CN112480027B - Polymerizable compound, polymerizable composition, polymer, optically anisotropic body, and liquid crystal display device - Google Patents
Polymerizable compound, polymerizable composition, polymer, optically anisotropic body, and liquid crystal display device Download PDFInfo
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- CN112480027B CN112480027B CN201910865996.5A CN201910865996A CN112480027B CN 112480027 B CN112480027 B CN 112480027B CN 201910865996 A CN201910865996 A CN 201910865996A CN 112480027 B CN112480027 B CN 112480027B
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Abstract
The present invention relates to a compound, a polymerizable composition, a polymer, an optical isomer, and a liquid crystal display device. The polymerizable compound of the present invention has a structure represented by the general formula (AO-1). The composition contains the polymerizable compound of the present invention, the polymer of the present invention obtained by polymerizing the composition, and the optically anisotropic body and the liquid crystal display device each of which is made of the polymer of the present invention, are less likely to cause crystal precipitation, and have high storage stability.
Description
Technical Field
The present invention relates to the field of liquid crystal displays.
Background
Currently, compounds having a polymerizable group (polymerizable compounds) are used in various optical materials; for example, a polymerizable composition containing a polymerizable compound is aligned in a liquid crystal state, and then polymerized, whereby a polymer having a uniform orientation can be produced, and such a polymer can be used for a polarizing plate, a retardation plate, and the like required for a display. In many cases, a polymerizable composition containing two or more kinds of polymerizable compounds is used in order to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, transparency, mechanical strength, surface hardness, heat resistance and light resistance of the polymer. In this case, the polymerizable compound to be used is required to have good physical properties to the polymerizable composition without adversely affecting other properties.
In order to increase the viewing angle of a liquid crystal display, it is required that the birefringence of the retardation film has small wavelength dispersion or reverse wavelength dispersion. As a material for this purpose, various polymerizable liquid crystal compounds having inverse wavelength dispersibility or low wavelength dispersibility have been developed. However, in the development of these materials, it was found that these polymerizable compounds tend to cause precipitation of crystals when added to a polymerizable composition, and the stability was not high. In addition, when the polymer composition is applied to a substrate and polymerized, there is a problem in that unevenness is likely to occur. Therefore, it is desired to develop a polymerizable liquid crystal compound having inverse wavelength dispersibility or low wavelength dispersibility, which can solve the problems of stability and unevenness.
Disclosure of Invention
The present invention has been made to solve the problems of obtaining a compound which has good miscibility and does not cause precipitation of crystals when added to a polymerizable composition.
In order to solve the above problems, the present inventors have found, after intensive studies, that the polymerizable compound of the present invention is excellent in stability and is less likely to deteriorate and polymerize during production and storage, and have completed the present invention.
Specifically, the invention provides the following technical scheme:
in one aspect, the present invention provides a polymerizable compound having a structure represented by the formula (AO-1):
in the formula (AO-1), A x Represents an aromatic cyclic hydrocarbon group having 6 to 30 carbon atoms, an aromatic heterocyclic group having 6 to 30 carbon atoms, or a hydrocarbon group having 6 to 30 carbon atoms optionally substituted with a heteroatom, the aromatic cyclic hydrocarbon group, the aromatic heterocyclic group optionally having a substituent;
A y represents a hydrogen atom, an aromatic group having 2 to 25 carbon atoms, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkynyl group having 2 to 25 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, one of the alkyl group, the alkynyl group, and the cycloalkyl group being-CH 2 -or a plurality of non-adjacent-CH 2 -optionally substituted by-O-, -S-, -C (=o) -O-, -O-C (=o) -O-, -C (=o) -NH-, -NH-C (=o) -, -ch=ch-C (=o) -O-, or, -C (=o) -O-ch=ch-, one or more hydrogen atoms optionally being substituted by halogen;
Q 1 represents a hydrogen atom or a cycloalkyl group having 3 to 20 carbon atoms, the hydrogen atom on the cycloalkyl group being optionally substituted by halogen.
In a second aspect of the present invention, there is provided a polymerizable composition comprising the aforementioned polymerizable compound of the present invention.
In a third aspect of the present invention, there is provided a polymer obtained by polymerizing the polymerizable compound of the present invention or polymerizing the liquid crystal composition of the present invention.
In a fourth aspect of the present invention, there is provided an optically anisotropic body comprising the polymer of the present invention.
In a fifth aspect of the present invention, there is provided a liquid crystal display device comprising the polymer of the present invention or the optically anisotropic body of the present invention.
The beneficial effects of the invention are that
The polymerizable compound of the present invention is a polymerizable compound having high storage stability, and is less likely to cause precipitation of crystals when added to a liquid crystal composition.
In addition, the polymerizable compound adopts a starting material with no toxicity and low cost, thereby effectively reducing the synthesis cost.
Detailed Description
[ polymerizable Compound ]
The polymerizable compound of the present invention has a structure represented by the formula (AO-1).
