JP2002020483A - Optically active liquid crystal polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically active liquid crystal polymer compound which exhibits liquid crystal properties singly or by adding it to a liquid crystal compound or a liquid crystal composition. SOLUTION: A polymer compound consisting of basic units of formula (I) can reveal a liquid crystal phase over a wide temperature range and can be easily produced industrially. It is therefore very useful for a phase compensation film, a cholesteric film, a pitch modifier for a nematic liquid crystal, a polymer dispersion type liquid crystal, a molecular ferroelectric liquid crystal, and optical isomer separation column chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optically active polymer compound having a liquid crystal skeleton, which is useful as a functional material.

[0002]

2. Description of the Related Art Optically active liquid crystal polymers are used in applications such as retardation compensation films, cholesteric films, pitch adjusting agents for nematic liquid crystals, polymer dispersed liquid crystals, molecular ferroelectric liquid crystals, and optical isomer separation column chromatography. Although expected, in particular, liquid crystal polymers having an optically active polymer main chain have few synthetic methods, and examples thereof are not so many. The present inventors have already developed that an optically active polyketone compound can be easily synthesized by reacting an olefin compound with carbon monoxide in the presence of an optically active palladium catalyst (J. Am. Chem. Soc. , 119,
12779 (1997)). However, a compound into which a functional group exhibiting liquid crystallinity has been introduced has not been produced.

[0003]

SUMMARY OF THE INVENTION The present invention exhibits liquid crystallinity alone.
Another object is to provide a liquid crystal material having a functionality by producing an optically active polymer compound exhibiting liquid crystallinity by adding the compound to a liquid crystal compound or a liquid crystal composition.

[0004]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above problems, an olefin compound having a structure corresponding to a liquid crystal core is reacted with carbon monoxide in the presence of an optically active palladium catalyst. As a result, optically active polymers can be easily produced, and moreover, they have been found to exhibit liquid crystallinity over a wide temperature range, and the present invention has been completed.

That is, the present invention provides a compound represented by the general formula (I)

[0006]

Embedded image

(Wherein X is a group in which 1 to 10 non-adjacent methylene groups may be substituted with an oxygen atom, 1 to 10 methylene groups may be substituted with a dimethylsilylene group, and Represents a saturated or unsaturated alkylene group having 1 to 20 carbon atoms, wherein the linking group L ¹ is a single bond, -O-, -S-, -COO-,-
Represents OCO, -COS- or -SCO-, and has linking groups L ² , L ³ and L ⁴
It represents a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - CH (CH 3) CH 2 -, - CH 2 C
H (CH ₃ )-, -CH (CH ₃ ) CH (CH ₃ )-, -CF ₂ CF _2- , -CF = CF-, -CH ₂
O-, -OCH _2- , -OCH (CH ₃ )-, -CH (CH ₃ ) O-, -C≡C-, -CF ₂ O
_{-, - OCF 2 -, -} COO -, - OCO -, - COS- or an -SCO-, Z
Is hydrogen, fluorine, chlorine, bromine, iodine, cyano, cyanato, trifluoromethyl,
It may be substituted by a trifluoromethoxy group, a difluoromethoxy group, a hydroxyl group, a carboxyl group, or 1 to 20 fluorine atoms or an alkoxyl group having 1 to 20 carbon atoms, and may contain a saturated or unsaturated group which may contain a branched chain. Represents a saturated alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkanoyloxy group or an alkoxycarbonyl group, and ring A, ring B, ring C and ring D each independently represent a trans-1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, trans-decahydronaphthalene-
2,4-diyl group, trans-1,3-dioxane-2,4-diyl group, or 1,4-optionally substituted with 1 to 4 fluorine atoms
Phenylene group, pyridine-2,5-diyl group which may be substituted by one or two fluorine atoms, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6- Diyl group, and naphthalene-2,6-diyl group which may be substituted with 1 to 6 fluorine atoms, tetrahydronaphthalene-2,6-diyl group which may be substituted with 1 to 3 fluorine atoms, decahydronaphthalene Represents a -2,6-diyl group, m represents 0 or 1, and n ¹
To n ³ each independently represent 0 or 1. The carbons marked with * represent chiral asymmetric carbons. A polymer compound having a structure represented by the formula (1) as a basic unit is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, in a polymer compound having a structure represented by the above general formula (I) as a basic unit, X ¹ , L ^{1 to} L ⁴ , ring A to ring D and Z are Are as follows.

