CN112159667A - Polymerizable compound and application thereof - Google Patents

Polymerizable compound and application thereof Download PDF

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CN112159667A
CN112159667A CN202010177391.XA CN202010177391A CN112159667A CN 112159667 A CN112159667 A CN 112159667A CN 202010177391 A CN202010177391 A CN 202010177391A CN 112159667 A CN112159667 A CN 112159667A
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carbon atoms
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fluorine
substituted
liquid crystal
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孙新战
李明
王一平
鲍永锋
姜军
梁志安
孟劲松
员国良
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Abstract

The invention relates to a polymerizable compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The polymerizable compound has the following structure shown in the formula I, and the liquid crystal composition containing the polymerizable compound has high voltage holding ratio and stable pretilt angle, and can reduce afterimage when being applied to a PS- (polymer stabilization) or PSA- (polymer stable alignment) type liquid crystal display device,The contrast is improved, and the product quality is improved.
Figure DDA0002411264450000011

Description

Polymerizable compound and application thereof
Technical Field
The invention belongs to the technical field of liquid crystal display, and particularly relates to a polymerizable compound, a liquid crystal composition containing the polymerizable compound, and a liquid crystal display element or a liquid crystal display containing the polymerizable compound or the liquid crystal composition.
Background
With the development of Display technology, flat panel Display devices such as Liquid Crystal Display (LCD) devices have advantages of high image quality, power saving, thin body, and wide application range, and thus are widely used in various consumer electronics products such as mobile phones, televisions, personal digital assistants, digital cameras, notebook computers, and desktop computers, and are becoming the mainstream of Display devices.
Reactive Mesogen (RM) is currently a very popular and important research direction in the lcd industry, and its possible applications include Polymer Sustained Alignment (PSA) lcd, polymer sustained blue phase (PS-BP) lcd, and patterned retardation Film (Pattern recorder Film).
However, the use of liquid crystal compounds in admixture with RMs in PSA mode displays still has some disadvantages. First, not all RMs are suitable for PSA displays to date; meanwhile, if the RM is polymerized using Ultraviolet light (Ultraviolet light) without adding a photoinitiator, the possibility of selecting RM species becomes less; also, it is often difficult to find a more suitable selection criterion than the direct PSA test with pre-tilt measurement; in addition, the liquid crystal compound is required to form a liquid crystal composition having a low rotational viscosity and good mutual solubility in combination with a selected RM, and a high Voltage Holding Ratio (VHR) to achieve a desired display effect. In the PSA-VA display mode, it is important that the liquid crystal composition after being irradiated with ultraviolet light still has a high VHR, otherwise the problems of image sticking and the like of the display can be caused; another problem is the stability of the pretilt angle, which can negatively affect the display performance if the pretilt angle is not kept constant during the manufacturing process of the display, for example by increasing the black state transmittance and thus reducing the contrast ratio.
Disclosure of Invention
The present inventors have conducted intensive studies to overcome the problems of poor miscibility with Reactive Mesogen (RM), low Voltage Holding Ratio (VHR), and poor stability of pretilt angle, and to solve the problems of image sticking and low contrast of liquid crystal display elements or liquid crystal displays, and have found that the problems can be solved by including the compound of the present invention in a liquid crystal composition, thereby completing the present invention.
Specifically, the present invention comprises the following:
in a first aspect of the invention, there is provided a polymerizable compound of formula I,
Figure BDA0002411264430000021
wherein the content of the first and second substances,
L1、L2、L3、L4each independently represents a F atom, a Cl atom, -CN, a straight-chain alkyl group having 1 to 25C atoms, a branched-chain alkyl group having 3 to 25C atoms, a cyclic alkyl group having 2 to 25C atomsAlkenyl or alkynyl having 2 to 25C atoms, one or more non-adjacent-CH2-the group is optionally substituted by-O-, -S-, -NH-, -CO-O-, -O-CO-O-, and wherein one or more H atoms are optionally substituted by halogen atoms;
r1、r3each independently represents 0, 1,2, 3 or 4;
r2、r4each independently represents 0, 1,2 or 3;
x1、x2、x3、x4each independently represents 0, 1 or 2, and x1+x2+x3+x4≥3；
Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2Each independently represents a single bond, a straight chain alkyl group having 1 to 25C atoms, a branched alkyl group having 3 to 25C atoms, a cyclic alkyl group having 3 to 25C atoms, an alkenyl group having 2 to 25C atoms, or an alkynyl group having 2 to 25C atoms, and wherein one or more non-adjacent-CH groups2-the group is optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms;
P1、P2、P3、P4each independently represents a polymerizable group.
In a second aspect of the invention, there is provided a liquid crystal composition comprising one or more polymerizable compounds of formula i.
In a third aspect of the present invention, there is provided a liquid crystal display element or a liquid crystal display comprising one or more polymerizable compounds represented by formula i or a liquid crystal composition comprising one or more polymerizable compounds represented by formula i.
Effects of the invention
Compared with the prior art, the polymerizable compound has good intersolubility with a liquid crystal composition, the commercial liquid crystal composition has higher Voltage Holding Ratio (VHR), and the liquid crystal composition containing the polymerizable compound has a larger and stable pretilt angle when being prepared into a display device, so that when being applied to a PS- (polymer stabilization) or PSA- (polymer stable alignment) type liquid crystal display device, the polymerizable compound can reduce residual images and improve contrast, thereby improving the product quality.