In the formula (AO-1), A x Represents an aromatic cyclic hydrocarbon group having 6 to 30 carbon atoms, an aromatic heterocyclic group having 6 to 30 carbon atoms, or a hydrocarbon group having 6 to 30 carbon atoms optionally substituted with a heteroatom, the aromatic cyclic hydrocarbon group, the aromatic heterocyclic group optionally having a substituent;
A y represents a hydrogen atom, an aromatic group having 2 to 25 carbon atoms, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkynyl group having 2 to 25 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, one of the alkyl group, the alkynyl group, and the cycloalkyl group being-CH 2 -or a plurality of non-adjacent-CH 2 -optionally substituted by-O-, -S-, -C (=o) -O-, -O-C (=o) -O-, -C (=o) -NH-, -NH-C (=o) -, -ch=ch-C (=o) -O-, or, -C (=o) -O-ch=ch-, one or more hydrogen atoms optionally being substituted by halogen;
Q 1 represents a hydrogen atom or a cycloalkyl group having 3 to 20 carbon atoms, the hydrogen atom on the cycloalkyl group being optionally substituted by halogen.
The asterisk in the formula (AO-1) indicates the position at which the formula (AO-1) is linked to the other moiety in the polymerizable compound of the present invention. The other moiety linked to the formula (AO-1) has a polymerizable group therein, so that the polymerizable compound of the present invention can be polymerized.
As the A x The aromatic hydrocarbon in the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by the above-mentioned aromatic heterocyclic group includes benzene ring, naphthalene ring, anthracene ring, fluorene ring, indane ring and the like, and the aromatic heterocyclic ring in the above-mentioned aromatic heterocyclic group includes five-membered ring such as pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring and thiazole ringAromatic heterocyclic rings, six-membered aromatic heterocyclic rings such as pyridine ring, pyridazine ring, pyrimidine ring and pyrazine ring, and condensed ring aromatic heterocyclic rings such as benzimidazole ring, benzothiophene ring, benzimidazole ring, benzoxazole ring, benzothiazole ring and carbazole ring.
As the A y The alkyl group having 1 to 25 carbon atoms represented means a straight chain or branched alkyl group having 1 to 25 carbon atoms. Preference is given to straight-chain or branched alkyl radicals having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, hexyl and the like.
As the A y The alkenyl group having 2 to 25 carbon atoms represented means a straight chain or branched alkenyl group having 2 to 25 carbon atoms. Straight or branched alkenyl groups having 2 to 6 carbon atoms are preferred, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl and the like.
As the A y The alkynyl group having 2 to 25 carbon atoms represented means a straight-chain or branched alkynyl group having 2 to 25 carbon atoms. Straight or branched alkynyl groups having 2 to 6 carbon atoms are preferred, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 1-hexynyl and the like.
As the A y The cycloalkyl group having 3 to 20 carbon atoms represented means a cycloalkyl group having 3 to 20 carbon atoms. Cycloalkyl groups having 3 to 7 carbon atoms are preferred, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Cyclopropyl, cyclobutyl, cyclopentyl are particularly preferred.
As the A y The aromatic group having 2 to 25 carbon atoms represented by the formula A is the same as the above x The same groups as those listed for the aromatic cyclic hydrocarbon group and the aromatic heterocyclic group.
Examples of the halogen include fluorine, chlorine, bromine and iodine atoms, and preferably fluorine atoms.
Q 1 Represents a hydrogen atom or a cycloalkyl group having 3 to 20 carbon atoms, any of which may be substituted with halogen.
As a means ofQ is as described above 1 Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and preferably cyclopropyl, cyclobutyl, and cyclopentyl, more preferably cyclopropyl and cyclopentyl.
The halogen is a fluorine, chlorine, bromine or iodine atom, preferably a fluorine atom.
The polymerizable compound of the present invention preferably containsThe structure shown serves as a parent structure. By incorporating the parent nucleus structure in the polymerizable compound of the present invention, the solubility of the polymerizable compound of the present invention can be increased, and thus higher film forming properties can be exhibited.
In addition, by using the polymerizable compound of the present invention in a liquid crystal composition, the advantageous effect of improving the refractive index can be obtained.
Among the polymerizable compounds of the present invention, preferred are compounds represented by the following formula (I),
in the formula (I), A x 、A y The meaning of (A) is the same as that in the aforementioned formula (AO-1);
Q 1 represents a hydrogen atom or a cycloalkyl group having 3 to 20 carbon atoms, the hydrogen atom on the cycloalkyl group being optionally substituted by halogen, and when Q 1 When representing a hydrogen atom, A 1 、A 2 At least one of them represents
G represents an aromatic ring structure optionally having a bond at any position and optionally unsubstituted or substituted by more than one L on the ring,
wherein L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group or a linear or branched alkyl group having 1 to 20 carbon atoms, one of the linear or branched alkyl groups having 1 to 20 carbon atoms being-CH 2 -or not adjacent two or more-CH 2 -optionally substituted by-O-, -S-, -C (=o) O-, -OC (=o) -, -C (=o) -S-, -S-C (=o) -, -O-C (=o) -O-, -C (=o) -NH-, -NH-C (=o) -, -ch=ch-C (=o) O-, -ch=ch-OC (=o) -, -C (=o) O-ch=ch-, -OC (=o) -ch=ch-, -cf=cf-, or-c≡c-, any hydrogen atom optionally being substituted by a fluorine atom, which may be the same or different when L is present in plurality;
A 1 、A 2 each independently represents a monocyclic or condensed ring structure having 4 to 10 carbon atoms, which is optionally substituted;
Z 1 、Z 2 each independently represents-C (=O) -O-, -C (=O) -, -CH 2 (C＝O)-O-、-C(＝O)-OCH 2 -、-CH 2 CH 2 C(＝O)-O-、-C(＝O)-OCH 2 CH 2 -、-O(CH 2 )m-、-(CH 2 ) nO-, or-S-, wherein m, n each independently represent 0, 1, 2 or 3, Z 1 When there are a plurality of, optionally the same or different, Z 2 Optionally the same or different when present in plurality;
m1, m2 each independently represent 1, 2 or 3;
Sp 1 、Sp 2 each independently represents a single bond, an alkenyl group having 2 to 25 carbon atoms, - (CH) 2 )p 1 -、-O(CH 2 )p 1 -、-OC(＝O)-(CH 2 )p 1 -or-C (=o) -O (CH 2 )p 1 -，p 1 Represents 2, 3, 4, 5 or 6, wherein the Sp 1 、Sp 2 One or more non-adjacent-CH(s) 2 -optionally-O-, -S-, -C (=o) -O-, -O-C (=o) -O-, -ch=ch-C (=o) -O-, or, -O-C (=o) -ch=ch-, one or more hydrogen atoms each independently optionally being substituted with a fluorine atom or a chlorine atom;
P 1 、P 2 each independently represents a polymerizable group.