X represents -CH ₂ -,-(CH ₂ ) ₂ -,-(CH ₂ ) _3- ,
_{- (CH 2) 4 -,} - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH 2) 8 -,
-(CH ₂ ) ₉ -,-(CH ₂ ) ₁₀ -,-(CH ₂ ) ₁₁ -,-(CH ₂ ) ₁₂ -,-(CH ₂ )
₁₃ -,-(CH ₂ ) ₁₄ -,-(CH ₂ ) ₁₅ -,-(CH ₂ ) ₁₆ -,-(CH ₂ ) _17- and other straight-chain saturated alkylene groups,

-CHMe-, -CH ₂ -CHMe-,-(CH ₂ ) ₂ -CHMe-,-(C
H ₂ ) ₃ -CHMe-,-(CH ₂ ) ₄ -CHMe-,-(CH ₂ ) ₅ -CHMe-,-(CH ₂ ) _6-
CHMe-,-(CH ₂ ) ₇ -CHMe-,-(CH ₂ ) ₈ -CHMe-,-(CH ₂ ) ₉ -CHMe
-, -CHMe-CH _2- , -CHMe- (CH ₂ ) _2- , -CHMe- (CH ₂ ) _3- , -CHMe
_{- (CH 2) 4 -,} - CHMe- (CH 2) 5 -, - CHMe- (CH 2) 6 -, - CHMe- (C
_{H 2) 7 -, - CHMe-} (CH 2) 8 -, - CHMe- (CH 2) 9 - branched saturated alkylene group such as,

-CH = CH-, -CH ₂ -CH = CH-,-(CH ₂ ) ₂ -CH = CH-,
-(CH ₂ ) ₃ -CH = CH-,-(CH ₂ ) ₄ -CH = CH-,-(CH ₂ ) ₅ -CH = CH-,-
(CH ₂ ) ₆ -CH = CH-,-(CH ₂ ) ₇ -CH = CH-,-(CH ₂ ) ₈ -CH = CH-,-(C
H ₂ ) ₉ -CH = CH-,-(CH ₂ ) ₁₀ -CH = CH-,-(CH ₂ ) ₁₁ -CH = CH-,-(C
H ₂ ) ₁₂ -CH = CH-,-(CH ₂ ) ₁₃ -CH = CH-,-(CH ₂ ) ₁₄ -CH = CH- or other unsaturated alkylene group,