Drawings
FIG. 1 shows an MS mass spectrum of a polymerizable compound represented by the formula I-2-1;
FIG. 2 shows a polymerizable compound represented by the formula I-2-11H-NMR spectrum;
Detailed Description
The invention discloses a polymerizable compound shown as the formula I.
The invention discloses polymerizable compounds of formula I, preferably, compounds of formula I:
L1、L2、L3、L4each independently represents an alkyl group having 1 to 5 carbon atoms, a fluorine-substituted alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine-substituted alkoxy group having 1 to 5 carbon atoms, an F atom or a Cl atom;
r1、r3each independently represents 0, 1 or 2; r is2、r4Each independently represents 0 or 1;
x1、x2、x3、x4each independently represents 0 or 1, and x1+x2+x3+x4≥3；
Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2Each independently represents a single bond, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms, wherein one or more non-adjacent-CH groups2-the group is optionally substituted by-O-, -CO-O-, -O-CO-, one or more H atoms are optionally substituted by F atoms;
P1、P2、P3、P4each independently represent
Figure BDA0002411264430000031
Figure BDA0002411264430000032
Wherein, the points in the structural formula represent the connecting positions of all groups and the compound main body shown in the formula I.
The polymerizable compound represented by the formula I disclosed in the present invention is more preferably selected from the group consisting of the compounds represented by the following formulae I-1-1 to I-17-3,
Figure BDA0002411264430000041
Figure BDA0002411264430000051
Figure BDA0002411264430000061
Figure BDA0002411264430000071
Figure BDA0002411264430000081
Figure BDA0002411264430000091
Figure BDA0002411264430000101
Figure BDA0002411264430000111
Figure BDA0002411264430000121
Figure BDA0002411264430000131
Figure BDA0002411264430000141
Figure BDA0002411264430000151
Figure BDA0002411264430000161
Figure BDA0002411264430000171
Figure BDA0002411264430000181
Figure BDA0002411264430000191
the present invention also provides a liquid crystal composition comprising one or more of the aforementioned polymerizable compounds of the present invention.
A liquid crystal composition according to one embodiment of the present invention comprises the compound represented by the formula I. The liquid crystal composition may contain a liquid crystal compound other than the compound represented by the formula I and other additive materials in addition to the compound represented by the formula I.
Preferably, the liquid crystal composition of the present invention further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,
Figure BDA0002411264430000201
in the formula II, R1、R2Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
Figure BDA0002411264430000202
each independently represent
Figure BDA0002411264430000203
In the formula III, R3、R4Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more non-adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;
Z1、Z2each independently represents a single bond, -CH2CH2-、-CH2O-or-OCH2-；
Figure BDA0002411264430000204
Each independently represent
Figure BDA0002411264430000205
Figure BDA0002411264430000206
m1Represents 1 or 2, when m1When the expression is shown in the figure 2,
Figure BDA0002411264430000207
the same or different;
n1represents 0, 1 or 2, when n1When the expression is shown in the figure 2,
Figure BDA0002411264430000208
the same or different.
By containing the combination of the compound represented by the formula II and the compound represented by the formula III in the liquid crystal composition, the obtained liquid crystal composition has low rotational viscosity, is favorable for improving the response speed of the liquid crystal composition, has negative dielectric anisotropy, and can adjust the driving voltage of the composition.
In the present invention, the total mass of the compounds other than the compound represented by the formula I is taken as 100%, and the percentage of the ratio of the mass of the compound represented by the formula I to the total mass of the other compounds is taken as the mass fraction of the compound represented by the formula I in the liquid crystal composition. For example, in the case where the liquid crystal composition contains only the compounds represented by the formulae I, II and III, the total content of the compounds represented by the formulae II and III is taken as 100%, and the percentage of the ratio of the amount of the compound represented by the formula I added to the total mass of the compounds represented by the formulae II and III is taken as the mass fraction of the compound represented by the formula I.
In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula II is selected from the group consisting of compounds represented by the formulae II-1 to II-17,
Figure BDA0002411264430000211
Figure BDA0002411264430000221
preferably, the aforementioned compound represented by the formula III is selected from the group consisting of compounds represented by the formulae III-1 to III-15,
Figure BDA0002411264430000222
Figure BDA0002411264430000231
wherein R is31、R41Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more non-adjacent-CH in the group2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.
The liquid crystal composition disclosed by the invention preferably further comprises one or more compounds shown as a formula IV,
Figure BDA0002411264430000232
wherein R is5、R6Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R5、R6Any one or more non-adjacent-CH2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH2O-。
By containing the compound shown in the formula IV in the liquid crystal composition, the liquid crystal composition has larger negative dielectric anisotropy, and is favorable for reducing the driving voltage of a device.
Further, the compound represented by the formula IV is selected from compounds represented by formulas IV-1 to IV-10,
Figure BDA0002411264430000233
Figure BDA0002411264430000241
wherein R is51、R61Represents an alkyl group having 1 to 6 carbon atoms;
the liquid crystal composition disclosed by the invention preferably further comprises one or more compounds shown as a formula V,
Figure BDA0002411264430000242
wherein R is7、R8Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
Figure BDA0002411264430000243
each independently represent
Figure BDA0002411264430000244
Further, the compound represented by the above formula V is preferably selected from the group consisting of compounds represented by the formulae V-1 to V-4,
Figure BDA0002411264430000245
wherein R is71、R81Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 2-propenyl group, or a 3-pentenyl group; r82Represents an alkoxy group having 1 to 5 carbon atoms;
by including the compound represented by the formula V in the liquid crystal composition of the present invention, a high clearing point and a high elastic constant, particularly a splay elastic constant K can be obtained33And is beneficial to improving the parameter performance of the liquid crystal composition.
