阅读说明：本技术 化合物、液晶组合物、液晶显示器 (Compound, liquid crystal composition and liquid crystal display ) 是由 魏天宇 李洪峰 姜军 邢杰浩 鲍永锋 李明 员国良 梁志安 于 2019-11-15 设计创作，主要内容包括：本发明涉及下述的式I所示的化合物、液晶组合物及液晶显示器。本发明的化合物在液晶组合物中能够作为自组装光配向剂(SAPA),通过光配向具有正或负介电各向异性的液晶组合物能够制造具有沿面配向的液晶(LC)显示器件。本发明的式I所示化合物经聚合能够得到稳定性好的光控取向膜,能够起到配向层的绝缘与对液晶分子水平配向的作用,能够避免配向层制程,使液晶显示元件或液晶显示器的制程得到简化,提高生产效率。(The invention relates to a compound shown in formula I, a liquid crystal composition and a liquid crystal display. The compound of the present invention can be used as a self-assembled photo-alignment agent (SAPA) in a liquid crystal composition, and a Liquid Crystal (LC) display device having a planar alignment can be manufactured by photo-aligning a liquid crystal composition having positive or negative dielectric anisotropy. The compound shown in the formula I can be polymerized to obtain a light-operated orientation film with good stability, can play a role in insulating an orientation layer and horizontally orienting liquid crystal molecules, can avoid the orientation layer process, simplifies the process of a liquid crystal display element or a liquid crystal display and improves the production efficiency.)

1. A compound represented by formula I,

wherein the content of the first and second substances,

P₁₁、P₁₂each independently represents P₁、P₁-Sp-、-Z₃-H、-Z₃-L¹H atom, F atom or C atom having 1 to 12Straight-chain or branched alkyl, in which one or more non-adjacent-CH₂The radical is optionally substituted by-C (L)⁰)＝C(L⁰⁰)-、-C≡C-、-N(L⁰⁰) -, -O-, -S-, -CO-O-, -O-CO-or-O-CO-O-, one or more H atoms being optionally replaced by F atoms, Cl atoms, Br atoms, I atoms, CN, P₁Or P₁-Sp-substitution, and P₁₁And P₁₂At least one of them represents a group P₁Or P₁-Sp-；

K₁、K₂、K₃Each independently represents an aromatic, heteroaromatic, alicyclic, heterocyclic or fused cyclic group having 4 to 25 carbon atoms, wherein any one of the groups-CH₂-optionally substituted by-O-, -S-or-CO-, at least one or more H atoms optionally substituted by L¹Substitution;

L¹represents a F atom, 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, a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms or-Sp-P₁And any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene;

P₁represents a polymerizable group;

Z₁、Z₂、Z₃each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_n1-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_n1-、-(CL⁰L⁰⁰)_n1-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-OCO-CH＝CH-COO-、-N＝N-、

n1 represents 1, 2, 3 or 4;

m, n, o, q each independently represent 0, 1, 2, 3 or 4, and m + o + n × q is 2 or more;

G₁、G₂、G₃each independently represents-Sp₁-R₁、-Sp₂-R₂、-Sp₃-R₃Or R, wherein one or more are not adjacent-CH₂-optionally substituted by-O-;

r represents

p represents 1, 2 or 3;

x represents a divalent, trivalent or tetravalent group;

R₁、R₂、R₃、R₄each independently represents-NL¹¹、-OL¹¹、-SL¹¹、-COOL¹¹、-CHO、-CONL¹¹、

L⁰、L⁰⁰、L¹¹Each independently represents a H atom or an alkyl group having 1 to 12C atoms;

Sp、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅each independently represents a spacer or a single bond.

2. The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by formula I1 through formula I11:

wherein the content of the first and second substances,

P₁₁、P₁₂each independently represents P₁、P₁-Sp-、-Z₃-H、-Z₃-L¹H atom, F atom or straight chain or branched chain alkyl with 1-12C atoms, wherein one or more non-adjacent-CH₂The radical is optionally substituted by-C (L)⁰)＝C(L⁰⁰)-、-C≡C-、-N(L⁰⁰) -, -O-, -S-, -CO-O-, -O-CO-or-O-CO-O-, one or more H atoms being optionally replaced by F atoms, Cl atoms, Br atoms, I atoms, CN, P₁Or P₁-Sp-substitution, and P₁₁And P₁₂At least one of them represents a group P₁Or P₁-Sp-；

L¹Represents a F atom, 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, a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms or-Sp-P₁And any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene;

P₁represents a polymerizable group;

Z₁、Z₂、Z₃each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_n1-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_n1-、-(CL⁰L⁰⁰)_n1-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-OCO-CH＝CH-COO-、-N＝N-、

n1 represents 1, 2, 3 or 4;

r represents 0, 1, 2 or 3;

R₁、R₂each independently represents-NL¹¹、-OL¹¹、-SL¹¹、-COOL¹¹、-CHO、-CONL¹¹、

L⁰、L⁰⁰、L¹¹Each independently represents a H atom or an alkyl group having 1 to 12C atoms;

Sp、Sp₁、Sp₂each independently represents a spacer or a single bond.