As the aromatic ring structure represented by G, G preferably represents a trivalent phenyl group or a trivalent naphthyl group from the viewpoints of liquid crystal property and ease of synthesis.
Further, from the viewpoints of liquid crystal property and ease of synthesis, A 1 、A 2 Each independently is preferablyOr (I)>
As P 1 、P 2 The polymerizable group represented by the formula (I) is preferably an alkenyloxy group, an acrylate group, a methacrylate group, a fluoromethyl acrylate group, an acrylamide group, an epoxy group, or a maleimide group, more preferably an alkenyloxy group, an acrylate group, or a methacrylate group, and particularly preferably an acrylate group, or a methacrylate group.
Optionally, the compound of formula (I) is selected from the group consisting of compounds of formula I-a, formula I-b, and formula I-c:
wherein P is 1 Representation ofOr a hydrogen atom. Preferably P 1 Representation ofOr a hydrogen atom.
Sp represents a single bond, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, any one or more of which are not adjacent to each other, -CH 2 -optionally-O-, -S-, -C (=o) -, -CH 2 O-、-OCH 2 -C (=o) -O-, -O-C (=o) -, -ch=ch-C (=o) -O-, or, -O-C (=o) -ch=ch-substituted.
Q 11 Represents a cycloalkyl group having 3 to 20 carbon atoms, any hydrogen atom on the cycloalkyl group being optionally substituted by halogen.
Examples of the cycloalkyl group having 3 to 20 carbon atoms include those described above and Q 1 The same groups as exemplified in (a) are used.
The halogen is a fluorine, chlorine, bromine or iodine atom, preferably a fluorine atom.
P' representsOr (I)>
Sp 11 、Sp 21 Independently represent an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 4 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms, wherein one or more of them is not adjacent to-CH 2 Optionally substituted by-O-, optionally substituted by fluorine atoms.
The alkyl group having 3 to 10 carbon atoms is a straight-chain or branched alkyl group having 3 to 10 carbon atoms, and examples thereof include propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, hexyl and the like. Preference is given to straight-chain alkyl having 3 to 10 carbon atoms, particularly preferably straight-chain alkyl having 3 to 6 carbon atoms, for example propyl, butyl, pentyl, hexyl.
The alkenyl group having 4 to 10 carbon atoms mentioned above means a straight-chain or branched alkenyl group having 4 to 10 carbon atoms. Such as 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, and the like. Straight or branched alkenyl groups having 4 to 10 carbon atoms are preferred.
The above-mentioned alkoxy group having 3 to 10 carbon atoms means a straight-chain or branched alkoxy group having 3 to 10 carbon atoms. Such as propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, sec-butoxy, pentoxy, neopentoxy, hexoxy, heptoxy, and the like. Straight-chain alkoxy groups having 3 to 10 carbon atoms are preferred.
n, m each independently represent 0, 1, 2 or 3.
As the compounds represented by the general formulae I-a, I-b, I-c, specifically, the compounds represented by the general formula I-a are preferably selected from the group consisting of the compounds represented by the following formulas I-a-1 to I-a-12; the compound represented by the formula I-b is preferably selected from the group consisting of compounds represented by the following formulas I-b-1 to I-b-9; the compound represented by the formula I-c is preferably selected from the group consisting of compounds represented by the following formulas I-c-1 to I-c-6,
the following methods are used for the preparation of the compound of formula (I) of the present invention, but are not limited thereto. Those skilled in the art will be able to select suitable other methods to prepare based on knowledge in the art:
(wherein P, sp, sp2, A 1 、A 2 、Z 1 、Z 2 、m1、m2、A x 、A y 、Q 1 G each independently represents the same as that in the general formula (I)
In the above production method, the compound represented by the formula (S-3) can be obtained by reacting the compound represented by the formula (S-1) with the compound represented by the formula (S-2) in the presence of a catalyst such as aluminum trichloride.