The liquid crystal composition disclosed by the invention preferably further comprises one or more compounds shown as a formula VI,
Figure BDA0002411264430000251
wherein R is9、R10Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
F1、F2、F3each independently represents a H atom or a F atom, and F2、F3Not being F atoms at the same time;
Figure BDA0002411264430000252
to represent
Figure BDA0002411264430000253
Further, the aforementioned compound represented by the formula VI is preferably selected from the group consisting of compounds represented by the formulae VI-1 to VI-3,
Figure BDA0002411264430000254
wherein R is91、R101Each independently preferably represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
The clearing point of the liquid crystal composition can be improved by containing the compound selected from the compounds shown in formulas VI-1 to VI-3 in the liquid crystal composition.
Preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 30-60% of a compound shown as a formula II, 30-60% of a compound shown as a formula III and 1-10% of a compound shown as a formula VI;
preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV and 1-10% of a compound shown as a formula VI;
preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 35-45% of a compound shown as a formula II, 45-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV and 2-5% of a compound shown as a formula VI.
Preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-30% of a compound shown as a formula V and 1-10% of a compound shown as a formula VI;
preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 25-40% of a compound shown as a formula II, 35-50% of a compound shown as a formula III, 5-20% of a compound shown as a formula V and 2-5% of a compound shown as a formula VI.
Preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV, 1-30% of a compound shown as a formula V and 1-10% of a compound shown as a formula VI;
preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV, 5-20% of a compound shown as a formula V and 2-5% of a compound shown as a formula VI.
In the liquid crystal composition disclosed by the present invention, a dopant having various functions may be added, and when the liquid crystal composition contains a dopant, the content of the dopant is preferably 0.01 to 1% by mass in the liquid crystal composition, and examples of the dopant include an antioxidant, an ultraviolet absorber, and a chiral agent.
Examples of the antioxidant and ultraviolet absorber include,
Figure BDA0002411264430000261
t represents an integer of 1 to 10.
The liquid crystal display device of the present invention comprises the polymerizable compound of the present invention or the liquid crystal composition of the present invention, and the display device is an active matrix display device or a passive matrix display device.
Preferably, the liquid crystal display device of the present invention is preferably an active matrix liquid crystal display device.
Preferably, the active matrix display device is a PSVA-TFT or IPS-TFT liquid crystal display device.
The liquid crystal display device of the present invention is not limited in its structure as long as the compound represented by formula I of the present invention is contained in the liquid crystal composition used for the liquid crystal display device, and those skilled in the art can select an appropriate structure of the liquid crystal display device according to the desired performance.
As an embodiment of the liquid crystal display device of the present invention, for example, the following structures can be cited: the liquid crystal display panel comprises a first substrate, a second substrate and a liquid crystal composition arranged between the first substrate and the second substrate, wherein the first substrate and the second substrate are arranged in parallel and oppositely, one sides of the first substrate and the second substrate, which are close to the liquid crystal composition, are provided with alignment layers, the first substrate is provided with a common electrode, the second substrate is provided with a pixel electrode, and spacers are scattered between the first substrate and the second substrate.
As the method for manufacturing the liquid crystal display of the present invention, those skilled in the art can select an appropriate method for manufacturing according to common knowledge in the art. As an example of the manufacturing method of the liquid crystal display of the present invention, for example, a manufacturing method including the steps of:
uniformly coating alignment materials, which can be selected from polyimide, on the surfaces of the first substrate and the second substrate, heating and curing the uniformly coated alignment materials at the heating temperature of 210-250 ℃ to form alignment layers; spreading a spacer on the surface of the second substrate, coating frame glue along the edge of the first substrate, and curing at 100-150 ℃; arranging the first substrate and the second substrate oppositely, and attaching to form a structure with an interlayer space; injecting a liquid crystal composition into the interlayer space between the first substrate and the second substrate, sealing and curing to seal the liquid crystal composition between the first substrate and the second substrate, and simultaneously performing electrification and ultraviolet irradiation. The ultraviolet irradiation is divided into two stages of first stage ultraviolet irradiation (UV1) and second stage ultraviolet irradiation (UV 2). At the UV1 stage, the wavelength of ultraviolet light is 360-370 nm, and the illumination of ultraviolet light is 60-72 mw/cm2. The time for the ultraviolet irradiation may be, for example, 50 to 65 seconds, preferably 50 to 60 seconds.
Second-stage light irradiation (UV2) is performed after the first-stage light irradiation is completed, and UV2 is usedExamples of the light include ultraviolet light. The second stage ultraviolet irradiation (UV2) has an ultraviolet wavelength of 360-370 nm, and the second stage UV2 uses an ultraviolet irradiation of 3-8 mw/cm2. By adopting the irradiance, the unpolymerized compound shown in the formula I can be slowly and completely polymerized, the conversion rate of the polymerizable compound is improved, and no polymerizable compound is remained in the liquid crystal composition. And since the polymerization is slow, the process does not affect the pretilt angle that has been formed. The ultraviolet irradiation time in the UV2 stage may be, for example, 100 to 150 min.