3. The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by formula I1-1 through formula I11-3:

wherein the content of the first and second substances,

P₁₁、P₁₂each independently represents P₁、P₁-Sp-、-Z₃-H、-Z₃-L¹H atom, F atom or straight chain or branched chain alkyl with 1-12C atoms, wherein one or more non-adjacent-CH₂The radical is optionally substituted by-C (L)⁰)＝C(L⁰⁰)-、-C≡C-、-N(L⁰⁰) -, -O-, -S-, -CO-O-, -O-CO-or-O-CO-O-, one or more H atoms being optionally replaced by F atoms, Cl atoms, Br atoms, I atoms, CN, P₁Or P₁-Sp-substitution, and P₁₁And P₁₂At least one of them represents a group P₁Or P₁-Sp-；

L¹Represents a F atom, 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, a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms or-Sp-P₁And any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene;

P₁represents a polymerizable group;

Z₁、Z₂、Z₃each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_n1-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_n1-、-(CL⁰L⁰⁰)_n1-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-OCO-CH＝CH-COO-、-N＝N-、

n1 represents 1, 2, 3 or 4;

r represents 0, 1, 2 or 3;

R₁、R₂each independently represents-NL¹¹、-OL¹¹、-SL¹¹、-COOL¹¹、-CHO、-CONL¹¹、

L⁰、L⁰⁰、L¹¹Each independently represents a H atom or an alkyl group having 1 to 12C atoms;

Sp、Sp₁、Sp₂each independently represents a spacer or a single bond.

4. The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by formula I1-1a through formula I11-3 a:

5. a liquid crystal composition comprising one or more compounds according to any one of claims 1 to 4.

6. The liquid crystal composition according to claim 5, further comprising one or more polymerizable compounds represented by the formula P,

P^a-(Sp^a)_s1-A²-(Z-A¹)_n2-(Sp^b)_s2-P^b P

wherein the content of the first and second substances,

P^a、P^beach independently represents a polymerizable group;

Sp^a、Sp^beach independently represents a spacer group;

s1, s2 are each independently 0 or 1;

A¹、A²each independently represents a group selected from the group consisting of:

a) trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene and 4, 4' -bicyclohexyl, one or more non-adjacent-CH₂-the group is optionally replaced by-O-or-S-, one or more H atoms are optionally replaced by F atoms,

b) from the group consisting of 1, 4-phenylene and 1, 3-phenylene in which one or two CH groups are optionally replaced by N and one or more H atoms are optionally replaced by L,

c) from the group consisting of tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydrofuran-2, 5-diyl, cyclobutane-1, 3-diyl, piperidine-1, 4-diyl, thiophene-2, 5-diyl and selenophene-2, 5-diyl, wherein one or more H atoms are optionally substituted by L,

d) by

A group of components selected from the group consisting of,

wherein one or more H atoms in these groups are optionally replaced by L, and/or one or more double bonds are optionally replaced by a single bond, and/or one or more CH are optionally replaced by N;

n2 is 0, 1, 2 or 3;

z represents-CO-O-, -O-CO-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-, straight-chain alkylene having 2 to 4 carbon atoms, -O-, -CO-, -C (R)⁰R⁰⁰)-、-CH₂CF₂-、-CF₂CF₂-or a single bond;

l, at each occurrence, independently represents a F atom, a Cl atom, CN, SCN, SF₅Or optionally fluorinated linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy having 1 to 12C atoms;

R⁰、R⁰⁰each independently of the others, represents a H atom, a F atom or a linear or branched alkyl group having 1 to 12C atoms, wherein one or more H atoms are optionally replaced by a F atom;

m represents-O-, -S-, -CH₂-、-CHY¹-or-CY¹Y²-；

Y¹、Y²Each independently of the others, represents a H atom, a F atom, a Cl atom, CN or a linear or branched alkyl group having 1 to 12C atoms, wherein one or more H atoms are optionally replaced by a F atom.

7. The liquid crystal composition of claim 5, further comprising one or more compounds of formula II and/or one or more compounds of formula III,

wherein, in the formula II,to represent

To represent

R₅、R₆Each independently represents an alkyl group having 1 to 12 carbon atoms, wherein one or more of-CH groups are not adjacent₂-the group is optionally replaced by-O-, -CH ═ CH-, -CO-, -O-CO-, or-CO-O-;

Z₄represents-CH₂CH₂-、-CH＝CH-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-C₂F₄-, -CF ═ CF-or a single bond;

in the formula (III), the reaction solution is prepared,each independently represent

R₇、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.

8. The liquid crystal composition of claim 7, further comprising one or more compounds of formula IV,

wherein the content of the first and second substances,

each independently selected from the group consisting of (i) and (ii):

trans 1, 4-cyclohexylene, 1, 4-cyclohexenyl, wherein one or more non-adjacent-CH' s₂-the group is optionally substituted by-O-or-S-;

(xii) 1, 4-phenylene in which one or two CH groups are optionally substituted by N and one or two H atoms are optionally substituted by F atoms;

R₉to representA linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms;

X₁、X₂each independently represents a H atom or a F atom;

Y³represents F atom, straight-chain alkyl with 1-6 carbon atoms or straight-chain alkenyl with 2-6 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by the F atom;

Z₅represents a single bond, -CH₂-、-CH₂CH₂-、-(CH₂)₃-、-(CH₂)₄-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-OCH₂-、-CH₂O-、-CF₂CH₂-、-CH₂CF₂-、-C₂F₄-or-CF ═ CF —;

r represents 0, 1 or 2.