The compound represented by the formula (S-4) can be obtained by subjecting the compound represented by the formula (S-3) to a demethylating agent such as boron tribromide.
The compound represented by the formula (S-5) can be obtained by reacting the compound represented by the formula (S-4) with a compound capable of reacting with a hydroxyl group, and the compound represented by the formula (S-6) can be obtained by the same or similar synthetic method. Examples of the compound capable of reacting with a hydroxyl group include Etc., wherein k represents 1, 2 or 3.
The compound represented by the formula (I) can be obtained by reacting the compound represented by the formula (S-6) with the compound represented by the formula (S-7) in the presence of an acid catalyst. Examples of the acid include p-toluenesulfonic acid, pyridinium p-toluenesulfonate, and 10-camphorsulfonic acid.
The reactions of all steps of all the above methods are carried out in a solvent; examples of the solvent include tetrahydrofuran, N-dimethylformamide, ethanol, methanol, methylene chloride, acetone, toluene, and deionized water.
[ polymerizable composition ]
The polymerizable composition of the present invention contains the polymerizable compound of the present invention.
In addition, the polymerizable composition of the present invention may contain other components.
The polymerizable composition of the present invention can be used as, for example, a liquid crystal composition. When used as a liquid crystal composition, a polymerizable compound which does not exhibit liquid crystallinity may be added to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, examples of such components include polymer-forming monomers and polymer-forming oligomers in the art.
The polymerizable composition of the present invention may contain, for example, a photopolymerization initiator or the like according to the purpose. Examples of such photopolymerization initiators include benzophenones, acetophenones, and benzil ketals.
In the polymerizable composition of the present invention, a stabilizer may be added for the purpose of improving storage stability. Examples of usable stabilizers include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, and the like.
The polymerizable composition of the present invention can be used for films, optical elements, coating agents, liquid crystal compositions, and the like.
[ Polymer ]
The polymer of the present invention is obtained by polymerizing the polymerizable compound of the present invention or by polymerizing the polymerizable composition.
Examples of the method for polymerizing the polymerizable compound or polymerizable composition of the present invention include a method for polymerizing the compound or polymerizable composition by irradiation with active energy rays such as ultraviolet rays or electron rays. In the case of using ultraviolet rays, a polarized light source may be used, or an unpolarized light source may be used.
The polymers of the present invention can be used in a variety of applications. For example, a polymer obtained by polymerizing a composition containing the polymerizable compound of the present invention in an unoriented manner can be used as a light scattering plate or the like. In addition, the polymer obtained by polymerizing the composition containing the polymerizable compound of the present invention after orientation has optical anisotropy, and can be used as an optical isomer.
Such an optical isomer can be produced, for example, by supporting a polymerizable composition containing the polymerizable compound of the present invention on a substrate and then polymerizing the polymerizable compound.
[ optical anisotropy isomer ]
The optical isomers of the present invention comprise the aforementioned polymers of the present invention.
The optical isomer can be produced, for example, by supporting a polymerizable composition containing the polymerizable compound of the present invention on a substrate and then polymerizing the polymerizable compound. The optical isomer of the present invention may be used by being peeled off from the substrate or may be used without being peeled off from the substrate. The obtained optically anisotropic body may be laminated, or may be bonded to another substrate for use.
[ liquid Crystal display device ]
The liquid crystal display device of the present invention contains the polymer of the present invention. In addition, the liquid crystal display device of the present invention is not particularly limited.
Examples
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are commercially available from the public sources unless otherwise specified.
The progress of the reaction is generally monitored by TLC, and the post-treatment after the completion of the reaction is generally washing with water, extracting, combining the organic phases, drying, evaporating the solvent under reduced pressure, and recrystallizing, column chromatography, all of which can be carried out by those skilled in the art as described below.
Example 1
Preparing a compound shown in a formula I-a-1, wherein the structural formula is as follows,
the synthetic route is as follows:
the specific synthesis steps are as follows:
step 1: terephthalyl ether (13.8 g,0.1 mol) and cyclopropylcarbonyl chloride (12.5 g,0.12 mol) were dissolved in DCM (200 mL) and added to a three-necked flask, cooled to 0deg.C and AlCl was added in portions 3 (17.4 g,0.13 mol), reacting for 3 hours under heat preservation, pouring into water, separating liquid, extracting water phase with DCM, spin-drying an organic phase, adding toluene into a crude product, passing through a silica gel column, evaporating solvent to obtain white solid, and pulping petroleum ether to obtain an intermediate 1 (17 g,0.08 mol), wherein the yield is 82.5%;
step 2: intermediate 1 (17 g,0.08 mol) was dissolved in DCM (200 mL) and added to a three-necked flask, cooled to 0deg.C, and BBr was slowly added dropwise 3 (40 g,0.16 mol) for 3 hours under heat preservation, pouring the mixture into water, separating liquid, extracting the water phase by DCM, concentrating and spin-drying to obtain brown solid, and pulping the product by petroleum ether to obtain intermediate 2 (12.1 g,0.068 mol) with the yield of 85%;
step 3: intermediate 3(39.6 g,0.15 mol) and intermediate 2 (12.1 g,0.068 mol) are dissolved in DMF (100 mL) and then added into a three-necked flask, potassium carbonate (20.7 g,0.15 mol) is added, the mixture is heated to 80 ℃, the temperature is kept for 3 hours, the reaction is reduced, the temperature is reduced, the reaction solution is filtered, toluene is added into a filter cake, a silica gel column is used for obtaining pale yellow liquid, a solvent is evaporated, and a petroleum ether beating product is obtained, so that intermediate 4 (26 g,0.05 mol) is obtained, and the yield is 74%;
step 4: dissolving intermediate 4 (26 g,0.05 mol) in tetrahydrofuran (40 mL), adding into a three-necked flask, adding lithium hydroxide (2.4 g,0.1 mol), heating to reflux, carrying out reflux reaction for 2 hours, cooling, pouring the reaction solution into a dilute hydrochloric acid aqueous solution, extracting the reaction solution with ethyl acetate, washing with water, drying with anhydrous sodium sulfate, spin-drying to obtain a yellow solid, and pulping with petroleum ether to obtain the product; yield of intermediate 5 (20 g,0.046 mol): 93%.
