl of 1-6 or are the monosubstituted or polysubstituted aromatic hydrocarbon by methyl;
R
2for hydrogen or methyl;
X is singly-bound or carbonyl;
Z is-COO-or-OCO-;
M is 0 or 1;
N is the integer of 1 to 11.
2. heterocycle polymerisable liquid crystal compound according to claim 1, is characterized in that, described compound is selected from the group of the composition of compound shown in formula I-1:
Wherein,
R
1for hydrogen or carbonatoms are the alkyl of 1-6;
R
2for hydrogen or methyl;
X is singly-bound or carbonyl;
M is 0 or 1;
N is the integer of 1 to 11.
3. heterocycle polymerisable liquid crystal compound according to claim 1, it is characterized in that, described compound is selected from the group be made up of compound shown in formula I-2:
Wherein,
R
2for hydrogen or methyl;
N is the integer of 1 to 11.
4. heterocycle polymerisable liquid crystal compound according to claim 2, is characterized in that, the compound of described formula I-1 is selected from the group be made up of compound shown in formula I-1-1 to I-1-6:
5. heterocycle polymerisable liquid crystal compound according to claim 3, is characterized in that, the compound of described formula I-2 is selected from the group be made up of compound shown in formula I-2-1 to I-2-4:
6. there is the preparation method of the polymerisable liquid crystal of heterocycle shown in formula I-1 compound, it is characterized in that, comprise the following steps:
The compd A of certain mol proportion and B are joined in reaction vessel, add corresponding stopper, catalysts and solvents, back flow reaction simultaneously, purify through post, obtain formula I-1 compound refined:
Wherein, R
1for hydrogen or carbonatoms are the alkyl of 1-6; R
2for hydrogen or methyl; X is singly-bound or carbonyl; M is 0 or 1; N is the integer of 1 to 11.
7. there is the preparation method of the polymerisable liquid crystal of heterocycle shown in formula I-2 compound, it is characterized in that, comprise the following steps:
The Compound C of certain mol proportion and D are joined in reaction vessel, add corresponding stopper, catalysts and solvents, back flow reaction simultaneously, purify through post, obtain formula I-2 compound refined:
Wherein, R
2for hydrogen or methyl; N is the integer of 1 to 11.
8. the application of the heterocycle polymerisable liquid crystal compound described in any one of claim 1 to 5 in preparation flat pannel display, Flexible Displays and other blooming.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082761A (en) * | 2017-04-17 | 2017-08-22 | 上海大学 | Phenanthridone or benzo phenanthridines ketone derivatives and its synthetic method |
| CN111033330A (en) * | 2017-08-21 | 2020-04-17 | 住友化学株式会社 | Phase difference plate with optical compensation function |
| JP2020128450A (en) * | 2019-02-07 | 2020-08-27 | 東ソー株式会社 | Polymerizable compound, polymer and retardation film |
| CN111954706A (en) * | 2018-05-03 | 2020-11-17 | 株式会社Lg化学 | Polymerizable liquid crystal compound, liquid crystal composition for optical element, polymer, optically anisotropic body, and optical element for display device |
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| EP0946513B1 (en) * | 1996-12-19 | 2002-01-30 | Aventis Research & Technologies GmbH & Co. KG | Derivatives of 6-fluorophenanthridine for liquid crystal mixtures |
| US20030008172A1 (en) * | 2001-04-10 | 2003-01-09 | Mario Leclerc | Conjugated polycarbazole derivatives in Organic Light Emitting Diodes |
| CN102977017A (en) * | 2012-12-24 | 2013-03-20 | 湖南大学 | Method for catalytically preparing 6(5H)-phenanthridine ketone by copper component |
| CN103275003A (en) * | 2013-05-22 | 2013-09-04 | 浙江大学 | Method for preparing phenanthridinone derivative |
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2015
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| EP0946513B1 (en) * | 1996-12-19 | 2002-01-30 | Aventis Research & Technologies GmbH & Co. KG | Derivatives of 6-fluorophenanthridine for liquid crystal mixtures |
| US20020006927A1 (en) * | 2000-05-19 | 2002-01-17 | Jia-He Li | Sulfonamide and carbamide derivatives of 6(5H)phenanthridinones and their uses |
| US20030008172A1 (en) * | 2001-04-10 | 2003-01-09 | Mario Leclerc | Conjugated polycarbazole derivatives in Organic Light Emitting Diodes |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082761A (en) * | 2017-04-17 | 2017-08-22 | 上海大学 | Phenanthridone or benzo phenanthridines ketone derivatives and its synthetic method |
| CN107082761B (en) * | 2017-04-17 | 2020-04-03 | 上海大学 | Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof |
| CN111033330A (en) * | 2017-08-21 | 2020-04-17 | 住友化学株式会社 | Phase difference plate with optical compensation function |
| CN111954706A (en) * | 2018-05-03 | 2020-11-17 | 株式会社Lg化学 | Polymerizable liquid crystal compound, liquid crystal composition for optical element, polymer, optically anisotropic body, and optical element for display device |
| US11365354B2 (en) * | 2018-05-03 | 2022-06-21 | Lg Chem, Ltd. | Polymerizable liquid crystal compound, liquid crystal composition for optical element, polymer, optically anisotropic body, and optical element for display device |
| CN111954706B (en) * | 2018-05-03 | 2023-09-08 | 株式会社Lg化学 | Polymerizable liquid crystal compound, liquid crystal composition for optical element, polymer, optically anisotropic body, and optical element for display device |
| JP2020128450A (en) * | 2019-02-07 | 2020-08-27 | 東ソー株式会社 | Polymerizable compound, polymer and retardation film |
| JP7279385B2 (en) | 2019-02-07 | 2023-05-23 | 東ソー株式会社 | Polymerizable compounds, polymers and retardation films |
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| CN105131974B (en) | 2017-04-12 |
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