Examples
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the invention, the preparation method is a conventional method if no special description is provided, the used raw materials can be obtained from a public commercial way if no special description is provided, the percentages refer to mass percentage, the temperature is centigrade (DEG C), the liquid crystal compound also becomes a liquid crystal monomer, and the specific meanings and test conditions of other symbols are as follows:
cp represents a liquid crystal clearing point (DEG C), and is measured by a DSC quantitative method;
Δ n represents optical anisotropy, and Δ n ═ ne-noWherein n isoRefractive index of ordinary light, neThe refractive index of the extraordinary ray is measured under the conditions of 25 +/-2 ℃ and 589nm, and the Abbe refractometer is used for testing;
Δ represents dielectric anisotropy, Δ ═/-, where/is the dielectric constant parallel to the molecular axis,/-is the dielectric constant perpendicular to the molecular axis, the test conditions were 25 ± 0.5 ℃, 20 micron vertical cell, INSTEC: ALCT-IR1 test;
VHR represents the voltage holding ratio (%), and the test conditions are 20 +/-2 ℃, voltage +/-5V, pulse width 10ms and voltage holding time 16.7 ms. The testing equipment is a TOYO Model6254 liquid crystal performance comprehensive tester;
γ1expressed as rotational viscosity (mPas) at 25. + -. 0.5 ℃ in a 20 μm vertical cell, INSTEC: ALCT-IR 1.
In the examples of the present invention, the apparatus and equipment used for the preparation of the liquid crystal composition were:
the preparation method of the liquid crystal composition comprises the following steps: weighing the polymerizable compounds according to a certain ratio, putting the polymerizable compounds into a stainless steel beaker, putting the stainless steel beaker filled with the polymerizable compounds on a magnetic stirring instrument for heating and melting, adding a magnetic rotor into the stainless steel beaker after the polymerizable compounds in the stainless steel beaker are melted, uniformly stirring the mixture, and cooling to room temperature to obtain the liquid crystal composition.
The method for manufacturing the liquid crystal display device in the embodiment of the invention is as follows: firstly, uniformly coating alignment materials, which can be selected from polyimide, on the surfaces of a first substrate and a second substrate, heating and curing the uniformly coated alignment materials at the heating temperature of 230 ℃ to form alignment layers; secondly, spreading spacers on the surface of the second substrate, coating frame glue along the edge of the first substrate, and curing at 120 ℃; then, the first substrate and the second substrate are oppositely arranged and are attached to form a structure with an interlayer space; finally, the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and cured, thereby sealing the liquid crystal composition between the first substrate and the second substrate, and simultaneously performing electrification and ultraviolet irradiation. The ultraviolet irradiation is divided into two stages, including first stage ultraviolet irradiation (UV1) and second stage ultraviolet irradiation (UV 2). In the UV1 stage, the wavelength of ultraviolet light is 365nm, and the irradiance is 64mw/cm2Irradiating with 5mw/cm of ultraviolet light with wavelength of 365nm in UV2 (UV2) after the first stage irradiation2The light irradiation time is 100-150 min.
The liquid crystal monomer structure used in the embodiment of the invention is represented by codes, and the code representation methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following tables 1 and 2.
Table 1 corresponding code of the ring structure
Figure BDA0002411264430000291
TABLE 2 corresponding codes for end groups and linking groups
Figure BDA0002411264430000292
Figure BDA0002411264430000301
Examples are:
Figure BDA0002411264430000302
the code is CC-Cp-V1;
Figure BDA0002411264430000303
the code is PGP-Cpr 1-2;
Figure BDA0002411264430000304
the code is CPY-2-O2;
Figure BDA0002411264430000305
the code is CCY-3-O2;
Figure BDA0002411264430000306
the code is COY-3-O2;
Figure BDA0002411264430000307
the code is CCOY-3-O2;
Figure BDA0002411264430000308
it is coded as Sb-CpO-O4；
Figure BDA0002411264430000311
The code is Sc-CpO-O4;
Figure BDA0002411264430000312
the code is COYL-Cprl-O2;
Figure BDA0002411264430000313
the code is COYL-1-OV 1.
The invention is illustrated below with the following specific examples:
[ liquid Crystal Compound ]
The compounds of formula I of the present invention can be synthesized according to the following scheme:
Figure BDA0002411264430000314
wherein L is1、L2、L3、L4、r1、r3、r2、r4、x1、x2、x3、x4、Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2、P1、P2、P3、P4Each independently of the other, is as defined above for the polymerizable compound of formula I;
S1、S2each independently represents an aldehyde group, a hydroxyl group, a carboxyl group;
B1、B2、B3、B4each independently represents a protecting group for a hydroxyl group.
The raw materials and reagents in the general formula of the synthesis can be obtained by conventional synthesis or commercial purchase, and the methods such as the method principle, the operation process, the conventional post treatment, silica gel column passing, recrystallization purification and the like are well known by synthesizers in the field, so that the synthesis process can be completely realized to obtain the target product.
The reactions of all the steps of all the above processes are carried out in a solvent; the solvent is at least one selected from tetrahydrofuran, N-dimethylformamide, ethanol, methanol, dichloromethane, acetone, toluene and deionized water.
Example 1
The structural formula of the compound is shown as the following formula I-1-1,
Figure BDA0002411264430000321
the preparation route is as follows:
Figure BDA0002411264430000322
the specific operation flow of the preparation is as follows:
intermediate 1
Under the protection of nitrogen, 0.3mol of p-benzyloxy phenylboronic acid, 0.3mol of 3-benzyloxy-6-bromo-2-fluorophenol, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate and 0.3g of catalyst are put into a 5L three-necked bottle, and the mixture is heated under reflux for reaction for 3 hours. Standing, separating, performing column chromatography separation, and recrystallizing with toluene/ethanol to obtain compound 1 as yellow solid. HPLC 90% and yield Y75%.
