CN110628440B - Wide-temperature-range blue-phase liquid crystal material and preparation method thereof - Google Patents

Wide-temperature-range blue-phase liquid crystal material and preparation method thereof Download PDF

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CN110628440B
CN110628440B CN201810643892.5A CN201810643892A CN110628440B CN 110628440 B CN110628440 B CN 110628440B CN 201810643892 A CN201810643892 A CN 201810643892A CN 110628440 B CN110628440 B CN 110628440B
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liquid crystal
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blue phase
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crystal material
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杨槐
胡威
王萌
张兰英
钟廷珺
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Peking University
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters

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Abstract

The invention belongs to the technical field of liquid crystal materials. In particular to a blue phase liquid crystal material, which comprises: component A, component B, component C and component D. The component A comprises a double liquid crystal elementary mixed liquid crystal material containing a biphenyl structure, and the basic structure of the material is that two rod-shaped liquid crystal segments are connected by a flexible carbon chain in the middle. The component B comprises a double liquid crystal elementary mixed liquid crystal material containing a terphenyl structure, and the basic structure of the material is that two rod-shaped liquid crystal segments are connected by a flexible carbon chain in the middle. The component C comprises a liquid crystal mixed material with a terphenyl structure, and the liquid crystal material has a high clearing point and high refractive index anisotropy. Component D comprises a chiral dopant for liquid crystals. By adopting the blue phase liquid crystal formula, the thermodynamic stability of the blue phase liquid crystal can be greatly improved by reasonably mixing the components A, B, C, D in different proportions, and the blue phase liquid crystal material with ultra-wide temperature range can be obtained.