9. The liquid crystal composition according to claim 7 or claim 8, further comprising one or more compounds of formula V,

wherein R is₁₀、R₁₁Each 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 R₁₀、R₁₁Any one or more non-adjacent-CH₂-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;

Z₆、Z₇each independently represents a single bond, -CH₂CH₂-or-CH₂O-；

Each independently represent

s represents 1 or 2; t represents 0, 1 or 2.

10. A liquid crystal display comprising the compound of any one of claims 1 to 4, or the liquid crystal composition of any one of claims 5 to 9, which is an active matrix display or a passive matrix display.

11. The liquid crystal display according to claim 10, wherein the display is an IPS display or an FFS display.

Technical Field

The invention relates to a compound capable of realizing a self-assembly photo-alignment function and a liquid crystal composition containing the compound, belonging to the field of liquid crystal display.

Background

Currently, alignment of liquid crystal molecules can be achieved using a specific polyimide alignment film. As a method for alignment treatment of a liquid crystal alignment film for imparting alignment controllability, a brushing method has been conventionally used in many cases. However, the brush rubbing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like has a problem of generating dust and static electricity. Further, in recent years, the liquid crystal display element has become more highly clear, and the surface of the liquid crystal alignment film has not been uniformly rubbed with a cloth due to irregularities caused by the electrode on the substrate or the switching active element for driving the liquid crystal, and thus uniform liquid crystal alignment has not been achieved.

On the other hand, the polymerizable mesogenic unit (RMs) is currently a very popular and important topic in the display industry, and the possible application fields include Polymer Sustained Alignment (PSA) liquid crystal display, polymer sustained blue phase (PS-BP) liquid crystal display, and patterned Retarder Film (Pattern recorder Film). In a liquid crystal display element of a polymer stabilized alignment type, the alignment of liquid crystal molecules can be controlled by using a polymer.

The prior art discloses that the liquid crystal composition containing polymer and polar compound is used in the liquid crystal display element without the orientation film to control the orientation of liquid crystal analysis, and the liquid crystal display elements such as PSA-VA, PSA-OCB, PS-IPS/FFS, PS-TN and the like can expect to achieve the effect by the combination of the polymer and the polar compound, but the application of LC mixture and RMs in IPS/FFS displays is still found to have some defects. For example, the panel process requires the application of alignment layer, which not only affects the production line throughput, but also causes the emission of organic contaminants, and N.A. Clark et al, Langmuir2010,26(22),17482-17488 have described that the following compounds can be used:self-assemble on the substrate to give a monolayer that can be photoaligned to induce planar alignment of the liquid crystal. However, a separate step of self-assembly is required before the fabrication of the LC cell, and the reversibility of alignment after exposure to light is reported, among other drawbacks.

Disclosure of Invention

The present invention provides a compound capable of self-assembly photoalignment, which can be aligned without using a polyimide alignment film when a liquid crystal composition containing the compound is applied to a liquid crystal display device, and which has a simplified liquid crystal alignment method and stable alignment.

In order to achieve the above objects, the present invention provides, in one aspect, a compound having a structural formula as shown in formula I,

wherein, P₁₁、P₁₂Each independently represents P₁、P₁-Sp-、-Z₃-H、-Z₃-L¹H atom, F atom or straight chain or branched chain alkyl with 1-12C atoms, wherein one or more non-adjacent-CH₂The radical is optionally substituted by-C (L)⁰)＝C(L⁰⁰)-、-C≡C-、-N(L⁰⁰) -, -O-, -S-, -CO-O-, -O-CO-or-O-CO-O-, one or more H atoms being optionally replaced by F atoms, Cl atoms, Br atoms, I atoms, CN, P₁Or P₁-Sp-substitution, and P₁₁And P₁₂At least one of them represents a group P₁Or P₁-Sp-；

K₁、K₂、K₃Each independently represents an aromatic, heteroaromatic, alicyclic, heterocyclic or fused cyclic group having 4 to 25 carbon atoms, wherein any one of the groups-CH₂-optionally substituted by-O-, -S-or-CO-, at least one or more H atoms optionally substituted by L¹Substitution;

L¹represents a F atom, 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, a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms or-Sp-P₁And any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene;

Z₁、Z₂、Z₃each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_n1-、 -CF₂CH₂-、-CH₂CF₂-、-(CF₂)_n1-、-(CL⁰L⁰⁰)_n1-、-CH＝CH-、-C≡C-、-CF＝CF-、 -CH＝CH-COO-、-OCO-CH＝CH-、-OCO-CH＝CH-COO-、-N＝N-、

n1 represents 1, 2, 3 or 4; m, n, o, q each independently represent 0, 1, 2, 3 or 4, and m + o + n × q is 2 or more;

G₁、G₂、G₃each independently represents-Sp₁-R₁、-Sp₂-R₂、-Sp₃-R₃Or R, wherein one or more are not adjacent-CH₂-optionally substituted by-O-; r represents

p represents 1, 2 or 3; x represents a divalent, trivalent or tetravalent group;

R₁、R₂、R₃、R₄each independently represents-NL¹¹、-OL¹¹、-SL¹¹、-COOL¹¹、-CHO、 -CONL¹¹、P₁Represents a polymerizable group;

L⁰、L⁰⁰、L¹¹each independently represents a H atom or an alkyl group having 1 to 12C atoms;

Sp、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅each independently represents a spacer or a single bond.

