CN105131974B - 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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- CN105131974B CN105131974B CN201510451695.XA CN201510451695A CN105131974B CN 105131974 B CN105131974 B CN 105131974B CN 201510451695 A CN201510451695 A CN 201510451695A CN 105131974 B CN105131974 B CN 105131974B
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- 0 CN(c(ccc(C(O*)=O)c1)c1-c1ccccc11)C1=O Chemical compound CN(c(ccc(C(O*)=O)c1)c1-c1ccccc11)C1=O 0.000 description 4
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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 its in blooming
In application.
Background technology
Polymerisable liquid crystal compound because its unique liquid fluidity and crystal order, in particular optical film such as bore hole
The lens pillar film (Lenticular Lens) of 3D, retardation film (Retarder), patterned retardation film (Patterned
) etc. Retarder field plays positive effect.
Phase shift films can realize conversion between various polarization states, the rotation of plane of polarization, and the modulation of all kinds of polarized light,
Have a wide range of applications in fields such as optical-fibre communications, photoelastic mechanics, optical precision measurement, and the optical compensations of flat pannel display.
Particularly in terms of the optical compensation of liquid crystal display, more and more important effect is played.For example, to passive-matrix vertical orientation
For liquid crystal display, in the case where electric field, light oblique incidence is not added with, when passing through liquid crystal layer due to incident illumination, angle deposits
, certain Phase delay can be produced, now, the Phase delay that just can effectively compensate for being caused by oblique incidence using phase shift films,
Containment angle of strabismus light leak, so as to improve the viewing angle characteristic of liquid crystal display, because high index of refraction can significantly reduce thickness, is easy to
Optical design, reduces thin film cost, so in terms of retardation film, having great demand to high index of refraction.In addition, to colored liquid
For brilliant display, it is to realize showing by the modulation to RGB three primary colours, not only wants precise control retardation, the color to phase shift films
The dispersion that scattered performance also has strict requirements, phase shift films is had a significant impact to Color Liquid Crystal Display.
With regard to the non-polymerisable liquid crystal of high index of refraction, there are many research works, such as Zhang Zhiyong et al. (high birefringences
The progress of liquid-crystal compoundss, liquid crystal with show, 2014,29,873-880) in review entering for high-birefringence liquid crystals chemical combination
Exhibition, mentions the liquid crystal of high birefringence rate, and structure is as follows, wherein mainly including central group (mesogenic groups) and side position base
Group.Central group is mainly made up of circulus, such as phenyl ring, naphthalene nucleus or hexamethylene etc., and bridging can be introduced between circulus
Group, can be with introducing side position group on ring.
Wherein, SL and SR is respectively the left side and the right group, and RL and RR is respectively the left side and the right cyclic group, and M is bridging
Group.
He Jun et al. (the Molecular design and simulation calculating of quick high birefringence rate nematic liquid crystal, liquid crystal and display,
2009,24,15-21) Semi-empirical quantum algorithm is utilized there is provided a whole set of, liquid crystal material can be calculated by simulation
Δ n.
The high refractive index resins in non-liquid crystal field, improve frequently with addition inorganic compound and containing fluorene group or sulfur atom-containing
Refractive index.But inorganic compound can produce harmful effect in liquid crystal to liquid crystal, and when sulfur atom-containing synthesizes, abnormal flavour is very big, is unfavorable for
Industrialized production.
Conventional polymerisable liquid crystal, refractive index is 0.15 or so.Existing high refractive index polymerizable liquid crystal, contains acetylene bond more
And cyano group, easily cause xanthochromia and viscosity too high.It is accordingly required in particular to a kind of new polymerizable liquid without acetylene bond and cyano group
Crystalline substance, meets the demand of blooming.
The content of the invention
Goal of the invention：The goal of the invention of the present invention is for many deficiencies for overcoming prior art, there is provided a kind of to contain heterocycle
High refractive index polymerizable liquid-crystal compoundss.It is a further object of the present invention to provide a kind of polymerisable liquid crystal compound containing heterocycle
Preparation method.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 purpose, the present invention provides a kind of heterocycle polymerisable liquid crystal compound, the liquid
Crystallization compound has formula I phenanthridone structure：
Wherein,
R1For hydrogen or carbon number for 1-6 alkyl, or can be by methyl is monosubstituted or polysubstituted aromatic hydrocarbon；
R2For hydrogen or methyl；
X is singly-bound or carbonyl；
Z is-COO- or-OCO-；
M is 0 or 1；
N is 1 to 11 integer.
In some embodiments of the present invention, the compound of the formula I selected from compound group shown in formula I -1 into
Group：
Wherein,
R1For hydrogen or carbon number for 1-6 alkyl；
R2For hydrogen or methyl；
X is singly-bound or carbonyl；
M is 0 or 1；
N is 1 to 11 integer.