Description

Wide-temperature-range blue-phase liquid crystal material and preparation method thereof
Technical Field
The invention belongs to the field of liquid crystal materials, and particularly relates to a wide-temperature-range blue-phase liquid crystal material and a preparation method thereof.
Background
Blue phase liquid crystal (BP) is a double-helical three-dimensional superstructure material, usually present in high chiral systems. The liquid crystal molecules are self-assembled to form a double-twisted cylinder with a double-helix structure under the twisting force provided by the chiral agent. According to different arrangement modes of the double-twisted cylinders, the blue phase can be roughly divided into three sub-phase states, namely body-centered cubic BP I, simple cubic BP II and irregular atomized phase BP III. Due to the complex three-dimensional structure of the blue phase, liquid crystal molecules have no average director on a macroscopic scale, and therefore, the blue phase liquid crystal has the characteristic of optical isotropy. However, the helical structure of the blue phase liquid crystal forms a periodic distribution of refractive index, resulting in bragg reflection. The Bragg reflection wavelengths of different crystal planes are different, so that a blue phase observed under a polarization microscope presents a color fragment structure.
Blue phase liquid crystals have many excellent optical characteristics, and have attracted more and more attention because of a series of special optical characteristics, such as the ability to selectively reflect visible light and the absence of birefringence, which is common in optics. The blue phase is a stable phase that often occurs in a very small temperature range near the clearing point of high chiral liquid crystal systems. In order to obtain the wide-temperature-range blue-phase liquid crystal, so that the blue-phase liquid crystal can be widely applied, the existing wide-temperature-range blue-phase liquid crystal technology can be mainly divided into two types. The first technique is to stabilize the defects of the blue phase liquid crystal to thereby stabilize the blue phase liquid crystal. For example, the documents Kikuchi H, Yokota M, Hisakado Y, Yang H, Kajiyama T,2002, nat. Mater.1,64 disclose a method for stabilizing the blue phase using a polymer, which yields a blue phase liquid crystal having a blue phase temperature width of up to 60 ℃ at room temperature. The second technology is to synthesize blue phase liquid crystal with wide temperature range through molecular design. For example, Coles HJ, Pivnecko MN, Nature,436(18),997. the synthesized fluorine-containing substituted dimer liquid crystal molecules are designed to have a wide blue phase temperature range of 44 ℃ inclusive of room temperature. Although the existing blue phase liquid crystal technology with wide temperature range solves the problem of wide and narrow blue phase temperature range of the blue phase liquid crystal to a certain extent, the blue phase temperature range of the existing blue phase liquid crystal system is widened and limited, and the blue phase temperature range can be adjusted only within the range of +/-30 ℃ of standard room temperature (25 ℃). That is, the existing blue phase liquid crystal cannot meet the application requirements in high environmental temperature areas and extreme low temperature environmental temperatures (such as high outdoor temperature areas in africa, high altitude environments and ultra-low temperature environments in high altitude areas such as north and south), so the application of the blue phase liquid crystal in extreme environmental temperature conditions is limited. Further intensive studies are required to further broaden the temperature range of the blue phase liquid crystal to a large extent.
Disclosure of Invention
The invention aims to provide a blue phase liquid crystal material which has an ultra-wide blue phase temperature range and completely covers the environmental temperature under extreme conditions.
Another object of the present invention is to provide a method for manufacturing a blue phase liquid crystal material with a wide temperature range, which is simple and has a significant effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a blue phase liquid crystal material, which comprises the following components in percentage by mass: the blue phase liquid crystal composite comprises a component A, a component B, a component C and a component D, wherein the total mass of the component A, the component B and the component C accounts for 50-95% of the total mass of the blue phase liquid crystal, and the total mass of the component D accounts for 5-50% of the total mass of the blue phase liquid crystal;
the component A comprises a double liquid crystal elementary mixed liquid crystal material containing a biphenyl structure, and the basic structure of the material is that two rod-shaped liquid crystal segments are connected by a flexible carbon chain in the middle;
the component B comprises a double liquid crystal elementary mixed liquid crystal material containing a terphenyl structure, and the basic structure of the material is that two rod-shaped liquid crystal segments are connected by a flexible carbon chain in the middle;
the component C comprises a liquid crystal mixed material with a terphenyl structure; such liquid crystal materials have a high clearing point and a high refractive index anisotropy.
Component D comprises a chiral dopant for liquid crystals.
Preferably, the mass ratio of the total mass of the component A and the component B to the mass of the component C is 1: 9-9: 1.
preferably, the mass ratio of the component A to the component B is 1: 9-9: 1.
preferably, the component A is prepared by mixing any one or more compounds shown in the following general formula in any proportion:
Figure BDA0001703057970000021
wherein n is 3, 5, 7, 9, 11, 13, R is F, CN or CmH2m+1And m is an integer of 1 to 9.
Preferably, the component B is prepared by mixing any one or more compounds shown in the following general formula in any proportion:
Figure BDA0001703057970000031
wherein n is 3, 5, 7, 9, 11, 13, R is F, CN or CmH2m+1And m is an integer of 1 to 9.
Preferably, the component C is prepared by mixing any one or more compounds shown in the following general formula in any proportion:
Figure BDA0001703057970000032
wherein, R group is F, CN or CmH2m+1And m is an integer of 1 to 9.
Preferably, the structures listed above are representative structural formulas and other similar structures derived from this invention are also within this invention.
Preferably, component D is prepared by mixing any one or more compounds shown in the following general formula in any proportion: preference for use with
Figure BDA0001703057970000033
Figure BDA0001703057970000041
Preferably, component D is not limited to these classes of chiral agents, and the use of other chiral agents is also within the scope of the invention.
The invention also provides a preparation method of the blue phase liquid crystal material, which comprises the following steps:
