Tetrahydrofuran polymerizable compound and preparation and application thereof
阅读说明：本技术 一种四氢呋喃类可聚合性化合物及其制备和应用 (Tetrahydrofuran polymerizable compound and preparation and application thereof ) 是由 于海龙 苏学辉 王迎运 田会强 储士红 王新颖 姜天孟 陈海光 于 2018-06-25 设计创作，主要内容包括：本发明属于液晶材料技术领域,涉及一种四氢呋喃类可聚合性化合物及其制备和应用。所述化合物具有通式I所示结构,使用了所述化合物或含有所述化合物的组合物具有较宽的向列相温度范围、合适的或较高的双折射率各向异性△n、较高的电阻率、良好的抗紫外线性能、高电荷保持率以及低蒸汽压等性能。<Image he="243" wi="700" file="DDA0001706226050000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention belongs to the technical field of liquid crystal materials, and relates to a tetrahydrofuran polymerizable compound, and preparation and application thereof. The compound has a structure shown in a general formula I, and the compound or the composition containing the compound has the performances of wide nematic phase temperature range, proper or higher birefringence anisotropy delta n, higher resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like.)
1. A tetrahydrofuran-based polymerizable compound having a structure represented by the general formula I:
wherein, in the general formula I, the P1、P2、P3Independently of one another, acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxetane or epoxy;
the ring A, the ring B and the ring C independently represent cyclohexyl or phenylene, and at least one of the cyclohexyl or the phenylene is phenylene;
z is1、Z2、Z3Independently of one another, represents a single bond, -O-, -S-, -CO-O-, -O-CO-O-, -CH ═ N-, -N ═ CH-, -N ═ N-, -C ≡ C-, C1-C12Alkylene or C2-C12Wherein said C is1-C12Alkylene or C2-C12May be independently substituted with F, Cl or CN, and one or more non-adjacent-CH2The radicals may be replaced, independently of one another, by-O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS-or an olefinic bond in such a way that they are not linked directly to one another;
said L1、L2、L3Independently of one another represent-F, -Cl, -CN, -NO2、-CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH(CH3)C2H5、-OCH3、-OC2H5、-COCH3、-COC2H5、-COOCH3、-COOC2H5、-CF3、-OCF3、-OCHF2or-OC2F5；
r1Represents 0, 1, 2 or 3;
r2、r3each independently represents 0, 1, 2, 3 or 4;
m, l and n represent 0 or 1, and m, l and n are not 0 at the same time.
2. The compound of claim 1, wherein P is1、P2、P3Represents a methacrylate group or an acrylate group.
3. A compound according to claim 1 or 2, wherein Z is1、Z2、Z3Independently of one another, represents a single bond, -O-, C1-C5Alkyl or alkoxy groups of (a).
4. A compound according to any one of claims 1 to 3, wherein L is1、L2、L3represents-F, -Cl or-CH3、-OCH3、-C2H5or-OC2H5(ii) a And/or, said r1、r2、r3Each independently represents 0, 1 or 2.
5. The compound of any one of claims 1-4, wherein the compound of formula I:
r1+r2+r3≤4；
or, when r1When > 1, L1Represents F or Cl; or, when r2When > 1, L2Represents F or Cl; or, when r3When > 1, L3Represents F or Cl;
or, when r1+r2+r3When equal to 4, L1、L2、L3Represents F or Cl;
or, when ring a is cyclohexyl and l + n ═ 1 or 2, r1Is 0;
or, when ring a and ring B are both cyclohexyl and l + n is 2, r1And/or r2Is 0.
6. The compound according to any one of claims 1 to 5, wherein the compound is selected from one of the following compounds:
7. the compound of claim 1, wherein the compound is selected from one of the following compounds:
8. a process for the preparation of a compound according to any one of claims 1 to 7, wherein the synthetic route is as follows:
l in the compound involved in the above reactions of each step1、L2、L3、r1、r2、r3、m、l、n、Z1、Z2、Z3With L in the product of the obtained compound1、L2、L3、r1、r2、r3、m、l、n、Z1、Z2、Z3In correspondence, X represents H or CH3；
Preferably, the method comprises the following steps:
(1) to be provided withThe raw material is subjected to metalation reaction with an organic lithium reagent and then is subjected to reaction with boric acid ester to obtain
(2) Subjecting the product obtained in step (1)Andby suzuki reaction, obtaining
(3) Subjecting the product obtained in the step (2)Through reduction reaction to obtain
(4) Subjecting the product obtained in step (3)Obtained by esterification
9. A liquid crystal composition comprising a compound according to any one of claims 1 to 7;
preferably, the mass percentage of the compound in the composition is 0.01-10%, more preferably 0.01-5%, and even more preferably 0.1-3%.