Intermediate 2
Under the protection of nitrogen, 0.22mol of 1, 0.1mol of 1, 2-dibromopropane, 0.22mol of anhydrous potassium carbonate, 1.2L of DMF, N are added into a 2L three-necked bottle2The temperature is controlled at 120 ℃ for 4 hours under protection. After the reaction is finished, cooling, pouring into ice water while stirring, stirring for 30min, filtering, and pulping by 0.5L of petroleum ether to obtain the compound 2, wherein the HPLC (high performance liquid chromatography) content is 90%, and the yield Y is 70%.
Intermediate 3
0.08mol of Compound 2, 6.6g of Pd/C, 0.3L of THF and 0.3L of EtOH are placed in a 1L three-necked flask, N2Three times of replacement, H2Replacing three times, and carrying out hydrogenation debenzylation at 40 ℃ for 6 hours. After the reaction is finished, filtering by diatomite, concentrating the filtrate,PE, EA is 10: pulping 1, and stirring for 10min to obtain compound 3, wherein HPLC (high performance liquid chromatography) accounts for 98%, and the yield Y is 75%.
Compound I-1
In a 500ml three-necked flask are added 0.02mol of 3, 0.1mol of triethylamine, 0.2L of DCM, N2Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of ethanol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked and filtered, the white solid compound I-1-1 is obtained by being recrystallized for three times according to the same method and dried in the air, the HPLC.
Example 2
The structural formula of the compound is shown as the following formula I-2-1,
Figure BDA0002411264430000331
the preparation route is as follows:
Figure BDA0002411264430000341
the specific operation flow of the preparation is as follows:
intermediate 1
Synthesis of intermediate 1 in route to reference Compound I-1-1
Intermediate 4
The starting material 1, 2-dibromopropane was replaced with 1, 2-dibromohexane, and the synthesis method was according to the synthesis of intermediate 2 in example 1.
Intermediate 5
Synthesis methods refer to the synthesis of intermediate 3 in example 1.
Compound I-2-1
Synthesis method refer to the synthesis of Compound I-1-1 in example 1.
The MS mass spectrum of the compound I-2-1 is shown in figure 1, and the H-NMR nuclear magnetic spectrum is shown in figure 2.
Example 3
The structural formula of the compound is shown as the following formula I-4-1,
Figure BDA0002411264430000351
the preparation route is as follows:
Figure BDA0002411264430000352
the specific operation flow of the preparation is as follows:
intermediate 6
Under the protection of nitrogen, 0.3mol of p-benzyloxy phenylboronic acid, 0.3mol of 3-benzyloxy-6-bromo-2-fluorobenzaldehyde, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate and 0.3g of catalyst are put into a 5L three-necked bottle, and the mixture is heated and refluxed for reaction for 3 hours. Standing, separating, performing column chromatography, and recrystallizing with toluene/ethanol to obtain compound 6 as light yellow solid. 93% for HPLC and 72% for yield Y.
Intermediate 7
Under the protection of nitrogen, 0.1mol of phosphonium salt is added into a 3L three-necked bottle, 1L of phosphonium salt is added, the temperature is reduced to 0 to minus 10 ℃, 0.2mol of potassium tert-butoxide is slowly added in batches, the temperature is controlled to be 0 to minus 10 ℃ for reaction for 1h, THF solution of a compound 6(0.2mol) is added dropwise, and the mixture is naturally heated to room temperature for reaction for 4 h. After the reaction is finished, water is added for separating liquid, the water phase is extracted by ethyl acetate, the organic phase is combined and washed by saturated sodium chloride, the drying and the spin drying are carried out, and the ethanol is recrystallized to obtain the compound 7, wherein the HPLC (high performance liquid chromatography) rate is 95 percent, and the yield Y is 60 percent.
Intermediate 8
0.06mol of Compound 7, 5.0g Pd/C, 0.3L THF and 0.2L EtOH were placed in a 1L three-necked flask, N2Three times of replacement, H2Replacing three times, and carrying out hydrogenation debenzylation at 40 ℃ for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: pulping 1, and stirring for 10min to obtain compound 8, wherein the HPLC rate is 97%, and the yield Y is 83%.
Compound I-4-1
In a 500ml three-necked flask are charged 0.02mol of 8, 0.1mol of triethylamine, 0.2L of DCM, N2Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of alcohol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked and filtered, the recrystallization is carried out for four times according to the same method, and the filtrate is dried to obtain a white solid compound I-4-1.
Example 4
The structural formula of the compound is shown as the following formula I-6-1,
Figure BDA0002411264430000361
the preparation route is as follows:
Figure BDA0002411264430000371
the specific operation flow of the preparation is as follows:
intermediate 9
Under the protection of nitrogen, 0.2mol of phosphonium salt is added into a 3L three-necked bottle, 1L of phosphonium salt is added, the temperature is reduced to 0 to minus 10 ℃, 0.2mol of potassium tert-butoxide is slowly added in batches, the temperature is controlled to be 0 to minus 10 ℃ for reaction for 1h, THF solution of a compound 6(0.2mol) is dropwise added, and the mixture is naturally heated to room temperature for reaction for 4 h. After the reaction is finished, water is added for separating liquid, ethyl acetate is used for extracting a water phase, an organic phase is combined, saturated sodium chloride is used for washing, drying and spin-drying are carried out, column chromatography separation (petroleum ether and ethyl acetate) is carried out, a solvent is spin-dried, and the compound 9 can be obtained, 95% of HPLC is carried out, and the yield Y is 70%.