1) respectively heating the component A and the component B until the components A and B are clear, and then uniformly mixing the component A and the component B;
2) mixing the component C with the mixture obtained in the step 1), and heating until the mixture is clear to obtain a uniform mixture;
3) adding component D to the mixture obtained in step 2); mixing them, heating to clear and obtain uniform mixture;
4) filling the mixture obtained in the step 3) into a liquid crystal box, placing the liquid crystal box on a hot table, observing the liquid crystal phase state along with the temperature by using a polarizing microscope, and recording the change temperature of the liquid crystal phase state.
Preferably, when component A, component B or component C is a mixture, the mixture in each component is heated separately and then mixed, and then the mixed component (A, B or C) is mixed with the other components.
Compared with the prior art, the invention has the advantages that:
the blue phase parent liquid crystal obtained by the method provided by the invention before adding the chiral agent (component D) has a super-wide liquid crystal temperature range, so that the system has low requirements on the chiral agent, and a large number of chiral agents can be selected. The widest blue phase temperature range of the existing micromolecule blue phase system is less than 50 ℃, the blue phase temperature range of the polymer stabilizing system is not about 60 ℃, and the practical requirements of the blue phase liquid crystal material are difficult to completely meet.
The blue phase liquid crystal material with ultra-wide temperature range can be obtained by reasonably mixing the four components mentioned in the invention, the temperature of the thermodynamically stable blue phase can be adjusted between-195 ℃ and 100 ℃, and the widest temperature range of the stably existing blue phase can exceed 280 ℃. The blue phase liquid crystal material has wide temperature range, flexibility and adjustability and simple preparation method.
Detailed Description
The present invention will be further described with reference to the following specific examples.
According to the formula of the blue phase liquid crystal material, uniformly mixing all components in the formula to prepare a mixture;
1) in the formula of the liquid crystal material, a component A and a component B are respectively heated to be clear and then are uniformly mixed, wherein the mass ratio of the component A to the component B is 1: 9-9: 1;
2) in the formula of the liquid crystal material, heating a component C to be clear to obtain a uniform mixture, and then mixing a mixture of a component A and a component B with the component C, wherein the mass ratio of the total mass of the component A and the component B to the component C is 1: 9-9: 1.
3) in the formula of the liquid crystal material, the component A, the component B and the component C are mixed according to a certain proportion, and a certain amount of the component D is added into the mixture, wherein the mass of the component D accounts for 5-50% of the total mass of the blue phase liquid crystal. Wherein, the component D can use one chiral agent alone or a plurality of chiral agents in a mixed way.
4) Heating the materials to be clear, mixing uniformly, pouring the materials into a liquid crystal box, placing the liquid crystal box on a hot table, observing the liquid crystal phase on the hot table by using a polarizing microscope, observing the change of the liquid crystal phase along with the temperature, and recording the change temperature of the liquid crystal phase. According to different use requirements, the sample proportion with parameters suitable for application requirements is selected.
Example 1
All the components in the table are mixed according to a given mass ratio by the method, and the mixture is poured into a liquid crystal box after being heated and stirred uniformly to represent the liquid crystal phase state on a hot table through a polarizing microscope. From a polarizing microscope, the phase transition point from the blue phase to the clearing point of the formula in the table is 72.5 ℃, the phase transition temperature from the blue phase to the chiral nematic phase is-35.0 ℃, and the temperature range of the blue phase exceeds 100.0 ℃.
Table 1 lists only one blue phase liquid crystal material and the temperature range of the blue phase liquid crystal material prepared by the formulation, so as to illustrate the excellent properties and preparation method of the blue phase liquid crystal material in the invention.
Table 1 shows the formulation and blue phase temperature range of a sample of the blue phase liquid crystalline material of the present invention.
Figure BDA0001703057970000061
Figure BDA0001703057970000071
Example 2
All the components in the table are mixed according to a given mass ratio by the method, and the mixture is poured into a liquid crystal box after being heated and stirred uniformly to represent the liquid crystal phase state on a hot table through a polarizing microscope. From a polarizing microscope, the phase transition point from the blue phase to the clearing point of the formula in the table is 85.5 ℃, the phase transition temperature from the blue phase to the chiral nematic phase is-28.0 ℃, and the temperature range of the blue phase exceeds 110.0 ℃.
Table 2 lists only one blue phase liquid crystal material and the temperature range of the blue phase liquid crystal material prepared by the formulation, so as to illustrate the excellent properties and preparation method of the blue phase liquid crystal material in the invention.
Table 2 shows the formulation and blue phase temperature range of a sample of the blue phase liquid crystalline material of the present invention.
Figure BDA0001703057970000072
Figure BDA0001703057970000081
Figure BDA0001703057970000091
Example 3
All the components in the table are mixed according to a given mass ratio by the method, and the mixture is poured into a liquid crystal box after being heated and stirred uniformly to represent the liquid crystal phase state on a hot table through a polarizing microscope. The phase transition point from the blue phase to the clearing point of the formula in the table is 91.2 ℃, the phase transition temperature from the blue phase to the chiral nematic phase is lower than-70 ℃, and the temperature range of the blue phase is over 160.0 ℃ as observed by a polarizing microscope.
Table 3 lists only one blue phase liquid crystal material and the temperature range of the blue phase liquid crystal material prepared by the formulation, so as to illustrate the excellent properties and preparation method of the blue phase liquid crystal material in the invention.
Table 3 shows the formulation and blue phase temperature range of a sample of the blue phase liquid crystalline material of the present invention.
Figure BDA0001703057970000092
Figure BDA0001703057970000101
Figure BDA0001703057970000111
The present invention may be embodied in many different forms and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (2)