In some embodiments of the present invention, the compound of the formula I selected from compound group shown in formula I -2 into
Group：
Wherein,
R2For hydrogen or methyl；
N is 1 to 11 integer.
In the certain preferred embodiments of the present invention, the compound of the formula I -1 is selected from the -1- of formula I -1-1 to I
Compound group shown in 6 into group：
And
In the certain preferred embodiments of the present invention, the compound of the formula I -2 is selected from the -2- of formula I -2-1 to I
Compound group shown in 4 into group：
And
- 1 synthetic route of formula I is as follows：
Wherein, R1For hydrogen or carbon number for 1-6 alkyl；R2For hydrogen or methyl；X is singly-bound or carbonyl；M is 0 or 1；n
For 1 to 11 integer.
The A and B of certain mol proportion are added in reaction vessel, while corresponding polymerization inhibitor (such as hydroquinone) is added,
Catalyst (such as p-methyl benzenesulfonic acid) and solvent (such as benzene and its substituted benzene solvent), back flow reaction is obtained crude product I -1, Jing
Post purification, you can obtain refined product I -1.
Formula I -2-in-1 as follows into route：
Wherein, R2For hydrogen or methyl；N is 1 to 11 integer.
The C and D of certain mol proportion are added in reaction vessel, while corresponding polymerization inhibitor (such as hydroquinone) is added,
Catalyst (such as p-methyl benzenesulfonic acid) and solvent (such as benzene and its substituted benzene solvent), back flow reaction is obtained crude product I -2, Jing
Post purification, you can obtain refined product I -2.
Present invention also offers a kind of above-mentioned compound with formula I is in flat pannel display, Flexible Displays and function optics
Application in film field.
Specific embodiment
The present invention is illustrated below with reference to specific embodiment.It should be noted that the following examples are the present invention
Example, only for illustrating the present invention, and be not limited to the present invention.
What in the present invention, parent liquid crystal was chosen is that the numbering of Jiangsu Hecheng Display Technology Co., Ltd.'s production is
The commodity liquid crystal of TS023-102.The compound of gained is dissolved in parent with 20% part by weight, using Abbe refractometer
To its noAnd neMeasure, and calculate △ n, further according to the ratio of compositionss in parent, according to the extrapolated polymerism of linear relationship
The birefringence △ n (25 DEG C, 589nm) of liquid-crystal composition.Wherein noAnd neNeed to adjust eyepiece angle, both 90 ° of differences, △ n
=ne-no。
Embodiment 1
The compound B-11 of the compound A1 and 1mmol of 1.1mmol is added in 50mL eggplant-shape bottles, adds 0.1mmol's
Hydroquinone, the p-methyl benzenesulfonic acid of 1mmol, 20mL toluene solutions, 115 DEG C of back flow reaction 4 hours.Product Jing ethyl acetate extracts
Take, cross post and obtain 0.22 gram of faint yellow compound I-1-1.
1H NMR(CHCl3)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).
Measure the Δ n=0.25 of compound I-1-1.
Embodiment 2
The compound B2 of the compound A1 and 1mmol of 1.1mmol is added in 50mL eggplant-shape bottles, adds 0.1mmol's
Hydroquinone, the p-methyl benzenesulfonic acid of 1mmol, 20mL toluene solutions, 115 DEG C of back flow reaction 4 hours.Product Jing ethyl acetate extracts
Take, cross post and obtain 0.31 gram of faint yellow compound I-1-5.
1H NMR(CHCl3)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)。
Measure the Δ n=0.26 of compound I-1-5.
Embodiment 3
The compound B3 of the compound A2 and 1mmol of 1.1mmol is added in 50mL eggplant-shape bottles, adds 0.1mmol's
Hydroquinone, the p-methyl benzenesulfonic acid of 1mmol, 20mL toluene solutions, 115 DEG C of back flow reaction 4 hours.Product Jing ethyl acetate extracts
Take, cross post and obtain 0.32 gram of faint yellow compound I-1-6.
1H NMR(CHCl3)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)。
Measure the Δ n=0.25 of compound I-1-6.
Embodiment 4
The compound B4 of the compound A-13 and 1.1mmol of 1mmol is added in 50mL eggplant-shape bottles, adds 0.1mmol's
Hydroquinone, the p-methyl benzenesulfonic acid of 1mmol, 20mL toluene solutions, 115 DEG C of back flow reaction 4 hours.Product Jing ethyl acetate extracts
Take, cross post and obtain 0.29 gram of faint yellow compound I-2-1.
1H NMR(CHCl3)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)。
Measure the Δ n=0.25 of compound I-2-1.