Intermediate 10
Under the protection of nitrogen, 0.14mol of the compound 9 and 0.14mol of the compound 1 are added into a 2L three-necked bottle, 0.15mol of triphenylphosphine is added, the temperature is reduced to 0 ℃, 0.15mol of DIAD is added dropwise, and the temperature is naturally raised to room temperature after the dropwise addition for reaction for 3 hours. And (5) finishing the reaction. Separating with water and ethyl acetate, extracting the water phase with ethyl acetate, combining the organic phases, drying, spin-drying, separating by column chromatography (petroleum ether, ethyl acetate), and spin-drying the solvent to obtain the compound 10, wherein HPLC (high performance liquid chromatography) is 96%, and the yield Y is 68%.
Intermediate 11
0.06mol of Compound 10, 5.2g of Pd/C, 0.3L of THF and 0.2L of EtOH are placed in a 1L three-necked flask, N2Three times of replacement, H2Replacing three times, and carrying out hydrogenation debenzylation at 40 ℃ for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: pulping 1, and stirring for 10min to obtain compound 8, wherein HPLC (high performance liquid chromatography) accounts for 98%, and the yield Y is 80%.
Intermediate I-6-1
In a 500ml three-necked flask are charged 0.02mol of 11, 0.1mol of triethylamine, 0.2L of DCM, N2Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of alcohol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked and filtered, the filtrate is recrystallized for four times by the same method, and the filtrate is dried to obtain a white solid compound I-6-1, wherein.
Example 5
The structural formula of the compound is shown as the following formula I-7-1,
Figure BDA0002411264430000381
the preparation route is as follows:
Figure BDA0002411264430000382
the specific operation flow of the preparation is as follows:
intermediate 12
Under the protection of nitrogen, 0.3mol of p-benzyloxy phenylboronic acid, 0.3mol of 3-benzyloxy-6-bromo-2-fluorobenzoic acid, 2.0L of toluene, 0.7L of water, 0.6mol of potassium carbonate and 0.3g of catalyst are put into a 5L three-necked bottle, and the mixture is heated and refluxed for reaction for 3 hours. Standing, separating, performing column chromatography, and recrystallizing with toluene/ethanol to obtain compound 12 as light yellow solid. 95% for HPLC, and 82% for yield Y.
Intermediate 13
In a 3L three-necked flask were charged 0.2mol of 12, 0.1mol of propylene glycol, 0.05mol of DMAP, 1.0L of THF, N2Under protection, 0.3mol of DCC in THF is added dropwise at 0 ℃. After dropping, the reaction was carried out at room temperature for 6 hours. After the reaction was completed, filtration was performed, the filtrate was concentrated, and 3-fold ethanol was recrystallized to obtain compound 13, GC: 93%, and yield Y: 75%.
Intermediate 14
0.06mol of Compound 13, 5.2g of Pd/C, 0.3L of THF and 0.2L of EtOH are placed in a 1L three-necked flask, N2Three times of replacement, H2Replacing three times, and carrying out hydrogenation debenzylation at 40 ℃ for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: pulping 1, and stirring for 10min to obtain compound 14, wherein the HPLC rate is 97%, and the yield Y is 85%.
Compound I-7-1
In a 500ml three-necked flask are charged 0.02mol of 14, 0.1mol of triethylamine, 0.2L of DCM, N2Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of alcohol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked and filtered, the filtrate is recrystallized for four times by the same method, and the filtrate is dried to obtain a white solid compound I-7-1, wherein.
Example 6
The structural formula of the compound is shown as the following formula I-7-1,
Figure BDA0002411264430000401
the preparation route is as follows:
Figure BDA0002411264430000402
the specific operation flow of the preparation is as follows:
synthesis of intermediate 15 referring to intermediate 13 in example 5, the starting material, propylene glycol, was replaced with 1, 6-hexanediol.
Synthesis of intermediate 16 reference was made to intermediate 14 in example 5.
Synthesis of Compound I-8-1 reference was made to Compound I-7-1 in example 5.
Example 7
The structural formula of the compound is shown as the following formula I-10-1,
Figure BDA0002411264430000411
the preparation route is as follows:
Figure BDA0002411264430000412
the specific operation flow of the preparation is as follows:
intermediate 17
0.2mol of 1, 0.1mol of adipic acid, 0.05mol of DMAP, 1.0L of THF, N are introduced into a 3L three-necked flask2Under protection, 0.3mol of DCC in THF is added dropwise at 0 ℃. After dropping, the reaction was carried out at room temperature for 6 hours. After the reaction was completed, the reaction mixture was filtered, the filtrate was concentrated, and 3-fold ethanol was recrystallized to obtain compound 17, GC: 92%, and yield Y: 80%.
Intermediate 18
0.06mol of Compound 17, 6.0g of Pd/C, 0.3L of THF and 0.2L of EtOH are placed in a 1L three-necked flask, N2Three times of replacement, H2Replacing three times, and carrying out hydrogenation debenzylation at 40 ℃ for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: pulping 1, stirring for 10min to obtain compound 18, HPLC: 97%, yield Y80%.
Compound I-10-1
0.02mo is dosed into a 500ml three-necked flaskL of 18, 0.1mol of triethylamine, 0.2L of DCM, N2Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of alcohol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked and filtered, the filtrate is recrystallized for four times by the same method, and the filtrate is dried to obtain a white solid compound I-10-1, wherein.
Preparing a liquid crystal composition:
mother liquid crystal composition 1
The formulation and corresponding properties of the liquid crystal compositions are shown in table 3 below.
