Liquid crystalline polyrotaxane

Abstract

The present invention provides a liquid crystalline material having flexibility and/or bendability and a method for preparing the material. The present invention provides a liquid crystalline polyrotaxane consisting essentially of a polyrotaxane, wherein the polyrotaxane comprises a linear molecule, a cyclic molecule(s) in which the linear molecule is included in cavity (cavities) of the cyclic molecule(s) in a skewered manner, and capping groups, each of which locates at each end of the linear molecule in order to prevent the dissociation of the cyclic molecule (s); the cyclic molecule of the liquid crystalline polyrotaxane comprises a mesogenic group, e.g., biphenyl groups represented by following formulae (1) to (3), and the liquid crystalline polyrotaxane has liquid crystalline property.

Description

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph showing DSC curves of CNBP—C₅-APR obtained in Example 1 for the third cycle of rising and decreasing temperature and DSC curves of unmodified polyrotaxane, which is a raw material, for the second cycle of rising and decreasing temperature on the inside, as a comparative control;

FIG. 2 shows a polarized light microscope image of CNBP—C₅-APR obtained in Example 1 in the cycle of rising and decreasing temperature;

FIG. 3 is a graph showing DSC curves of CNBP-(EO)₂-APR obtained in Example 2 for the second cycle of rising and decreasing temperature and DSC curves of unmodified polyrotaxane, which is a raw material, for the second cycle of rising and decreasing temperature on the inside similarly as in FIG. 1, as a control; and

FIG. 4 shows a polarized light microscope image of CNBP-(EO)₂-APR obtained in Example 2 in the cycle of rising and decreasing temperature.

Claims

1. A liquid crystalline polyrotaxane consisting essentially of a polyrotaxane, wherein the polyrotaxane comprises a linear molecule, a cyclic molecule(s) in which the linear molecule is included in cavity (cavities) of the cyclic molecule(s) in a skewered manner, and capping groups, each of which locates at each end of the linear molecule in order to prevent the dissociation of the cyclic molecule(s)the cyclic molecule of the liquid crystalline polyrotaxane comprises a mesogenic group, andthe liquid crystalline polyrotaxane has liquid crystalline property.

2. The liquid crystalline polyrotaxane according to claim 1, wherein the mesogenic group is represented by the formula A-X—B—C—Y— wherein A and B are 6-membered rings; C is a single bond or a liner chain group; and X and Y are bonding groups.

3. The liquid crystalline polyrotaxane according to claim 2, wherein the 6-membered rings of A and B each independently represents a saturated or unsaturated homo- or heterocycle, which may be substituted.

4. The liquid crystalline polyrotaxane according to claim 2, wherein C has a linear chain consisting of 0 to 100 elements.

5. The liquid crystalline polyrotaxane according to claim 3, wherein C has a linear chain consisting of 0 to 100 elements.

6. The liquid crystalline polyrotaxane according to claim 2, wherein X is selected from the group consisting of a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, —CH═N—, —CH═CH— and —C≡C—.

7. The liquid crystalline polyrotaxane according to claim 2, wherein Y is selected from the group consisting of a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NH—CO—, —CO—NH—, —NH—CO—O— and —O—CO—NH—.

8. The liquid crystalline polyrotaxane according to claim 2, wherein A-X—B— is selected from the group consisting of D-1 to D-20 wherein R1 to R20 each independently represents a substituent:

9. The liquid crystalline polyrotaxane according to claim 1, wherein the mesogenic group represents any one of biphenyl substituents represented by following formulae 1 to 3, wherein n is an integer of 1 to 20; m is an integer of 1 to 10; R21, R23 and R25 each independently represents 0 to 5 substituents; and R22, R24 and R26 each independently represents 0 to 4 substituents:

10. The liquid crystalline polyrotaxane according to claim 9, wherein the biphenyl substituent is represented by the formula 1, wherein R21 has one substituent which is a cyano group in p-position, and R22 has no substituent.

11. The liquid crystalline polyrotaxane according to claim 9, wherein the biphenyl substituent is represented by the formula 2, wherein n is an integer of 2 to 10, R23 has one substituent which is a cyano group in p-position, and R24 has no substituent.

12. The liquid crystalline polyrotaxane according to claim 9, wherein the biphenyl substituent is represented by the formula 3, wherein m is an integer of 1 to 5, R25 has one substituent which is a cyano group in p-position, and R26 has no substituent.

13. The liquid crystalline polyrotaxane according to claim 1, wherein the linear molecule is selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, poly(meth) acrylic acid, cellulose-based resins, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal-based resins, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and the like and/or copolymers thereof, polyolefin-based resins such as polyethylene, polypropylene, and copolymer resins with other olefinic monomers, polyester resins, polyvinyl chloride resins, polystyrene-based resins, acrylic resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resin, polyvinylbutyral resin and the like; and derivatives and modifications thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon and the like, polyimides, polydienes such as polyisoprene, polybutadiene and the like, polysiloxanes such as polydimethylsiloxane and the like, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof.

14. The liquid crystalline polyrotaxane according to claim 1, wherein the linear molecule has a molecular weight of 500 or more.

15. The liquid crystalline polyrotaxane according to claim 1, wherein the capping group is selected from the group consisting of dinitrophenyl groups; cyclodextrins; adamantane groups; trityl groups; fluoresceins; pyrenes; substituted benzenes; polycyclic aromatics which may be substituted; and steroids.

16. The liquid crystalline polyrotaxane according to claim 1, wherein the cyclic molecule is a cyclodextrin molecule which may be substituted.

17. The liquid crystalline polyrotaxane according to claim 1, wherein the cyclic molecule is a cyclodextrin molecule which may be substituted, and the cyclodextrin molecule is selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, and derivatives thereof.

18. The liquid crystalline polyrotaxane according to claim 1, wherein the cyclic molecule is α-cyclodextrin which may be substituted, and the linear molecule is polyethylene glycol.

19. The liquid crystalline polyrotaxane according to claim 1, wherein the linear molecule may have the cyclic molecule included in a skewered manner at an amount of 0.01 to 0.99 of a maximum inclusion amount, which is defined as an amount at which the cyclodextrin molecule can be included at maximum when the linear molecule has the cyclic molecules included in a skewered manner, and the amount at maximum is normalized to be 1.

20. The liquid crystalline polyrotaxane according to claim 1, which is used for at least one selected from the group consisting of materials for display, display elements, recording materials, lithium ion cells, fuel cells, solar cells, actuator, electric double layer capacitors, light-emitting devices, electrochromism elements, sensors, ionics circuits, polyelectrolyte, electrochemical materials, catalysts, separation membranes, and coating agents.

21. A method for preparing a liquid crystalline polyrotaxane consisting essentially of polyrotaxanes and exhibiting liquid crystallinity, comprising the steps of: a) mixing a cyclic molecule(s) and a linear molecule to make the linear molecule being included in the cyclic molecule (s) in a skewered manner; andb) capping each end of the linear molecule with a capping group to prevent the dissociation of the cyclic molecule(s) from the linear molecule, to prepare the polyrotaxane;

22. The method according to claim 21, wherein step (c) is conducted at the timing (v) after step b).