Step 5: parahydroxybenzoic acid (6 g,43 mmol), chlorohexanol (7.1 g,52 mmol), sodium hydroxide (3.44 g,86 mmol), potassium iodide (0.7 g,4.3 mmol) and water (50 mL) were added to a three-necked flask, heated to reflux, reacted for 4 hours under reflux, cooled, hydrochloric acid was added to the reaction solution, the reaction solution was filtered, and the filter cake ethyl acetate was recrystallized 2 times to give intermediate 6 (6.1 g,26 mmol) in 60% yield.
Step 6: dissolving intermediate 6 (6 g,25 mmol) in toluene (100 mL), adding p-toluenesulfonic acid (0.43 g,2.5 mmol) and acrylic acid (3.6 g,50 mmol) into a three-necked flask, heating to reflux, reacting for 4 hours under reflux, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, recrystallizing the product with ethanol twice to obtain intermediate 7 (5.84 g,20 mmol) with a yield of 80%;
step 7: dissolving intermediate 7 (10 g,34 mmol), intermediate 5 (6.63 g,15.4 mmol) and DMAP (0.38 g,3.1 mmol) in dichloromethane (100 mL), adding into a three-port bottle, maintaining the temperature at 0-10 ℃, dropwise adding a dichloromethane mixed solution of DCC (7 g,34 mmol) after half an hour, heating to room temperature, reacting for 4 hours, filtering the reaction solution, spinning, adding toluene to dissolve the product, performing column chromatography to obtain pale yellow liquid, spinning the reaction solution, recrystallizing the product isopropanol and toluene for 1 time to obtain intermediate 8 (10.1 g,10.3 mmol), and obtaining the yield of 66.8%;
step 8: 2-benzothiazole hydrazine (5 g,30 mmol) and(6.1 g,36 mmol) was dissolved in DMF (50 mL) and added into a three-necked flask, potassium carbonate (4.9 g,36 mmol) was added, the temperature was raised to 80 ℃, the reaction was carried out for three hours under heat preservation, the temperature was lowered, the reaction solution was poured into ice water, the reaction solution was filtered, and toluene and ethanol as a filter cake were recrystallized to obtain a product intermediate 9 (6.7 g,22.5 mmol) in 75% yield;
step 9: adding the intermediate 9 (8.9 g,30 mmol), (±) -10-camphorsulfonic acid (1.4 g,6 mmol), tetrahydrofuran (100 mL), ethanol (100 mL) and the intermediate 8 (24.5 g,25 mmol) into a three-necked flask, heating to 60 ℃, preserving heat for reaction for 6 hours, cooling, rotationally steaming to remove the solvent, pulping with isopropanol, and performing column chromatography to obtain a product intermediate 10 (18.8 g,14.9 mmol) with a yield of 59.6%;
step 10: intermediate 10 (18.8 g,14.9 mmol) was dissolved in toluene (200 mL) and added to a three-necked flask, p-toluenesulfonic acid (0.25 g,1.49 mmol) and acrylic acid (2.15 g,29.8 mmol) were added, heated to reflux, reacted for 4 hours under reflux, cooled, the reaction mixture was poured into water, extracted with dichloromethane, washed with water, dried by spin, the product was toluene column chromatography, and toluene ethanol was recrystallized to give I-a-1 (9.8 g,7.5 mmol) in 50% yield.