-O-CH_Two-, -O- (CH_Two)_Two-, -O- (CH_Two)_Three-, -O- (C
H_Two)_Four-, -O- (CH_Two)_Five-, -O- (CH_Two)₆-, -O- (CH_Two)₇-, -O- (C
H_Two)₈-, -O- (CH_Two)₉-, -O- (CH_Two)_Ten-, -O- (CH_Two)₁₁-, -O- (C
H_Two)₁₂-, -O- (CH_Two)₁₃-, -O- (CH_Two)₁₄-, -O- (CH_Two)_Fifteen-, -O-
(CH_Two)₁₆-, -O- (CH_Two)₁₇-, -CH_Two-O-CH_Two-, -CH_Two-O- (CH_Two)
_Two-, -CH_Two-O- (CH_Two)_Three-, -CH_Two-O- (CH_Two)_Four-, -CH_Two-O- (CH_Two)
_Five-, -CH_Two-O- (CH_Two)₆-, -CH_Two-O- (CH_Two)₇-, -CH_Two-O- (CH_Two)
₈-, -CH_Two-O- (CH_Two)₉-, -CH_Two-O- (CH _Two)_Ten-, -CH_Two-O- (CH_Two)
₁₁-, -CH_Two-O- (CH_Two)₁₂-, -CH_Two-O- (CH_Two)₁₃-, -CH_Two-O- (C
H_Two)₁₄-, -CH_Two-O- (CH_Two)_Fifteen-, -CH_Two-O- (CH_Two)₁₆-, -CH_Two-O-
(CH_Two)₁₇-,-(CH_Two)_Two-O-CH_Two-,-(CH_Two)_Two-O- (CH_Two)_Two-,-(C
H_Two)_Two-O- (CH_Two)_Three-,-(CH_Two)_Two-O- (CH_Two)_Four-,-(CH_Two)_Two-O- (CH_Two)
_Five-,-(CH_Two)_Two-O- (CH_Two)₆-,-(CH_Two)_Two-O- (CH_Two)₇-,-(CH_Two)_Two-
O- (CH_Two)₈-,-(CH_Two)_Two-O- (CH _Two)₉-,-(CH_Two)_Two-O- (CH_Two)_Ten-,
-(CH_Two)_Two-O- (CH_Two)₁₁-,-(CH_Two)_Two-O- (CH_Two)₁₂-,-(CH_Two) _Two-O-
(CH_Two)₁₃-,-(CH_Two)_Two-O- (CH_Two)₁₄-,-(CH_Two)_Two-O- (CH_Two)_Fifteen-,
-(CH_Two)_Two-O- (CH_Two)₁₆-, -O- (CH_Two)_Two-O- (CH_Two)_Two-, -O- (CH_Two)_Two
-O- (CH_Two)_Two-O- (CH_Two)_Two-, -O- (CH_Two)_Two-O- (CH_Two)_Two-O- (CH_Two)_Two-O
-(CH_Two)_TwoAn oxygen-containing alkylene group such as-

[0013] -SiMe_Two-CH_Two-, -SiMe_Two-(CH_Two)_Two-, -SiMe_Two-(C
H_Two)_Three-, -SiMe_Two-(CH_Two)_Four-, -SiMe_Two-(CH_Two)_Five-, -SiMe_Two-(C
H_Two)₆-, -SiMe_Two-(CH_Two)₇-, -SiMe_Two-(CH_Two)₈-, -SiMe_Two-(C
H_Two)₉-, -SiMe_Two-(CH_Two)_Ten-, -SiMe_Two-(CH_Two)₁₁-, -SiMe_Two-(C
H_Two)₁₂-, -SiMe_Two-(CH_Two)₁₃-, -SiMe_Two-(CH_Two)₁₄-, -SiMe_Two-
(CH_Two)_Fifteen-, -SiMe_Two-(CH_Two)₁₆-, -SiMe_Two-(CH_Two)₁₇-, -CH_Two-S
iMe_Two-CH_Two-, -CH_Two-SiMe_Two-(CH_Two)_Two-, -CH_Two-SiMe_Two-(CH_Two)
_Three-, -CH_Two-SiMe_Two-(CH_Two)_Four-, -CH_Two-SiMe_Two-(CH_Two)_Five-, -CH_Two-S
iMe_Two-(CH_Two)₆-, -CH_Two-SiMe_Two-(CH_Two)₇-, -CH_Two-SiMe_Two-(CH_Two)
₈-, -CH_Two-SiMe_Two-(CH_Two)₉-, -CH_Two-SiMe_Two-(CH_Two)_Ten-, -CH_Two-
SiMe_Two-(CH_Two)₁₁-, -CH_Two-SiMe_Two-(CH_Two)₁₂-, -CH_Two-SiMe_Two-(C
H_Two)₁₃-, -CH_Two-SiMe_Two-(CH_Two)₁₄-, -CH_Two-SiMe_Two-(CH_Two)_{1 Five}-,
-CH_Two-SiMe_Two-(CH_Two)₁₆-, -CH_Two-SiMe_Two-(CH_Two)₁₇-,-(CH_Two)_Two-
SiMe_Two-CH_Two-,-(CH_Two) _Two-SiMe_Two-(CH_Two)_Two-,-(CH_Two)_Two-SiMe_Two-
(CH_Two)_Three-,-(CH_Two)_Two-SiMe_Two-(CH_Two)_Four-,-(CH_Two)_Two-SiMe_Two-(C
H_Two)_Five-,-(CH_Two)_Two-SiMe_Two-(CH_Two)₆-,-(CH_Two)_Two-SiMe_Two-(CH_Two)₇
-,-(CH_Two)_Two-SiMe _Two-(CH_Two)₈-,-(CH_Two)_Two-SiMe_Two-(CH_Two)₉-,-
(CH_Two)_Two-SiMe_Two-(CH_Two)_Ten-,-(CH_Two)_Two-SiMe_Two-(CH_Two)₁₁-,-(C
H_Two)_Two-SiMe_Two-(CH_Two)₁₂-,-(CH_Two)_Two-SiMe_Two-(CH_Two)₁₃-,-(C
H_Two)_Two-SiMe_Two-(CH_Two)₁₄-,-(CH_Two)_Two-SiMe_Two-(CH_Two)_Fifteen-,-(C
H_Two)_Two-SiMe_Two-(CH_Two)₁₆-, -SiMe_Two-(CH_Two)_Two-SiMe_Two-(CH_Two)_Two-,
-SiMe_Two-(CH_Two)_Two-SiMe_Two-(CH_Two)_Two-SiMe_Two-(CH_Two)_Two-, -SiMe_Two-
(CH_Two)_Two-SiMe_Two-(CH_Two)_Two-SiMe_Two-(CH_Two)_Two-SiMe_Two-(CH_Two)_Two-, -S
iMe_Two-O-SiMe_Two-, -SiMe_Two-O-SiMe_Two-O-SiMe_Two-, -SiMe_Two-O-S
iMe_Two-O-SiMe_Two-O-SiMe_Two-Silicon-containing alkylene group such as-
But a straight-chain saturated alkylene group and a branched saturated alkylene group.
Alkylene groups and oxygen-containing alkylene groups are preferred, and linear
Saturated alkylene groups are particularly preferred.