In another aspect of the invention, a liquid crystal composition is provided, which comprises one or more compounds of formula I.

In still another aspect of the present invention, there is provided a liquid crystal display element or a liquid crystal display comprising the compound of the present invention, or the liquid crystal composition of the present invention, the display element or display being an active matrix display element or display or a passive matrix display element or display.

The compounds of the present invention are capable of acting as self-assembling photoalignment agents (SAPAs) by virtue of the polar side groups of the compounds interacting with the substrate surface, thereby enabling the SAPAs to phase separate from the LC mixture after filling the LC cell, forming a layer photoalignable by linearly polarised UV light on the substrate. Then, the compound shown in the formula I is subjected to in-situ stepwise polymerization by polarized ultraviolet irradiation to obtain a photo-alignment film with good stability, the photo-alignment film can play roles in insulating an alignment layer and horizontally aligning liquid crystal molecules, and the liquid crystal follows the alignment of aligned SAPA so as to provide uniform planar alignment across the whole display. Therefore, the alignment layer manufacturing process can be avoided, the manufacturing process of the liquid crystal display element or the liquid crystal display is simplified, and the production efficiency is improved.

Further, the liquid crystal composition has low viscosity, can realize quick response, and simultaneously has moderate dielectric anisotropy delta epsilon and moderate optical anisotropy delta n.

Drawings

FIG. 1 is a nuclear magnetic resonance spectrum of a compound represented by formula I1-1 a.

Detailed Description

[ Compound ]

The above-mentioned compounds of formula I of the present invention are preferably selected from the group consisting of compounds represented by formula I1 to formula I11 below:

wherein r represents 0, 1, 2 or 3; the remaining groups and parameters have the meanings indicated above for formula I.

Preferably, the compound of formula I is selected from the group consisting of compounds of formula I1-1 through formula I11-3 as follows:

wherein r represents 0, 1, 2 or 3; the remaining groups and parameters have the meanings indicated above for formula I.

More preferably, the compound of formula I is selected from the group consisting of compounds of formula I1-1a through formula I11-3a as follows:

the method for producing the compound represented by formula I of the present invention is not particularly limited. As one embodiment, for example, a method of synthesizing according to the following synthetic route is exemplified, but not limited thereto:

scheme 1:

scheme 2:

wherein G is₁、G₂、L¹、L₀₀、Sp₁、Sp₂R is as defined above, L represents a hydrogen atom, a methyl group, a trifluoromethyl group or the like, and L' represents L¹Or an aromatic group.

The raw materials and reagents in the general formula of the synthesis can be purchased from commercial sources, the method principle, the operation process, the conventional post treatment, the silica gel column passing, the recrystallization purification and other means are well known by synthesizers in the field, and the synthesis process can be completely realized to obtain the target product.

The reactions of all the steps of all the above methods are carried out in a solvent selected from at least one of tetrahydrofuran, N-dimethylformamide, ethanol, methanol, dichloromethane, acetone, toluene and deionized water.

[ liquid Crystal composition ]

The liquid crystal composition of the present invention comprises one or more compounds of the present invention.

In the liquid crystal composition, the content of the compound shown in the formula I in the liquid crystal composition is preferably 0.01-10%. Preferably, the content of the compound shown in the formula I in the liquid crystal composition is 0.01-1%.

In one embodiment of the liquid crystal composition of the present invention, one or more polymerizable compounds represented by the formula P may be further contained,

P^a-(Sp^a)_s1-A²-(Z-A¹)_n2-(Sp^b)_s2-P^b P

wherein, P^a、P^bEach independently represents a polymerizable group; sp^a、Sp^bEach independently represents a spacer group;

s1, s2 are each independently 0 or 1;

A¹、A²each independently represents a group selected from the group consisting of:

a) trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene and 4, 4' -bicyclohexyl, one or more non-adjacent-CH₂-the group is optionally replaced by-O-or-S-, one or more H atoms are optionally replaced by F atoms,

b) from the group consisting of 1, 4-phenylene and 1, 3-phenylene in which one or two CH groups are optionally replaced by N and one or more H atoms are optionally replaced by L,

c) from the group consisting of tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydrofuran-2, 5-diyl, cyclobutane-1, 3-diyl, piperidine-1, 4-diyl, thiophene-2, 5-diyl and selenophene-2, 5-diyl, wherein one or more H atoms are optionally mono-or polysubstituted by L,

d) by

A group of (a);

wherein one or more H atoms in these groups are optionally replaced by L, and/or one or more double bonds are optionally replaced by a single bond, and/or one or more CH are optionally replaced by N; n2 is 0, 1, 2 or 3;

z represents-CO-O-, -O-CO-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-, straight-chain alkylene having 2 to 4 carbon atoms, -O-, -CO-, -C (R)⁰R⁰⁰)-、-CH₂CF₂-、-CF₂CF₂-or a single bond;

l, at each occurrence, independently represents a F atom, a Cl atom, CN, SCN, SF₅Or optionally fluorinated linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy having 1 to 12C atoms;

R⁰、R⁰⁰each independently of the others, represents a H atom, a F atom or a linear or branched alkyl group having 1 to 12C atoms, wherein one or more H atoms are optionally replaced by a F atom; m represents-O-, -S-, -CH₂-、-CHY¹-or-CY¹Y²-；

Y¹、Y²Each independently of the others, represents a H atom, a F atom, a Cl atom, CN or a linear or branched alkyl group having 1 to 12C atoms, in which one or more H atoms are optionally replaced by a F atom.