10. Use of a compound according to any one of claims 1 to 7 and/or a composition according to claim 9 in the field of liquid crystal displays; preferably in liquid crystal display devices; more preferably, the liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.
Technical Field
The invention belongs to the technical field of liquid crystal materials, and relates to a tetrahydrofuran polymerizable compound, and preparation and application thereof.
Background
In recent years, liquid crystal display devices have been widely used in various electronic devices, such as smart phones, tablet computers, car navigators, televisions, and the like. Representative liquid crystal display modes include a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an in-plane switching (IPS) mode, a Fringe Field Switching (FFS) mode, and a Vertical Alignment (VA) mode. Among them, the VA mode receives increasing attention because of having a fast fall time, a high contrast ratio, a wide viewing angle, and a high quality image.
However, the liquid crystal medium used for the display element of the active matrix addressing type such as VA mode has its own disadvantages, such as a significantly inferior image sticking level to that of the display element of positive dielectric anisotropy, a relatively slow response time, a relatively high driving voltage, and the like. In order to solve the above problems, some new VA display technologies, such as MVA technology, PVA technology, PSVA technology, have appeared. The PSVA technology not only realizes a wide-viewing-angle display mode similar to MVA/PVA, but also simplifies the CF process, improves the aperture opening ratio while reducing the CF cost, and can obtain higher brightness and further obtain higher contrast. In addition, because the liquid crystal on the whole surface has a pretilt angle, the domino delay phenomenon is avoided, the faster response time can be obtained under the condition of keeping the same driving voltage, and the afterimage level is not influenced.
Disclosure of Invention
It is a first object of the present invention to provide a polymerizable compound useful in polymer stabilization techniques. The liquid crystal composition containing the compound has better alignment effect, more complete polymerization and lower residue. And the compound has low price and stable performance, can be widely applied to the field of liquid crystal display and has important application value.
The liquid crystal compound has the following structure:
wherein, in the general formula I, the P1、P2、P3Independently of one another, acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxetane or epoxy; the ring A, the ring B and the ring C independently represent cyclohexyl or phenylene, and at least one of the cyclohexyl or the phenylene is phenylene; z is1、Z2、Z3Independently of each other, represents a single bond,-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CH＝N-、-N＝CH-、-N＝N-、-C≡C-、C1-C12Alkylene or C2-C12Wherein said C is1-C12Alkylene or C2-C12May be independently substituted with F, Cl or CN, and one or more non-adjacent-CH2The radicals may be replaced, independently of one another, by-O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS-or an olefinic bond in such a way that they are not linked directly to one another; said L1、L2、L3Independently of one another represent-F, -Cl, -CN, -NO2、-CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH(CH3)C2H5、-OCH3、-OC2H5、-COCH3、-COC2H5、-COOCH3、-COOC2H5、-CF3、-OCF3、-OCHF2or-OC2F5；r1Represents 0, 1, 2 or 3; r is2、r3Each independently represents 0, 1, 2, 3 or 4; m, l and n represent 0 or 1, and m, l and n are not 0 at the same time.
The compounds of the present invention, in formula I, are related to P1、P2、P3: preferably, said P1、P2、P3Represents a methacrylate group or an acrylate group.
With respect to Z1、Z2、Z3: preferably, Z is1、Z2、Z3Independently of one another, represents a single bond, -O-, C1-C5Alkyl or alkoxy groups of (a).
With respect to L1、L2、L3: preferably, said L1、L2、L3represents-F, -Cl or-CH3、-OCH3、-C2H5or-OC2H5。
About r1、r2、r3: preferably, r1、r2、r3Each independently represents 0, 1 or 2.