The linking group L ¹ is a single bond, -O-, -S-, -COO-, -OC
O, -COS- or -SCO-, but a single bond, -O-,-
COO- or -OCO- is preferred.

The linking groups L ² , L ³ and L ⁴ are a single bond, —CH ₂ CH
_{2 -, - CH = CH -} , - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CH (CH 3) C
H (CH ₃ )-, -CF ₂ CF _2- , -CF = CF-, -CH ₂ O-, -OCH _2- , -OCH (C
H ₃ )-, -CH (CH ₃ ) O-, -C≡C-, -CF ₂ O-, -OCF _2- , -COO-,-
OCO -, - COS- or -SCO- but are mentioned, a single bond, -CH ₂
CH _2- , -CF = CF-, -CH ₂ O-, -OCH _2- , -C≡C-, -COO- or
-OCO- is preferred, and a single bond, -C≡C-, -COO- or -OCO-
Is particularly preferred.

The ring A to ring D include, for example, the structures shown in formula group 1.

[0017]

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Z is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a cyanato group, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group, a hydroxy group, a carboxyl group, or
A saturated or unsaturated C 1-20 alkyl group which may be substituted with up to 20 fluorine atoms or an alkoxyl group having 1 to 20 carbon atoms and which may contain a branched chain;
Represents an alkoxyl group, an alkanoyloxy group or an alkoxycarbonyl group, wherein the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Straight-chain saturated alkyl of hexyl, peptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl Group,

A 1-methylethyl group, a 1-methylpropyl group,
2-methylpropyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group,
2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2- Dimethylpentyl group, 1,3-dimethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,2-dimethylheptyl Group, 1,3-dimethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl Group, 1,2-dimethyloctyl group, 1,3-dimethyloctyl group 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, 5-methylnonyl group, 6-methylnonyl group, 7-methylnonyl group, 8-methylnonyl branched saturated alkyl group such as a group,