When the liquid crystal composition of the present invention contains the compound represented by the formula P, the content of the compound represented by the formula P in the liquid crystal composition is preferably 0.01 to 10%. Preferably, the content of the compound represented by the formula P in the liquid crystal composition is 0.01-1%.

Preferably, the polymerizable compound of formula P is selected from polymerizable compounds represented by the following formula P1,

wherein, P^a、P^bEach independently represents a polymerizable group; sp^a、Sp^bEach independently represents a spacer group;

L¹represents an F atom, a Cl atom, an alkyl group having 1 to 12C atoms, an alkoxy group having 1 to 12C atoms;

r represents 0, 1 or 2.

Preferably, the polymerizable compound represented by the formula P1 is selected from the group consisting of compounds represented by the following formulas P1-1 to P1-3,

in one embodiment of the liquid crystal composition of the present invention, one or more compounds represented by formula II and/or compounds represented by formula III may be further included,

wherein, in the formula II,to represent To represent

R₅、R₆Each independently represents an alkyl group having 1 to 12 carbon atoms, wherein one or more of-CH groups are not adjacent₂-the group is optionally replaced by-O-, -CH ═ CH-, -CO-, -O-CO-, or-CO-O-;

Z₄represents-CH₂CH₂-、-CH＝CH-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-COO-、 -OCO-、-C₂F₄-, -CF ═ CF-or a single bond;

in the formula (III), the reaction solution is prepared,each independently represent

R₇、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.

Preferably, the one or more compounds of formula II are selected from the group consisting of compounds of formulae II-1 to II-17:

preferably, the one or more compounds of formula III are selected from the group consisting of compounds of formulae III-1 to III-4,

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; r₈₂Represents an alkoxy group having 1 to 5 carbon atoms. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 2-propenyl group and a 3-pentenyl group.

When the liquid crystal composition of the present invention contains the compound represented by the formula ii, the amount (mass ratio) of the compound represented by the formula ii added to the liquid crystal composition is not particularly limited, and the total amount of other components in the liquid crystal composition excluding the compound represented by the formula I may be, for example, 15 to 70%, and preferably 30 to 70%. When the liquid crystal composition of the present invention contains the compound represented by the formula III, the amount (mass ratio) of the compound represented by the formula III added to the liquid crystal composition is not particularly limited, and may be, for example, 1 to 30%, preferably 5 to 20%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula I.

By combining the compound shown in the formula II and the compound shown in the formula I in the invention in a liquid crystal composition, the beneficial effects of improving intersolubility and response speed are obtained. By using the compound represented by formula III in combination in the liquid crystal composition of the present invention, a liquid crystal composition having a large optical anisotropy Δ n and a low rotational viscosity is obtained.

In one embodiment of the liquid crystal composition of the present invention, further comprising one or more compounds of formula IV,

wherein the content of the first and second substances,

each independently represents a group selected from the group consisting of the following (i) and (ii):

trans 1, 4-cyclohexylene, 1, 4-cyclohexenyl, wherein one or more non-adjacent-CH' s₂-the group is optionally substituted by-O-or-S-;

(xii) 1, 4-phenylene in which one or two CH groups are optionally substituted by N and one or two H atoms are optionally substituted by F atoms;

R₉to representA linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms;

X₁、X₂each independently represents a H atom or a F atom;

Y³represents F atom, straight-chain alkyl with 1-6 carbon atoms, straight-chain alkoxy with 1-6 carbon atoms or straight-chain alkenyl with 2-6 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by the F atom;

Z₅represents a single bond, -CH₂-、-CH₂CH₂-、-(CH₂)₃-、-(CH₂)₄-、-CH＝CH-、-C≡C-、 -COO-、-OOC-、-OCH₂-、-CH₂O-、-CF₂CH₂-、-CH₂CF₂-、-C₂F₄-or-CF ═ CF —;

r represents 0, 1 or 2.

Preferably, the aforementioned one or more compounds of formula IV are selected from the group consisting of compounds of formulae IV 1 to IV 15:

wherein R is₉With R in the compound of the formula IV₉Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and R₉Any one or more-CH of the groups shown₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; (F) in the formulae IV 1 to IV 6 each independently represents H or F; - (O) CF in the formula IV 7₃represents-CF₃or-OCF₃。

As R in the aforementioned compound of formula IV₉One or more non-adjacent-CH in the alkyl with 1-10 carbon atoms₂After substitution by cyclopropylene, cyclobutylene or cyclopentyleneExamples of the group to be obtained include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropylidene, ethylcyclopropylidene, propylcyclopropylidene, isopropylcyclopropylidene, n-butylcyclopropylidene, isobutylcyclopropylidene, tert-butylcyclopropylidene, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, isopropylcyclobutyl, n-butylcyclobutyl, isobutylcyclobutyl, tert-butylcyclobutyl, methylcyclopentyl, ethylcyclopentylidene, propylcyclopentylidene, isopropylcyclopentylidene, n-butylcyclopentylidene, isobutylcyclopentylidene, and the like. R₉Among the groups shown, preferred from the viewpoint of the rotational viscosity, solubility and clearing point of the liquid crystal compound is cyclopropyl or cyclopentyl.