Embodiment 5
The I-1-1 that above-described embodiment 1 to 4 is prepared, I-1-5, I-1-6 and I-2-1 polymerisable liquid crystal compound, Gu
Blooming sunlight is obtained to irradiate 10 days after change, does not turn yellow.Thin film no pin-hole defect and color fringe after solidification, good film-forming property.
Above test result indicate that, the present invention provide the heterocycle polymerisable liquid crystal compound containing phenanthridone structure have height
Birefringence, Δ n be more than 0.25.And test result indicate that, the polymerisable liquid crystal compound that the present invention is provided is inhibited from yellowing,
Long service life, is obtained thin film no pin-hole defect and color fringe, good film-forming property, can meet the various requirement of blooming, and existing
There is technology to compare and achieve extraordinary technique effect.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of heterocycle polymerisable liquid crystal compound, the liquid-crystal compoundss have the phenanthridone structure of formula I：
Wherein,
R1For hydrogen or carbon number are for the alkyl of 1-6 or be by methyl substituted phenyl；
R2For hydrogen or methyl；
X is singly-bound or carbonyl；
Z is-COO- or-OCO-；
M is 0 or 1；
N is 1 to 11 integer.
2. heterocycle polymerisable liquid crystal compound according to claim 1, it is characterised in that the compound selected from formula I-
Compound group shown in 1 into group：
Wherein,
R1For hydrogen or carbon number for 1-6 alkyl；
R2For hydrogen or methyl；
X is singly-bound or carbonyl；
M is 0 or 1；
N is 1 to 11 integer.
3. heterocycle polymerisable liquid crystal compound according to claim 1, it is characterised in that the compound is selected from formula
Compound group shown in I -2 into group：
Wherein,
R2For hydrogen or methyl；
N is 1 to 11 integer.
4. heterocycle polymerisable liquid crystal compound according to claim 2, it is characterised in that the compound of the formula I -1
Selected from compound group shown in the -1-6 of formula I -1-1 to I into group：
5. heterocycle polymerisable liquid crystal compound according to claim 3, it is characterised in that the compound of the formula I -2
Selected from compound group shown in the -2-4 of formula I -2-1 to I into group：
6. there is the preparation method of heterocycle polymerisable liquid crystal compound shown in formula I -1, it is characterised in that comprise the following steps：
The compound A and B of certain mol proportion are added in reaction vessel, while add corresponding polymerization inhibitor, catalyst and molten
Agent, back flow reaction are purified through post, obtain refined -1 compound of formula I：
Wherein, R1For hydrogen or carbon number for 1-6 alkyl；R2For hydrogen or methyl；X is singly-bound or carbonyl；M is 0 or 1；N be 1 to
11 integer.
7. there is the preparation method of heterocycle polymerisable liquid crystal compound shown in formula I -2, it is characterised in that comprise the following steps：
The compound C and D of certain mol proportion are added in reaction vessel, while add corresponding polymerization inhibitor, catalyst and molten
Agent, back flow reaction are purified through post, obtain refined -2 compound of formula I：
Wherein, R2For hydrogen or methyl；N is 1 to 11 integer.
8. the heterocycle polymerisable liquid crystal compound described in any one of claim 1 to 5 prepare flat pannel display, Flexible Displays and its
Application in its blooming.
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| CN107082761B (en) * | 2017-04-17 | 2020-04-03 | 上海大学 | Phenanthridinone or benzophenanthridinone derivative and synthesis method thereof |
| JP7491660B2 (en) * | 2017-08-21 | 2024-05-28 | 住友化学株式会社 | Retardation plate with optical compensation function |
| KR102195455B1 (en) * | 2018-05-03 | 2020-12-28 | 주식회사 엘지화학 | Polymerizable liquid crystal compound, liquid crystal composition for optical element, polymer, optically anisotropic body, and optical element for display device |
| JP7279385B2 (en) * | 2019-02-07 | 2023-05-23 | 東ソー株式会社 | Polymerizable compounds, polymers and retardation films |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0946513B1 (en) * | 1996-12-19 | 2002-01-30 | Aventis Research & Technologies GmbH & Co. KG | Derivatives of 6-fluorophenanthridine for liquid crystal mixtures |
| 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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|---|---|---|---|---|
| US6723733B2 (en) * | 2000-05-19 | 2004-04-20 | Guilford Pharmaceuticals, Inc. | Sulfonamide and carbamide derivatives of 6(5H)phenanthridinones and their uses |
| US6630254B2 (en) * | 2001-04-10 | 2003-10-07 | National Research Council Of Canada | Conjugated polycarbazole derivatives in Organic Light Emitting Diodes |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0946513B1 (en) * | 1996-12-19 | 2002-01-30 | Aventis Research & Technologies GmbH & Co. KG | Derivatives of 6-fluorophenanthridine for liquid crystal mixtures |
| 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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