Vinyl group, trans-1-propenyl group, 2-
Propenyl group, trans-1-butenyl group, trans-2-butenyl group, cis-2-butenyl group, 3-butenyl group, trans-1-pentenyl group, trans-2-pentenyl group, cis-2
-Pentenyl group, trans-3-pentenyl group, 4-pentenyl group, trans-1-hexenyl group, trans-2-hexenyl group, cis-2-hexenyl group, trans-3-hexenyl group, trans-4-hexenyl group , Cis-4-hexenyl group,
5-hexenyl group, trans-1-heptenyl group, trans-
2-heptenyl group, cis-2-heptenyl group, trans-3-heptenyl group, trans-4-heptenyl group, cis-4-heptenyl group, trans-5-heptenyl group, 6-heptenyl group,
Trans-1-octenyl group, trans-2-octenyl group,
Cis-2-octenyl group, trans-3-octenyl group, trans-4-octenyl group, cis-4-octenyl group, trans
-5-octenyl group, trans-6-octenyl group, 7-octenyl group, trans-1-nonenyl group, 8-nonenyl group, trans-1-decenyl group, 9-decenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 1-heptynyl group, 2-heptynyl group, 3-heptynyl group, 4-heptynyl group, 5-heptynyl group, 6-heptynyl group, 1-octynyl group, 2-octynyl group, 3-octynyl group, 4-octynyl group, 5-octynyl group, 6-octynyl group, 7-octynyl group, 1-noninyl group,
8-noninyl group, 1-decynyl group, unsaturated alkyl group such as 9-decynyl group,

A fluoromethyl group, a difluoromethyl group,
Trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,
2,2-pentafluoroethyl group, 3-fluoropropyl group,
2-fluoropropyl group, 1-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group,
2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4-fluoro Butyl group, 3-fluorobutyl group,
2-fluorobutyl group, 1-fluorobutyl group, 4,4-difluorobutyl group, 4,4,4-trifluorobutyl group, 3,3,4,4-
Tetrafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 5-fluoropentyl group, 4-fluoropentyl group , 3-fluoropentyl, 2-fluoropentyl, 1-fluoropentyl, 5,5-difluoropentyl, 5,5,5-trifluoropentyl, 4,4,5,5-tetrafluoropentyl , 4,4,
5,5,5-pentafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 6-fluorohexyl group, 5-fluorohexyl group, 4-fluorohexyl group, 3- Fluorohexyl group, 2-fluorohexyl group, 1-fluorohexyl group, 6,6-difluorohexyl group, 6,6,6-trifluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 4,4,
5,5,6,6-heptafluorohexyl group, 7-fluoroheptyl group, 6-fluoroheptyl group, 5-fluoroheptyl group, 4-fluoroheptyl group, 3-fluoroheptyl group, 2-
Fluoroheptyl group, 1-fluoroheptyl group, 7,7-difluoroheptyl group, 7,7,7-trifluoroheptyl group, 6,
6,7,7-tetrafluoroheptyl group, 6,6,7,7,7-pentafluoroheptyl group, 5,5,6,6,7,7,7-heptafluoroheptyl group, 8-fluorooctyl group , 7-fluorooctyl group, 6-fluorooctyl group, 5-fluorooctyl group, 4-
Fluorooctyl group, 3-fluorooctyl group, 2-fluorooctyl group, 1-fluorooctyl group, 8,8-difluorooctyl group, 8,8,8-trifluorooctyl group, 7,7,8,8-
A fluorine-substituted alkyl group such as a tetrafluorooctyl group, a 7,7,8,8,8-pentafluorooctyl group, a 6,6,7,7,8,8,8-heptafluorooctyl group,