When the compound represented by the formula iv is contained in the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by the formula iv added to the liquid crystal composition is not particularly limited, and may be, for example, 1 to 55%, preferably 30 to 50%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula I.

The compound represented by the formula IV has positive dielectric anisotropy, and the liquid crystal composition of the invention contains the compound represented by the formula IV, so that the threshold voltage of the liquid crystal composition can be further adjusted.

In one embodiment of the liquid crystal composition of the present invention, further comprising one or more compounds represented by formula V,

wherein R is₁₀、R₁₁Each 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 R₁₀、 R₁₁Any one or more non-adjacent-CH₂-renOptionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; z₆、Z₇Each independently represents a single bond, -CH₂CH₂-or-CH₂O-；

Each independently represent

s represents 1 or 2; t represents 0, 1 or 2.

Preferably, the aforementioned one or more compounds represented by formula V are selected from the group consisting of compounds represented by formula V-1 to formula V-15,

wherein R in the compounds shown in the formulas V-1 to V-15₁₀、R₁₁With R in the compound of the formula V₁₀、R₁₁Each 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 R is₁₀、R₁₁Any one or more non-adjacent-CH in the group₂-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.

The compound shown in the formula V and the compound shown in the formula I are used in combination in the liquid crystal composition, so that the beneficial effect of increasing the negative dielectric anisotropy of the liquid crystal composition is obtained.

As R in the aforementioned formula V₁₀、R₁₁As shown, a carbon atomOne or more non-adjacent-CH in alkyl with a sub-number of 1-10₂Examples of the group substituted with a cyclopropylene group, a cyclobutylene group or a cyclopentylene group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a methylcyclopropylidene group, an ethylcyclopropylidene group, a propylcyclopropylidene group, an isopropylcyclopropylidene group, a n-butylcyclopropylidene group, an isobutylcyclopropylidene group, a tert-butylcyclopropylidene group, a methylcyclobutylene group, an ethylcyclobutylidene group, a propylcyclobutylidene group, an isopropylidene group, a n-butylidene group, an isobutylidene group, a tert-butylidene group, a methylcyclopentylene group, an ethylcyclopentylidene group, a propylcyclopentylidene group, an isopropylidene group, a n-butylcyclopentylidene group and an isobutylcyclopentylidene group. R₁₀、R₁₁Among the groups shown, preferred from the viewpoint of the rotational viscosity, solubility and clearing point of the liquid crystal compound is cyclopropyl, cyclobutyl or cyclopentyl.

When the compound represented by the formula V is contained in the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by the formula V added to the liquid crystal composition is not particularly limited, and may be, for example, 10 to 65%, preferably 20 to 50%, based on the total amount of other components in the liquid crystal composition excluding the compound represented by the formula I.

One embodiment of the liquid crystal composition according to the invention further comprises one or more compounds of formula VI,

wherein R is₁₂、R₁₃Each 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-CH₂Optionally cyclopentylene, cyclopentyleneButyl or cyclopropylene substitution; w represents-O-, -S-or-CH₂O-。

Preferably, the compound of formula VI is selected from the group consisting of compounds of formulae VI-1 to VI-6:

wherein R is₁₃₁Represents an alkyl group having 2 to 6 carbon atoms.

When the compound represented by the formula VI is contained in the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by the formula VI added to the liquid crystal composition is not particularly limited, and may be, for example, 1 to 15%, preferably 2 to 10%, based on the total amount of other components in the liquid crystal composition excluding the compound represented by the formula I. By adding the compound shown in the formula VI into the liquid crystal composition, the liquid crystal composition has larger negative dielectric anisotropy, and is favorable for reducing the driving voltage of a device.

In addition, in the liquid crystal composition of the present invention, a dopant having various functions may be added, and when a dopant is contained, 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, a light stabilizer, and a chiral agent.

Examples of the antioxidant and the light stabilizer include,

u represents an integer of 1 to 10.

By irradiating the liquid crystal composition of the present invention with light, preferably linearly polarized light, photoalignment of the liquid crystal composition can be induced. In a preferred embodiment, the linearly polarized light is ultraviolet light, and the polymerizable compound is cured by irradiation with ultraviolet light to cause fixation of the alignment, whereby the self-assembling photoalignment agent and the polymerizable compound can be photoaligned simultaneously.

The liquid crystal display comprises the liquid crystal composition, and is an active matrix display or a passive matrix display.

Alternatively, the aforementioned liquid crystal display may be, for example, an IPS or FFS display.

The liquid crystal display of the present invention is not limited in structure as long as the compound represented by formula I of the present invention is contained in the liquid crystal composition used in the liquid crystal display, and those skilled in the art can select an appropriate structure of the liquid crystal display according to the desired properties.

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 comprises a first substrate, a second substrate, and a liquid crystal composition which is arranged between the first substrate and the second substrate and consists of a compound shown in a formula I, a compound shown in a formula P and other liquid crystal molecules, wherein the first substrate and the second substrate are oppositely arranged in parallel, 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.

Examples

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. 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 ═ n_e-n_oWherein n is_oRefractive index of ordinary light, n_eThe 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 ∈ ═ ε/ε ×, where ε/is the dielectric constant parallel to the molecular axis, ε × is the dielectric constant perpendicular to the molecular axis, the test conditions were 25 ± 0.5 ℃, 20 μm parallel 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;

γ 1 represents rotational viscosity (mPas) and the test conditions are 25. + -. 0.5 ℃ in 20 μm parallel cells, INSTEC: ALCT-IR1 test.