The compounds of the invention, preferably in formula I, P1、P2、P3Represents a methacrylate group or an acrylate group; the ring A, the ring B and the ring C independently represent cyclohexyl or phenylene, and at least one of the cyclohexyl or the phenylene is phenylene; z is1、Z2、Z3Independently of one another, represents a single bond, -O-, -S-, -CO-O-, -O-CO-O-, -CH ═ N-, -N ═ CH-, -N ═ N-, -C ≡ C-, C1-C12Alkylene or C2-C12Wherein said C is1-C12Alkylene or C2-C12May be independently substituted with F, Cl, or CN, and one or more non-adjacent-CH2The radicals may be replaced, independently of one another, by-O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS-or an olefinic bond in such a way that they are not linked directly to one another; l is1、L2，L3represents-F, -Cl or-CH3、-OCH3、-C2H5or-OC2H5；r1、r2、r3Each independently represents 0, 1 or 2; m, l and n represent 0 or 1, and m, l and n are not 0 at the same time;
even more preferably, in formula I, P1、P2、P3Represents a methacrylate group or an acrylate group; the ring A, the ring B and the ring C independently represent cyclohexyl or phenylene, and at least one of the cyclohexyl or the phenylene is phenylene; z is1、Z2、Z3Independently of one another, represents a single bond, -O-, C1-C5Alkyl or alkoxy of (a); l is1、L2、L3represents-F, -CH3、-OCH3、-C2H5or-OC2H5；r1、r2、r3Each independently represents 0, 1 or 2; m, l and n represent 0 or 1, and m, l and n are not 0 at the same time.
As a further preferred embodiment of the present invention, the compound is represented by formula I:
r1+r2+r3≤4；
or, when r1When > 1, L1Represents F or Cl; when r is2When > 1, L2Represents F or Cl; when r is3When > 1, L3Represents F or Cl;
or, when r1+r2+r3When equal to 4, L1、L2、L3Represents F or Cl;
or, when ring a is cyclohexyl and l + n ═ 1 or 2, r1Is 0;
or, when ring a and ring B are both cyclohexyl and l + n is 2, r1And/or r2Is 0.
As the most preferable technical scheme of the present invention, the liquid crystal compound is selected from one of the following compounds:
as the best embodiment of the present invention, the compound is selected from one of the following compounds:
the second object of the present invention is to provide a method for preparing the liquid crystal compound.
The synthetic route is as follows:
the method specifically comprises the following steps:
(1) to be provided withThe raw material is subjected to metalation reaction with an organic lithium reagent and then is subjected to reaction with boric acid ester to obtain
(2) Subjecting the product obtained in step (1)Andby suzuki reaction, obtaining
(3) Subjecting the product obtained in the step (2)Through reduction reaction to obtain
(4) Subjecting the product obtained in step (3)Obtained by esterification
L in the compound involved in the above reactions of each step1、L2、L3、r1、r2、r3、m、l、n、Z1、Z2、Z3With L in the resulting liquid-crystalline compound product1、L2、L3、r1、r2、r3、m、l、n、Z1、Z2、Z3Corresponding to (above), X represents H or CH3。
In the step (1) of the above method,the feeding molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0; the feeding molar ratio of the boric acid ester to the boric acid ester is 1: 1.0-3.0; the reaction temperature can be between-50 and-100 ℃.
Wherein, the raw materialsAre available through public commercial routes; the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium; the boric acid ester is selected from one or more of trimethyl borate, triisopropyl borate, tributyl borate or triisobutyl borate.
In the step (2) of the above method,andthe feeding molar ratio of (A) to (B) is 1.0: 1.0 to 1.5; the reaction temperature can be 50-150 ℃.
Wherein, the raw materialsAre commercially available through the open.
In the step (3), the reaction temperature is controlled to be 10-50 ℃.
Step (4) of the above method) In (1),the feeding mol ratio of the monomer to the methacrylic chloride or the acryloyl chloride is 1.0: 3.0 to 4.0; the reaction temperature can be-20-0 ℃.
A third object of the present invention is to protect a composition containing the liquid crystal compound. Preferably, the mass percentage of the compound in the composition is 0.01-10%, more preferably 0.01-5%, and even more preferably 0.1-3%.
The fourth purpose of the invention is to protect the application of the liquid crystal compound and the composition containing the liquid crystal compound in the field of liquid crystal display, preferably in a liquid crystal display device. The liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS or IPS liquid crystal display. The liquid crystal compound or the composition containing the liquid crystal compound has the properties of wide nematic phase temperature range, proper or high birefringence anisotropy delta n, high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like.
Detailed Description
The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the invention, which is intended to include within the scope of the appended claims all such equivalent changes and modifications as may be made without departing from the spirit of the invention disclosed herein.
The liquid crystal compounds used in the following examples can be synthesized by a known method or obtained from a publicly available commercial source, unless otherwise specified, and these synthesis techniques are conventional, and the resulting liquid crystal compounds are tested to meet the standards for electronic compounds.
According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz); γ 1 represents rotational viscosity (mpa.s, 25 ℃); cp represents a clearing point; epsilon‖Representing parallel to the fingerThe dielectric constant of the director.