Example 2
Preparing a compound shown in a formula I-a-4, wherein the structural formula is as follows,
the synthetic route is as follows:
the specific synthesis steps are as follows:
step 1: the terephthalyl ether (13.8 g,0.1 mol) and cyclopropylcarbonyl chloride (12.5 g,0.12 mol) were dissolved in DCM (200 mL) and added to a three-necked flask, cooled to 0deg.C and AlCl was added 3 (17.4 g,0.13 mol), reacting for 3 hours under heat preservation, pouring into water, separating liquid, extracting water phase with DCM, spin-drying an organic phase, adding toluene into a crude product, passing through a silica gel column, evaporating solvent to obtain white solid, and pulping petroleum ether to obtain an intermediate 1 (17 g,0.08 mol), wherein the yield is 82.5%;
step 2: intermediate 1 (17 g,0.08 mol) was dissolved in DCM (200 mL) and added to a three-necked flask, cooled to 0deg.C, and BBr was slowly added dropwise 3 (40 g,0.16 mol) for 3 hours under heat preservation, pouring the mixture into water, separating liquid, extracting the water phase by DCM, concentrating and spin-drying to obtain brown solid, and pulping the product by petroleum ether to obtain intermediate 2 (12.1 g,0.068 mol) with the yield of 85%;
step 3: intermediate 3(39.6 g,0.15 mol) and intermediate 2 (12.1 g,0.068 mol) were dissolved in DMF (100 mL) and added into a three-necked flask, and then potassium carbonate (20.7 g,0.15 mol) was added and heated to 80℃for 3 hours of reaction at a constant temperature, cooled and filtered to give a solutionAdding toluene into the reaction solution, passing through a silica gel column to obtain pale yellow liquid, evaporating the solvent and pulping the petroleum ether to obtain intermediate 4 (26 g,0.05 mol) with a yield of 74%;
step 4: dissolving intermediate 4 (26 g,0.05 mol) in tetrahydrofuran (40 mL), adding into a three-necked flask, adding lithium hydroxide (2.4 g,0.1 mol), heating to reflux, carrying out reflux reaction for 2 hours, cooling, pouring the reaction solution into a dilute hydrochloric acid aqueous solution, extracting the reaction solution with ethyl acetate, washing with water, drying with anhydrous sodium sulfate, spin-drying to obtain a yellow solid, and pulping with petroleum ether to obtain the product; yield of intermediate 5 (20 g,0.046 mol): 93%.
Step 5: parahydroxybenzoic acid (6 g,43 mmol), chlorohexanol (7.1 g,52 mmol), sodium hydroxide (3.44 g,86 mmol), potassium iodide (0.7 g,4.3 mmol) and water (50 mL) were added to a three-necked flask, heated to reflux, reacted for 4 hours under reflux, cooled, hydrochloric acid was added to the reaction solution, the reaction solution was filtered, and the filter cake ethyl acetate was recrystallized 2 times to give intermediate 6 (6.1 g,26 mmol) in 60% yield.
Step 6: dissolving intermediate 6 (6 g,25 mmol) in toluene (100 mL), adding p-toluenesulfonic acid (0.43 g,2.5 mmol) and acrylic acid (3.6 g,50 mmol) into a three-necked flask, heating to reflux, reacting for 4 hours under reflux, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, recrystallizing the product with ethanol twice to obtain intermediate 7 (5.84 g,20 mmol) with a yield of 80%;
step 7: dissolving intermediate 7 (10 g,34 mmol), intermediate 5 (6.63 g,15.4 mmol) and DMAP (0.38 g,3.1 mmol) in dichloromethane (100 mL), adding into a three-port bottle, maintaining the temperature at 0-10 ℃, dropwise adding a dichloromethane mixed solution of DCC (7 g,34 mmol) after half an hour, heating to room temperature, reacting for 4 hours, filtering the reaction solution, spinning, adding toluene to dissolve the product, performing column chromatography to obtain pale yellow liquid, spinning the reaction solution, recrystallizing the product isopropanol and toluene for 1 time to obtain intermediate 8 (10.1 g,10.3 mmol), and obtaining the yield of 66.8%;
step 8: 2-benzothiazole hydrazine (5 g,30 mmol) and(4.9 g,36 mmol) in DMF (50 mL) is added into a three-mouth bottle, potassium carbonate (4.9 g,36 mmol) is added, the temperature is raised to 80 ℃, the reaction is carried out for three hours under the heat preservation, the temperature is reduced, the reaction liquid is poured into ice water, the reaction liquid is filtered, the toluene and ethanol of a filter cake are recrystallized, and the product intermediate 9 (7.4 g,22.5 mmol) is obtained, and the yield is 83%;
step 9: adding intermediate 9 (8.9 g,30 mmol), (±) -10-camphorsulfonic acid (1.4 g,6 mmol), tetrahydrofuran (100 mL), ethanol (100 mL) and intermediate 8 (24.5 g,25 mmol) into a three-necked flask, heating to 60 ℃, preserving heat for reaction for 6 hours, cooling, rotary steaming to remove solvent, pulping with isopropanol, and performing column chromatography to obtain I-a-4 (20.1 g,16.4 mmol), wherein the yield is 66%;
example 3
Preparing a compound shown in a formula I-b-2, wherein the structural formula is as follows,
the synthetic route is as follows:
the specific synthesis steps are as follows:
step 1: the terephthalyl ether (13.8 g,0.1 mol) and cyclopropylcarbonyl chloride (12.5 g,0.12 mol) were dissolved in DCM (200 mL) and added to a three-necked flask, cooled to 0deg.C and AlCl was added 3 (17.4 g,0.13 mol), reacting for 3 hours under heat preservation, pouring into water, separating liquid, extracting water phase with DCM, spin-drying an organic phase, adding toluene into a crude product, passing through a silica gel column, evaporating solvent to obtain white solid, and pulping petroleum ether to obtain an intermediate 1 (17 g,0.08 mol), wherein the yield is 82.5%;