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 ring structure

Table 2: corresponding codes for end groups and linking groups

Examples are:

the code is CC-Cp-V1;

the code is PGP-Cpr 1-2;

the code is CPY-2-O2;

the code is CCY-3-O2;

the code is COY-3-O2;

the code is CCOY-3-O2;the code is Sb-CpO-O4;

the code is Sc-CpO-O4;

the code is COYL-Cprl-O2;

the code is COYL-1-OV 1.

Example 1

The compound has a structural formula shown as formula I1-1 a:

step 1

Into a reaction flask were charged 11.5g (0.05mol) of Compound 1-1 and 15.7g (0.05mol) of Compound 1-2, pinacol diborate 12.7g (0.05mol), potassium carbonate 16.6g (0.12mol), Pd (dppf)₂Cl₂0.5g, toluene 300mL and water 100 mL. Heating to reflux under the protection of nitrogen, and after reacting for 2 hours, detecting the disappearance of the raw materials by a point plate. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, and recrystallizing with toluene and ethanol for 3 times to obtain white solid 20.5g, GC: 99.1%.

Step 2

26.1g (0.067mol) of the compound 1-3, 12.6g (0.143mol) of methacrylic acid and 100ml of dichloromethane are added into a reaction bottle and stirred to be dissolved completely, 29.5g (0.143mol) of DCC is added at room temperature, then the mixture is stirred for 4 hours at room temperature, and the disappearance of the compound 1-3 is detected by a dot-on-plate method; adding water, stirring, separating, extracting water layer with dichloromethane twice, mixing dichloromethane layers, washing with water, drying with anhydrous sodium sulfate, spin-drying solvent, dissolving with toluene, performing silica gel column chromatography, recrystallizing with toluene and ethanol for 3 times to obtain white solid 19.1g, HPLC: 99.7%.

Step 3

19.6g (0.043mol) of Compound 1-4 and 250mL of tetrahydrofuran were added to the reaction flask. 50mL of 2N aqueous hydrochloric acid was added at room temperature, and the reaction was carried out at room temperature for 4 hours, and disappearance of compounds 1 to 4 was detected by dot plate. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, and recrystallizing with toluene and ethanol for 3 times to obtain white solid 13.5g, GC: 98.3%.

Step 4

17.3g (0.038mol) of Compound 1-5, 6.4g (0.080mmol) of 2-chloroethanol, 11.0g (0.080mmol) of potassium carbonate and 150mL of DMF were added to a reaction flask, heated and stirred, and reacted at 100 ℃ until disappearance of Compound 1-5 was detected on a plate. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, recrystallizing with toluene and petroleum ether for 3 times to obtain I1-1a, white solid 11.5g, and LC 99.3%. The NMR spectrum of the compound represented by formula I1-1a obtained is shown in the attached FIG. 1.

Example 2

The structural formula of the compound is shown as the following formula I1-1I:

step 1

Into a reaction flask were charged 18.1g (0.05mol) of Compound 2-1 and 11.6g (0.05mol) of Compound 2-2, pinacol diborate 12.7g (0.05mol), potassium carbonate 16.6g (0.12mol), Pd (dppf)₂Cl₂0.5g, toluene 300mL and water 100 mL. Heating to reflux under the protection of nitrogen, and after reacting for 2 hours, detecting the disappearance of the raw materials by a point plate. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, and recrystallizing with toluene and ethanol for 3 times to obtain white solid 20.5g, GC: 99.1%.

Step 2

Adding 29.2g (0.067mol) of compound 2-3, 12.6g (0.143mol) of methacrylic acid and 100ml of dichloromethane into a reaction bottle, stirring to dissolve completely, adding 29.5g (0.143mol) of DCC at room temperature, stirring for 4 hours at room temperature, and detecting the disappearance of the compound 2-3 by a dot-on-plate method; adding water, stirring, separating, extracting water layer with dichloromethane twice, mixing dichloromethane layers, washing with water, drying with anhydrous sodium sulfate, spin-drying solvent, dissolving with toluene, performing silica gel column chromatography, recrystallizing with toluene and ethanol for 3 times to obtain white solid 19.1g, HPLC: 99.7%.

Step 3

21.7g (0.043mol) of Compound 2-4 and 250mL of tetrahydrofuran were added to the reaction flask. 50mL of 2N aqueous hydrochloric acid was added at room temperature, the reaction was carried out at room temperature for 4 hours, and disappearance of compound 2-4 was detected by dot plate. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, and recrystallizing with toluene and ethanol for 3 times to obtain white solid 13.5g, GC: 98.3%.

Step 4

15.8g (0.038mol) of Compound 2-5, 5.2g (0.080mmol) of 2-chloroethylamine, 11.0g (0.080mmol) of potassium carbonate and 150mL of DMF were added to a reaction flask, heated and stirred, and reacted at 100 ℃ until disappearance of Compound 1-5 was detected on a plate. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, recrystallizing with toluene and petroleum ether for 3 times to obtain I1-1a, white solid 11.5g, and LC 99.3%.