2,2-difluoroethenyl group, (E) -1,2-difluoroethenyl group, (Z) -1,2-difluoroethenyl group, 3,2
3-difluoro-2-propenyl group, (E) -2,3-difluoro-2-
Propenyl group, (Z) -2,3-difluoro-2-propenyl group,
4,4-difluoro-3-butenyl group, (E) -3,4-difluoro-3-
Butenyl group, (Z) -3,4-difluoro-3-butenyl group, 5,5-
Difluoro-4-pentenyl group, (E) -4,5-difluoro-4-pentenyl group, (Z) -4,5-difluoro-4-pentenyl group, 6,6
-Difluoro-5-hexenyl group, (E) -5,6-difluoro-5-
Hexenyl group, (Z) -5,6-difluoro-5-hexenyl group,
(E) -1,2-difluoro-1-propenyl group, (E) -1,2-difluoro-1-butenyl group, (E) -1,2-difluoro-1-pentenyl group, (E) -1 , 2-difluoro-1-hexenyl group, (Z) -1-fluoro-1-propenyl group, (Z) -1-fluoro-1-butenyl group,
(Z) -1-fluoro-1-pentenyl group, (Z) -1-fluoro-1-hexenyl group, (Z) -2-fluoro-1-propenyl group, (Z) -2-
Fluoro-1-butenyl group, (Z) -2-fluoro-1-pentenyl group, (Z) -2-fluoro-1-hexenyl group, (E) -2,3-difluoro-2-butenyl group, (E ) -2,3-difluoro-2-pentenyl group, (E) -2,3-difluoro-2-hexenyl group, (Z) -2-fluoro-2-butenyl group, (Z) -2-fluoro-2 -Pentenyl group,
(Z) -2-fluoro-2-hexenyl group, (Z) -3-fluoro-2-butenyl group, (Z) -3-fluoro-2-pentenyl group, (Z) -3-fluoro-2-hexenyl A fluorine-substituted unsaturated alkyl group such as a group,

Methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-ethoxy
Propoxyethyl group, 1-butoxyethyl group, 1-pentyloxyethyl group, 1-hexyloxyethyl group, 1-heptyloxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2 -Butoxyethyl group,
2-pentyloxyethyl group, 2-hexyloxyethyl group, 2-heptyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-propoxypropyl group,
1-butoxypropyl group, 1-pentyloxypropyl group,
1-hexyloxypropyl group, 1-heptyloxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group,
2-propoxypropyl, 2-butoxypropyl, 2-pentyloxypropyl, 2-hexyloxypropyl, 2-heptyloxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl ,
3-butoxypropyl group, 3-pentyloxypropyl group,
3-hexyloxypropyl group, 3-heptyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-propoxybutyl group, 4-butoxybutyl group, 4-pentyloxybutyl group, 4-hexyloxybutyl Group, 4-heptyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-propoxypentyl group, 5-butoxypentyl group, 5-pentyloxypentyl group, 5-hexyloxypentyl group, 5-heptyl Oxypentyl, 6-methoxyhexyl, 6-ethoxyhexyl, 6-propoxyhexyl, 6-butoxyhexyl, 6-pentyloxyhexyl, 6-hexyloxyhexyl, 6-heptyloxyhexyl, etc. And an alkoxyl-substituted alkyl group.

When the compound contains an asymmetric carbon, it may be optically active or racemic. Further, as the alkoxyl group, alkanoyloxy group or alkoxycarbonyl group, -O-, -OC
O- and -COO- are introduced.

The polymer compound having a structure represented by the general formula (I) as a basic unit is represented by the general formula (II)

[0026]

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(Wherein X, linking groups L ¹ , L ² , L ³ and L ⁴ ,
Z, ring A, ring B, ring C and ring D, m and n ^{1 to} n ³ are a general formula
Same as (I). )) In the presence of an optically active palladium catalyst to react with carbon monoxide.

Here, the compound represented by the general formula (II) is
It is a well-known compound as a liquid crystal compound,
Its manufacture is also easy.

The polymer compound having a structure represented by the general formula (I) as a basic unit includes X, linking groups L ¹ , L ² , L ³ and L ⁴ , Z,
Various compounds may be mentioned according to ring A, ring B, ring C and ring D, m, and n ^{1 to} n ³ , and typical compounds and a high molecular compound having the following structure as a basic unit Can be mentioned.

[0030]

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A polymer having a number average molecular weight of 5,000 and having (Ia) as a basic unit actually exhibited liquid crystallinity in a wide temperature range from 147 ° C. to room temperature when the temperature was lowered. Further, a high molecular compound having a number average molecular weight of 9,000 having (Ib) as a basic unit,
It exhibited liquid crystallinity over a wide temperature range from 4 ° C to 176 ° C and from 174 ° C to room temperature when cooled. The polymer compound having a number average molecular weight of 11,000 having (Ic) as a basic unit is 153 from 51 ° C. when the temperature is raised.
It exhibited liquid crystallinity over a wide temperature range from 152 ° C to room temperature when cooled.