step 2: intermediate 1 (17 g,0.08 mol) was dissolved in DCM (200 mL) and added to a three-necked flask, cooled to 0deg.C, and BBr was slowly added dropwise 3 (40 g,0.16 mol) for 3 hours under heat preservation, pouring the mixture into water, separating liquid, extracting the water phase by DCM, concentrating and spin-drying to obtain brown solid, and pulping the product by petroleum ether to obtain intermediate 2 (12.1 g,0.068 mol) with the yield of 85%;
step (a)3: intermediate 3(59.4 g,0.15 mol) and intermediate 2 (12.1 g,0.068 mol) are dissolved in DMF (100 mL) and then added into a three-necked flask, potassium carbonate (20.7 g,0.15 mol) is added, the mixture is heated to 80 ℃, the temperature is kept for 3 hours, the reaction is reduced, the temperature is reduced, the reaction solution is filtered, toluene is added into a filter cake, a silica gel column is used for obtaining pale yellow liquid, the solvent is evaporated, and petroleum ether is used for pulping products, thus obtaining intermediate 4 (39 g,0.05 mol) with the yield of 74%;
step 4: benzothiazole hydrazine (5 g,30 mmol) and(4.9 g,36 mmol) was dissolved in DMF (50 mL) and added into a three-necked flask, potassium carbonate (4.9 g,36 mmol) was added, the temperature was raised to 80 ℃, the reaction was carried out for three hours under heat preservation, the temperature was lowered, the reaction solution was poured into ice water, the reaction solution was filtered, and toluene and ethanol as a filter cake were recrystallized to obtain a product intermediate 5 (6.7 g,22.5 mmol) in 75% yield;
step 5: intermediate 5 (8.9 g,30 mmol), (±) -10-camphorsulfonic acid (1.4 g,6 mmol), tetrahydrofuran (100 mL), ethanol (100 mL) and intermediate 4 (19.5 g,25 mmol) are put into a three-necked flask, the temperature is raised to 60 ℃, the reaction is carried out for 6 hours under the heat preservation, the temperature is reduced, the solvent is removed by rotary evaporation, isopropanol is beaten, and the product intermediate 6 (15.8 g,15 mmol) is obtained by column chromatography, and the yield is 60%;
step 6: intermediate 6 (10.6 g,10 mmol) was dissolved in 100mL toluene and added to a three-necked flask, p-toluenesulfonic acid (0.17 g,1 mmol) and acrylic acid (1.44 g,20 mmol) were added, heated to reflux, the reflux reaction was carried out for 4 hours, the temperature was lowered, the reaction solution was poured into water, dichloromethane extraction, water washing, spin drying, toluene column chromatography of the product, and toluene ethanol recrystallization gave (5.3 g,5 mmol) of the compound of formula I-b-2 in 50% yield.
Example 4
Preparing a compound shown in a formula I-c-6, wherein the structural formula is as follows,
the synthetic route is as follows:
the specific synthesis steps are as follows:
step 1: will be(59.4 g,0.15 mol) and(12.1 g,0.068 mol) is dissolved in DMF (100 mL) and then added into a three-mouth bottle, then potassium carbonate (20.7 g,0.15 mol) is added, the temperature is kept for 3 hours, the reaction is reduced, the temperature is reduced, the reaction liquid is filtered, toluene is added into a filter cake and passes through a silica gel column, light yellow liquid is obtained, the solvent is evaporated, petroleum ether is pulped to obtain an intermediate 1 (39 g,0.05 mol) with the yield of 74%;
step 2: benzothiazole hydrazine (5 g,30 mmol) and(4.9 g,36 mmol) was dissolved in DMF (50 mL) and added into a three-necked flask, potassium carbonate (4.9 g,36 mmol) was added, the temperature was raised to 80 ℃, the reaction was carried out for three hours under heat preservation, the temperature was lowered, the reaction solution was poured into ice water, the reaction solution was filtered, and toluene and ethanol as a filter cake were recrystallized to obtain product intermediate 2 (6.7 g,22.5 mmol) in 75% yield;
step 3: intermediate 2 (8.9 g,30 mmol), (+ -.) -10-camphorsulfonic acid (1.4 g,6 mmol), tetrahydrofuran (100 mL), ethanol (100 mL) and intermediate 1 (19.5 g,25 mmol) were put into a three-necked flask, heated to 60℃and reacted for 6 hours with heat preservation, cooled, the solvent was removed by rotary evaporation, isopropanol was beaten, and column chromatography was performed to obtain I-c-6 (15.8 g,15 mmol) with a yield of 60%.
The compounds represented by the formulas I-a-4, I-b-2 and I-c-6 described in examples 2 to 4 and the compounds represented by the formulas R-1, R-2 and R-3 described in patent document 1 were evaluated for the maximum solubility and other properties.
The evaluation method of the maximum solubility is as follows: a liquid crystal composition is selected as a mother liquid crystal, and 5 to 25% of a compound is added to the mother liquid crystal at a mass percentage content of 5% respectively. Examples of adding the compound of formula I-a-4 as example 5, adding the compound of formula I-b-2 as example 6, adding the compound of formula I-c-6 as example 7, adding the compound of formula R-1 as comparative example 1, adding the compound of formula R-2 as comparative example 2, and adding the compound of formula R-3 as comparative example 3 were uniformly mixed and subjected to maximum solubility evaluation. And respectively placing the uniformly mixed evaluation objects of examples 5-7 and comparative examples 1-3 in an environment of 20+/-3 ℃ for 30 days, wherein the mass percentage content of the evaluation object with no crystal precipitation is the maximum solubility of the compound.