Example 3

The compound has a structural formula shown as formula I1-2 a:

step 1

To a reaction flask were added 10g (0.027mol) of Compound 3-1, 5.0g (0.06mol) of sodium hydrogencarbonate, 9.7g (0.03mol) of tetrabutylammonium bromide, 6g (0.06mol)100mg of palladium acetate and 100mL of dimethylformamide were heated to 100 ℃ and held for 6 hours. The mixture was cooled and then acidified with 100mL of dilute hydrochloric acid (1N). The aqueous layer was extracted twice with toluene, the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was dried, and purified by distillation under reduced pressure to give 7.1g of a pale yellow oil, 96.5% GC.

Step 2

To a reaction flask was added 7.1g (0.018mol) of compound 3-2, 7mL of aqueous potassium hydroxide solution (2N), 100mL of ethanol. The reaction was stirred and heated to reflux for 1 hour and the plate checked for the disappearance of compound 4. Adjusting pH to acidity with dilute hydrochloric acid (0.5N), extracting water layer with ethyl acetate twice, mixing organic phases, drying with anhydrous sodium sulfate, spin-drying solvent, and recrystallizing with ethanol to obtain off-white solid 4.6g, LC: 97.3%.

Step 3

Adding 4.6g (0.013mol) of compound 3-3, 4.7g (0.015mol) of compound 3-4 and 100ml of dichloromethane into a reaction bottle, stirring to dissolve completely, adding 3.1g (0.015mol) of DCC at room temperature, stirring for 4 hours at room temperature, and detecting the disappearance of compound 3-3 by a dot-on-plate method; adding water, stirring, separating, extracting water layer with dichloromethane twice, mixing dichloromethane layers, washing with water, drying with anhydrous sodium sulfate, spin-drying solvent, dissolving with toluene, performing silica gel column chromatography, recrystallizing with toluene and ethanol for 2 times to obtain white solid 6.1g, HPLC: 98.1%.

Step 4

6.1g (0.009mol) of Compound 3-5 and 100mL of tetrahydrofuran were charged in a reaction flask, after which 2.3g (0.020mol) of tetrabutylammonium fluoride were added in portions. After 2 hours reaction at room temperature, the plate was spotted to detect the disappearance of compounds 3-5. Adding water and ethyl acetate, stirring, extracting, separating, extracting the water layer with ethyl acetate twice, mixing the organic layers, washing with water, drying, spin-drying the solvent, and recrystallizing with toluene petroleum ether for 2 times to obtain off-white solid 3.3g, LC: 97.1%.

Step 5

Referring to step 3 in example 1, the objective monomer I1-2a, 1.5g, was obtained as a white solid.

Example 4

The compound has a structural formula shown as formula I8-3 a:

step 1

6.8g (0.018mol) of Compound 4-1, 0.99g (0.009mol) were charged into a reaction flaskAnd 100mL of tetrahydrofuran, after which 2.3g (0.020mol) of tetrabutylammonium fluoride are added in portions. After 2 hours reaction at room temperature, the plate was spotted to detect the disappearance of compound 4-1. Adding water and ethyl acetate, stirring, extracting, separating, extracting the water layer with ethyl acetate twice, mixing the organic layers, washing with water, drying, spin-drying the solvent, and recrystallizing with toluene petroleum ether for 2 times to obtain off-white solid 3.3g, LC: 97.1%.

Step 2

Referring to step 3 in example 1, the objective monomer I8-3a was obtained as a white solid, 8g, LC: 99.3%.

Manufacturing display box

The display cell was made from virgin, untreated, alkali-free glass with a Norland 65 adhesive using 5 μm spacer beads. The box was assembled by hand and then used with a power supply having 50mW/cm²And 3000mJ/cm²The high-pressure mercury lamp of (1) is cured.

Box filling and curing

The LC mixture was capillary filled at room temperature using capillary action, annealed at 100 ℃ for 1 hour and then passed through linearly polarized UV light (50 mW/cm) at the same temperature²) The irradiation was carried out for 60 seconds. The cartridge was then allowed to cool to room temperature.

Mother liquid crystal composition

TABLE 3 mother liquid Crystal composition A-1

TABLE 4 mother liquid Crystal composition A-2

TABLE 5 mother liquid Crystal composition A-3

TABLE 6 mother liquid Crystal composition A-4

TABLE 7 mother liquid Crystal composition A-5

TABLE 8 mother liquid Crystal composition A-6

Liquid crystal composition examples

The liquid-crystal compositions B-1 to B-6 according to the invention were prepared from the parent liquid-crystal compositions a-1 to a-6 listed above and the compounds of the formula I according to the combinations given in the table below.

Alignment test

The test displays were produced using virgin untreated glass or ITO glass, then filled with nematic mixtures according to mixture examples B-1 to B-6, respectively, and then cured as described above.

Alignment quality was then investigated between crossed polarizers on a light box (light box). A good dark state was observed when the cell was placed between crossed polarizers. A good transmission state was observed when the cell was rotated 45 °. This shows the excellent uniform planar alignment achieved by the mixtures from examples B-1 to B-6. The liquid crystal box continuously applies voltage and switches a dark state and a bright state at the temperature of 78-80 ℃, and the alignment stably exists for 500 hours. In a comparative experiment, the test displays were filled with nematic host mixtures A-1 to A-6 without the compound of formula I and cured in the same manner as described for the mixture examples B-1 to B-6 according to the invention. In comparative experiments, a non-uniform transmission state was observed for all polarizer configurations.

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.