1. A blue phase liquid crystal material, comprising: a component A, a component B, a component C and a component D, wherein, in percentage by mass,
the component A is 20%
Figure FDA0002789078280000011
And 20% of
Figure FDA0002789078280000012
The component B is 10%
Figure FDA0002789078280000013
10% of
Figure FDA0002789078280000014
6% of
Figure FDA0002789078280000015
And 6% of
Figure FDA0002789078280000016
The component C is 5%
Figure FDA0002789078280000017
And 5% of
Figure FDA0002789078280000018
The component D is 8%
Figure FDA0002789078280000019
10% of
Figure FDA0002789078280000021
Alternatively, the first and second electrodes may be,
the component A is 15 percent
Figure FDA0002789078280000022
And 15% of
Figure FDA0002789078280000023
The component B is 10%
Figure FDA0002789078280000024
10% of
Figure FDA0002789078280000025
6% of
Figure FDA0002789078280000026
And 6% of
Figure FDA0002789078280000027
The component C is 10%
Figure FDA0002789078280000028
And 10% of
Figure FDA0002789078280000029
The component D is 8%
Figure FDA0002789078280000031
And 10% of
Figure FDA0002789078280000032
Alternatively, the first and second electrodes may be,
the component A is 16 percent
Figure FDA0002789078280000033
And 16% of
Figure FDA0002789078280000034
The component B is 10%
Figure FDA0002789078280000035
10% of
Figure FDA0002789078280000036
6% of
Figure FDA0002789078280000037
And 6% of
Figure FDA0002789078280000038
The component C is 5%
Figure FDA0002789078280000041
5% of
Figure FDA0002789078280000042
10% of
Figure FDA0002789078280000043
And 10% of
Figure FDA0002789078280000044
The component D is 3%
Figure FDA0002789078280000045
And 3% of
Figure FDA0002789078280000046
2. A method of preparing the blue phase liquid crystalline material of claim 1, the method comprising the steps of:
1) respectively heating the component A and the component B until the components A and B are clear, and then uniformly mixing the component A and the component B;
2) mixing the component C with the mixture obtained in the step 1), and heating until the mixture is clear to obtain a mixture;
3) adding component D to the mixture obtained in step 2); mixing them uniformly, heating to clear and obtain uniform mixture;
4) filling the mixture obtained in the step 3) into a liquid crystal box, placing the liquid crystal box on a hot table, observing the liquid crystal phase state along with the temperature by using a polarizing microscope, and recording the change temperature of the liquid crystal phase state.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2356629A (en) * 1999-10-04 2001-05-30 Merck Patent Gmbh Bimesogenic compounds and their use in flexoelectric liquid crystal devices
EP1477547A1 (en) * 2003-05-09 2004-11-17 MERCK PATENT GmbH Liquid crystalline medium and liquid crystal display
CN1934222A (en) * 2004-01-30 2007-03-21 陶氏康宁公司 Liquid crystal materials
CN102031121A (en) * 2009-09-29 2011-04-27 奇美电子股份有限公司 Liquid crystals composition and liquid crystal display
CN102443402A (en) * 2011-10-27 2012-05-09 北京科技大学 Preparation method for wide-temperature blue-phase liquid crystal composite material
CN103562347A (en) * 2011-06-01 2014-02-05 默克专利股份有限公司 Liquid crystal medium and liquid crystal display
CN106281359A (en) * 2015-06-04 2017-01-04 江苏和成显示科技股份有限公司 Liquid-crystal composition and display device thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2356629A (en) * 1999-10-04 2001-05-30 Merck Patent Gmbh Bimesogenic compounds and their use in flexoelectric liquid crystal devices
EP1477547A1 (en) * 2003-05-09 2004-11-17 MERCK PATENT GmbH Liquid crystalline medium and liquid crystal display
CN1934222A (en) * 2004-01-30 2007-03-21 陶氏康宁公司 Liquid crystal materials
CN102031121A (en) * 2009-09-29 2011-04-27 奇美电子股份有限公司 Liquid crystals composition and liquid crystal display
CN103562347A (en) * 2011-06-01 2014-02-05 默克专利股份有限公司 Liquid crystal medium and liquid crystal display
CN102443402A (en) * 2011-10-27 2012-05-09 北京科技大学 Preparation method for wide-temperature blue-phase liquid crystal composite material
CN106281359A (en) * 2015-06-04 2017-01-04 江苏和成显示科技股份有限公司 Liquid-crystal composition and display device thereof

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