The mother liquid crystal comprises 30% of compound of formula Y-1, 30% of compound of formula Y-2 and 40% of compound of formula Y-3 by mass percentage.
Table 1: maximum solubility of examples 5-7 and comparative examples 1-3
| Evaluation object | Maximum solubility | |
| Example 5 | Formula I-a-4Composition | 25％ |
| Example 6 | Compounds of formula I-b-2 | 25％ |
| Example 7 | Compounds of formula I-c-6 | 25％ |
| Comparative example 1 | Compounds of formula R-1 | 20％ |
| Comparative example 2 | Compounds of formula R-2 | 25％ |
| Comparative example 3 | Compounds of formula R-3 | 20％ |
As is clear from Table 1, examples 5 to 7, which respectively include the compounds of the present invention represented by the formulas I-a-4, I-b-2 and I-c-6, have the same or higher maximum solubility than those represented by comparative examples 1 to 3, which respectively include the compounds represented by the formulas R-1, R-2 and R-3.
20% of the compound of the formula I-a-4 as example 8, 20% of the compound of the formula I-b-2 as example 9, 20% of the compound of the formula I-c-6 as example 10, 20% of the compound of the formula R-1 as comparative example 4, 20% of the compound of the formula R-2 as comparative example 5, 20% of the compound of the formula R-3 as comparative example 6, the photopolymerization initiator Irgacure907 (manufactured by BASF corporation) 1%, 4-methoxyphenol 0.1% andchloroform 80%, and a coating liquid was prepared. The coating liquid was applied to the rubbed glass substrate by spin coating. After drying at 80℃for 1 minute, further drying at 120℃for 1 minute was carried out. Then using a high pressure mercury lamp at 40mW/cm 2 Ultraviolet rays were irradiated for 25 seconds to produce a display unevenness evaluation target.
For the aforementioned display unevenness evaluating object, the degree of display unevenness was evaluated by observation with a polarizing microscope. 10 films each containing the compound to be evaluated for unevenness were produced, and the number of unevenness to be displayed was counted. The number of display irregularities observed in 10 films was counted up, and a is counted up when the number of display irregularities is 0, B is counted up when the number of display irregularities is 1, C is counted up when the number of display irregularities is 2 to 5, and D is counted up when the number of display irregularities is 6 or more. The evaluation results are shown in Table 2.
Table 2: evaluation results showing the degree of unevenness of examples 8 to 10 and comparative examples 4 to 6
| Evaluation object | Uneven display | |
| Example 8 | Compounds of formula I-a-4 | A |
| Example 9 | Compounds of formula I-b-2 | A |
| Example 10 | Compounds of formula I-c-6 | A |
| Comparative example 4 | Compounds of formula R-1 | A |
| Comparative example 5 | Compounds of formula R-2 | A |
| Comparative example 6 | Compounds of formula R-3 | A |
As is clear from Table 2, examples 8 to 10 using the compound of the present invention can obtain a degree of display unevenness which is as excellent as that of comparative examples 4 to 6 using the compound of the prior art.
Claims (7)
1. A polymerizable compound characterized by: the polymerizable compound is a compound shown in a formula I-b or a formula I-c,
in the formula I-b and the formula I-c, P 1 Each independently represents: or a hydrogen atom;
sp each independently represents a single bond, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, any one or more of which are not adjacent to each other, -CH 2 -optionally by-O-,-S-、-C(＝O)-、-CH 2 O-、-OCH 2 -C (=o) -O-, -O-C (=o) -, -ch=ch-C (=o) -O-, or, -O-C (=o) -ch=ch-substituted;
Q 11 each independently represents a cycloalkyl group having 3 to 20 carbon atoms, and a hydrogen atom on the cycloalkyl group having 3 to 20 carbon atoms is optionally substituted with halogen;
p' each independently representsOr->
Sp 11 、Sp 21 Each independently represents an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 4 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms, wherein one or more of them is not adjacent to-CH 2 -optionally substituted by-O-, any hydrogen atom being optionally substituted by a fluorine atom;
n and m each independently represent 1, 2 or 3.
2. The polymerizable compound according to claim 1, wherein the compound represented by the formula I-b is selected from the group consisting of compounds represented by the formulas I-b-2 to I-b-3, formulas I-b-5 to I-b-6, and formulas I-b-8 to I-b-9; the compound shown in the formula I-c is selected from the group consisting of compounds shown in the formulas I-c-2 to I-c-3 and the formulas I-c-5 to I-c-6,
3. a polymerizable composition comprising the polymerizable compound according to any one of claims 1 to 2.
4. The polymerizable composition according to claim 3, which exhibits a liquid crystal phase.
5. A polymer obtained by polymerizing the polymerizable compound according to any one of claims 1 to 2 or polymerizing the polymerizable composition according to claim 3 or 4.
6. An optically anisotropic body comprising the polymer according to claim 5.
7. A liquid crystal display device comprising the polymer according to claim 5 or the optically anisotropic body according to claim 6.
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