Table 3: formulation and corresponding Properties of the mother liquid Crystal composition 1
Figure BDA0002411264430000421
Mother liquid crystal composition 2
The formulation and corresponding properties of the liquid crystal compositions are shown in table 4 below.
Table 4: formulation and corresponding Properties of mother liquid Crystal composition 2
Figure BDA0002411264430000422
Figure BDA0002411264430000431
Mother liquid Crystal composition 3
The formulation and corresponding properties of the liquid crystal compositions are shown in table 5 below.
Table 5: formulation and corresponding Properties of mother liquid Crystal composition 3
Figure BDA0002411264430000432
Mother liquid Crystal composition 4
The formulation and corresponding properties of the liquid crystal compositions are shown in table 6 below.
Table 6: formulation and corresponding Properties of mother liquid Crystal composition 4
Figure BDA0002411264430000433
Mother liquid Crystal composition 5
The formulation and corresponding properties of the liquid crystal compositions are shown in table 7 below.
Table 7: formulation and corresponding Properties of mother liquid Crystal composition 5
Figure BDA0002411264430000441
Mother liquid crystal composition 6
The formulation and corresponding properties of the liquid crystal compositions are shown in Table 8 below.
Table 8: master liquid crystal composition 6 formulation and corresponding properties
Figure BDA0002411264430000442
Mother liquid Crystal composition 7
The formulation and corresponding properties of the liquid crystal compositions are shown in table 9 below.
Table 9: master liquid crystal composition 7 formulation and corresponding properties
Figure BDA0002411264430000443
Figure BDA0002411264430000451
Mother liquid crystal composition 8
The formulation and corresponding properties of the liquid crystal composition are shown in table 10 below.
Table 10: mother liquid crystal composition 8 formulation and corresponding properties
Figure BDA0002411264430000452
Comparative compound (c):
Figure BDA0002411264430000461
for the measurement of the solubility, the polymerizable compounds I-1-1, I-1-2, I-2-1, I-3-1, I-5-1, I-7-1, I-9-1, I-16-1 and the monomers RM-1, RM-2 from the prior art were each dissolved in the parent liquid crystal composition in different concentrations of from 0.1 to 2.0% by weight. Samples were stored at Room Temperature (RT) for 1000 hours and checked to see if they remained as a homogeneous solution. The sample was then centrifuged and filtered and the concentration of remaining monomer in the supernatant determined. Maximum residual monomer concentration at RT after 1000 hours:
table 11: solubility data for examples and comparative examples
Figure BDA0002411264430000462
Figure BDA0002411264430000471
It can be seen that the monomers according to the invention exhibit significantly better solubility than the monomers of the prior art. It can be seen that the monomers of the invention all show residual concentrations of > 0.40%, which are higher than the 0.3% RM concentration normally used in PSA displays, meeting the industrial requirements, whereas the monomers RM-1, RM-2 have a lower RM concentration than the 0.30% RM concentration normally used.
Adding a certain amount of polymerizable compounds shown as a formula I into the test mother liquid crystal compositions 1-6 respectively; for comparison, to the test master 1, amounts of RM-1, RM-2, RM-3 were added as comparative examples 1,2, 3, respectively, to prepare liquid crystal compositions by the above-mentioned liquid crystal composition preparation methods.
The reliability of the liquid crystal composition is carried out by carrying out ultraviolet and high temperature aging tests and VHR tests, and the smaller the VHR data change before and after the ultraviolet and high temperature tests of the liquid crystal panel, the stronger the ultraviolet and high temperature resistance. Therefore, the ultraviolet and high temperature resistance can be judged by comparing the difference of VHR data of each example and comparative example before and after the test.
Ultraviolet aging test: the liquid crystal composition was irradiated with 5000mJ energy under an ultraviolet lamp having a wavelength of 365 nm.
High-temperature aging test: the liquid crystal composition was placed in an oven at 100 ℃ for one hour.
The smaller the change of the VHR data after the aging test relative to the initial VHR data, the stronger the ultraviolet and high temperature resistance of the liquid crystal composition is, so that the stronger the resistance of the liquid crystal composition to the external environment during the working process can be judged, and therefore, the higher the reliability of the liquid crystal composition is. The VHR data for the liquid crystal composition examples and comparative examples are shown in table 12.
Table 12: VHR data for liquid Crystal composition examples and comparative examples
Figure BDA0002411264430000472
Figure BDA0002411264430000481
Filling the liquid crystal composition to prepare a liquid crystal display device, testing an initial pretilt angle, irradiating UV light in a UV1 process to promote polymerization of a polymerizable compound, aligning liquid crystal by using a film formed after polymerization, and testing the pretilt angle after a UV2 process. An aging experiment was performed to test the pretilt angles 24h, 48h and 72h after applying 30V to the backlight. The pretilt angle data for the liquid crystal composition examples and comparative examples are shown in Table 13.