[0032]

EXAMPLES Example 1 Asymmetric Polymerization of 4- (3-Butenyl) -4′-cyanobiphenyl and Carbon Monoxide Pd (CH ₃ ) Cl [(R, S) -BINAPHOS] (Argon atmosphere) 15.7 m
g) in dichloromethane (2 ml) was added with a solution of sodium tetra [3,5-bis (trifluoromethyl) phenyl] boron (15 mg) in acetonitrile (1 ml), and the mixture was stirred at room temperature for 1 hour. The reaction solution was dried under reduced pressure, and dichloromethane (3 ml) was added thereto.
Was added, and the mixture was stirred under a carbon monoxide atmosphere for 30 minutes. The reaction solution was transferred to a 50 ml autoclave, and 4- (3-butenyl)-
4′-Cyanobiphenyl (384 mg) was added, and the mixture was stirred at 20 ° C. under 20 atm of carbon monoxide for 7 days. The reaction solution was treated with methanol (100
ml), the white precipitate was separated by filtration, washed with hexane, dried in vacuo, and a polymer compound (165 m
g) was obtained. ¹ H NMR δ 2.40-2.75 (m, 2H), 3.60-4.20 (m, 3H), 4.00-
4.20 (m, 2H), 6.90-7.10 (m, 2H), 7.40-7.90 (m, 6H) Mn (Mn / Mw) 4600 (1.16) [Φ] _D -501 (c 0.15, HFIP (1,1, 1,3,3,3-Hexafluoro-2-p
ropanol), 22.8 ° C)

(Example 2) Asymmetric polymerization of 4- (5-hexenyl) -4'-cyanobiphenyl and carbon monoxide In the same manner as in Example 1, 4- (3-butenyl) -4'-cyanobiphenyl Was used instead of 4- (5-hexenyl) -4′-cyanobiphenyl to obtain a polymer compound having (Ib) as a basic unit. ¹ H NMR δ 1.10-1.50 (m, 2H), 1.50-1.90 (m, 4H), 2.50-
2.80 (m, 1H), 2.80-3.20 (m, 2H), 3.70-4.10 (m, 2H), 6.80
-7.10 (m, 2H), 7.30-7.80 (m, 6H) ¹³ C NMR δ 23.43, 29.13, 31.00, 44.40, 45.18, 67.5
5, 109.85, 114.93, 118.90, 126.90, 128.25, 131.30,
132.54, 144.92, 159.46, 212.67 Mn (Mn / Mw) 8800 (1.53) [Φ] _D -86 (c 0.15, HFIP, 22.8 ℃)

Example 3 Asymmetric polymerization of 4- (7-octenyl) -4'-cyanobiphenyl and carbon monoxide In the same manner as in Example 1, 4- (3-butenyl) -4'-cyanobiphenyl Was used instead of 4- (7-octenyl) -4′-cyanobiphenyl to obtain a polymer compound having (Ic) as a basic unit. ^{1 H NMR δ 1.10-1.55 (m,} 8H), 1.55-1.65 (m, 2H), 1.65-
1.90 (m, 2H), 2.55-2.80 (m, 1H), 3.91 (t, 2H), 6.78-7.10
(m, 2H), 7.40-7.80 (m, 6H) ¹³ C NMR δ 25.709, 26.81, 29.08, 29.24, 29.40, 31.3
2, 44.62, 45.18, 67.91, 110.10, 114.95, 118.94, 12
6.92, 128.27, 131.27, 132.53, 144,92, 159.59, 212.
63 Mn (Mn / Mw) 11000 (1.36) [Φ] _D -28 (c 0.15, HFIP, 22.8 ℃)

[0035]

Most of the polymer compounds provided by the present invention exhibit liquid crystallinity over a wide temperature range. Further, it is easy to manufacture industrially. Therefore, they are extremely useful as retardation compensation films, cholesteric films, pitch adjusters for nematic liquid crystals, polymer-dispersed liquid crystals, molecular ferroelectric liquid crystals, and optical isomer separation column chromatography.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Hasebe 4-12-8 Midorioka, Ageo-shi, Saitama 107 Tomiyoshi Corp. F-term (reference) 4H027 BA06 BA13 BD02 4J005 AB01

Claims (8)

[Claims] 1. A compound of the general formula (I) (In the formula, 1 to 10 non-adjacent methylene groups may be substituted with an oxygen atom, 1 to 10 methylene groups may be substituted with a dimethylsilylene group, and a saturated chain may contain a branched chain. Or an unsaturated alkylene group having 1 to 20 carbon atoms, wherein the linking group L ¹ is a single bond, -O-, -S-, -COO-, -OCO, -COS-
Or -SCO-, wherein the linking groups L ² , L ³ and L ⁴ are a single bond, -CH ₂ CH _2- , -CH = CH-, -CH (CH ₃ ) CH _2- , -CH ₂ CH ( CH ₃ )
-, -CH (CH ₃ ) CH (CH ₃ )-, -CF ₂ CF _2- , -CF = CF-, -CH ₂ O-, -O
CH _2- , -OCH (CH ₃ )-, -CH (CH ₃ ) O-, -C≡C-, -CF ₂ O-, -OCF
_2- , -COO-, -OCO-, -COS- or -SCO-, wherein Z is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,
A cyano group, a cyanato group, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group, a hydroxyl group, a carboxyl group, or even substituted by 1 to 20 fluorine atoms or an alkoxyl group having 1 to 20 carbon atoms. Well, represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, which may include a branched chain, an alkoxyl group, an alkanoyloxy group or an alkoxycarbonyl group, wherein ring A, ring B, ring C and ring D are each independently Trance
-1,4-cyclohexylene group, bicyclo [2.2.2] octane-
1,4-diyl group, trans-decahydronaphthalene-2,6-diyl group, trans-1,3-dioxane-2,4-diyl group, or optionally substituted with 1 to 4 fluorine atoms , 4-phenylene group, pyridine-2,5-diyl group optionally substituted by one or two fluorine atoms, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3 , 6-diyl group, and
Naphthalene-2,6 which may be substituted by 1 to 6 fluorine atoms
-Diyl group, tetrahydronaphthalene-2,6-diyl group even when substituted with 1-3 fluorines, decahydronaphthalene-2,
Represents a 6-diyl group, m represents 0 or 1, and n ^{1 to} n ³ each independently represent 0 or 1. The carbons marked with * represent chiral asymmetric carbons. A polymer compound having a structure represented by) as a basic unit. 2. The polymer compound according to claim 1, wherein the average molecular weight is 1,000 to 10,000,000. 3. The polymer compound according to claim 1, which exhibits liquid crystallinity by itself. 4. The compound according to claim 1, wherein in the general formula (I), X is a saturated or unsaturated alkylene group having 1 to 20 carbon atoms which may contain a branched chain. 5. The compound according to claim 1, wherein in the general formula (I), X is a saturated alkylene group having 1 to 20 carbon atoms which may contain a branched chain. 6. The method according to claim 1, wherein in the general formula (I), the linking groups L ² , L ³ and L ⁴ are each independently a single bond, —C≡C—, —COO—, or —OCO—. 6. The compound according to any one of 1 to 5. 7. The compound according to claim 1, wherein in the general formula (I), the linking group L ¹ is a single bond, —O—, —COO— or —OCO. 8. In the general formula (I), ring A, ring B, ring C and ring D may be each independently substituted with a trans-1,4-cyclohexylene group and 1 to 4 fluorine atoms. 1,4-phenylene group, pyrimidine-2,5-diyl group which may be substituted with 1 or 2 fluorine atoms, or naphthalene-2,6- which may be substituted with 1 to 6 fluorine atoms The compound according to any one of claims 1 to 7, which is a diyl group.