Table 13: pretilt angle data for liquid crystal composition examples and comparative examples
Figure BDA0002411264430000482
As can be seen from the VHR data and the pretilt angle data, the liquid crystal composition containing the polymerizable compound of the present invention has a high Voltage Holding Ratio (VHR) and a stable pretilt angle (here, the difference between 90 ° and the pretilt angle data is represented, that is, the actual pretilt angle is larger as the pretilt angle data is smaller) when the liquid crystal composition containing the polymerizable compound of the present invention or the liquid crystal composition containing the polymerizable compound of the present invention is manufactured into a display device, compared to the comparative example.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A polymerizable compound of the formula I,
Figure FDA0002411264420000011
wherein the content of the first and second substances,
L1、L2、L3、L4each independently represents a F atom, a Cl atom, -CN, a straight-chain alkyl group having 1 to 25C atoms, a branched-chain alkyl group having 3 to 25C atoms, a cyclic alkyl group having 2 to 25C atomsAlkenyl of 25C atoms or alkynyl of 2 to 25C atoms, one or more non-adjacent-CH2-the group is optionally substituted by-O-, -S-, -NH-, -CO-O-, -O-CO-O-, and wherein one or more H atoms are optionally substituted by halogen atoms;
r1、r3each independently represents 0, 1,2, 3 or 4;
r2、r4each independently represents 0, 1,2 or 3;
x1、x2、x3、x4each independently represents 0, 1 or 2, and x1+x2+x3+x4≥3；
Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2Each independently represents a single bond, a straight chain alkyl group having 1 to 25C atoms, a branched alkyl group having 3 to 25C atoms, a cyclic alkyl group having 3 to 25C atoms, an alkenyl group having 2 to 25C atoms, or an alkynyl group having 2 to 25C atoms, and wherein one or more non-adjacent-CH groups2-the group is optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms;
P1、P2、P3、P4each independently represents a polymerizable group.
2. The polymerizable compound according to claim 1, wherein the compound represented by formula i:
L1、L2、L3、L4each independently represents an alkyl group having 1 to 5 carbon atoms, a fluorine-substituted alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine-substituted alkoxy group having 1 to 5 carbon atoms, an F atom or a Cl atom;
r1、r3each independently represents 0, 1 or 2; r is2、r4Each independently represents 0 or 1;
x1、x2、x3、x4each independently represents 0 or 1, and x1+x2+x3+x4≥3；
Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2Each independently represents a single bond, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms, wherein one or more non-adjacent-CH groups2-the group is optionally substituted by-O-, -CO-O-, -O-CO-, one or more H atoms are optionally substituted by F atoms;
P1、P2、P3、P4each independently represent
Figure FDA0002411264420000021
Figure FDA0002411264420000022
3. The polymerizable compound according to claim 2, which is selected from the group consisting of compounds represented by the following formulae I-1-1 to I-17-3,
Figure FDA0002411264420000023
Figure FDA0002411264420000031
Figure FDA0002411264420000041
Figure FDA0002411264420000051
Figure FDA0002411264420000061
Figure FDA0002411264420000071
Figure FDA0002411264420000081
Figure FDA0002411264420000091
Figure FDA0002411264420000101
Figure FDA0002411264420000111
Figure FDA0002411264420000121
Figure FDA0002411264420000131
Figure FDA0002411264420000141
Figure FDA0002411264420000151
Figure FDA0002411264420000161
Figure FDA0002411264420000171
Figure FDA0002411264420000181
4. a liquid crystal composition comprising one or more polymerizable compounds according to any one of claims 1 to 3.
5. The liquid crystal composition according to claim 4, further comprising one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,
Figure FDA0002411264420000182
in the formula II, R1、R2Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
Figure FDA0002411264420000183
each independently represent
Figure FDA0002411264420000184
In the formula III, R3、R4Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more non-adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;
Z1、Z2each independently represents a single bond, -CH2CH2-、-CH2O-or-OCH2-；
Figure FDA0002411264420000191
Each independently represent
Figure FDA0002411264420000192
Figure FDA0002411264420000193
m1Represents 1 or 2, when m1When the expression is shown in the figure 2,
Figure FDA0002411264420000194
the same or different;
n1represents 0, 1 or 2, when n1When the expression is shown in the figure 2,
Figure FDA0002411264420000195
the same or different.
6. The liquid crystal composition of claim 5, wherein the compound of formula II is selected from the group consisting of compounds of formulae II-1 to II-17,
Figure FDA0002411264420000196
Figure FDA0002411264420000201
the compound shown in the formula III is selected from the group consisting of compounds shown in formulas III-1 to III-15,
Figure FDA0002411264420000202
Figure FDA0002411264420000211
wherein R is31、R41Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any one or more of them is not adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.
7. The liquid crystal composition of any one of claims 4 to 6, further comprising one or more compounds represented by formula IV,
Figure FDA0002411264420000212
wherein R is5、R6Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine atomA substituted C1-10 alkyl group, a C1-10 alkoxy group, a fluorine-substituted C1-10 alkoxy group, a C2-10 alkenyl group, a fluorine-substituted C2-10 alkenyl group, a C3-8 alkenyloxy group or a fluorine-substituted C3-8 alkenyloxy group, wherein any one or more of-CH groups are not adjacent to each other2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH2O-。
8. The liquid crystal composition of claim 7, further comprising one or more compounds of formula V,
Figure FDA0002411264420000221
wherein R is7、R8Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
Figure FDA0002411264420000222
each independently represent
Figure FDA0002411264420000223
9. The liquid crystal composition of claim 8, further comprising one or more compounds of formula VI,
Figure FDA0002411264420000224
wherein R is9、R10Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
Figure FDA0002411264420000225
to represent
Figure FDA0002411264420000226
F1、F2、F3Each independently represents a H atom or a F atom, and F2、F3Not simultaneously being F atoms.
10. A liquid crystal display element or a liquid crystal display comprising the compound according to any one of claims 1 to 3 or the liquid crystal composition according to any one of claims 4 to 9, which is an active matrix display element or a display or a passive matrix display element or a display.
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CN108084029B (en) * 2017-12-20 2021-08-31 石家庄诚志永华显示材料有限公司 Liquid crystal composition and liquid crystal display element

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