JPH04218513A - Polymerizable monomer and polymer having mesogen group - Google Patents

Abstract

PURPOSE:To obtain a polymerizable monomer, having an alkylene group containing a siloxane bond in a spacer and capable of providing a polymer liquid crystal material exhibiting stable liquid crystallinity within a relatively low temperature range and having polymerizable groups and mesogen groups linked through the spacer. CONSTITUTION:A polymer is obtained by dissolving a polymerizable monomer expressed by formula I (R is H, halogen, alkyl or phenyl; R<1> to R<6> are alkyl or phenyl; X is single bond or group of O, COO or OCO; Q is mesogen group; m and p are integers of 2-20; n is an integer of 0 to 50) in tetrahydrofuran, etc., adding azobisisobutyronitrile to the resultant solution and carrying out polymerizing reaction at 60 deg.C temperature for 24hr. The aforementioned polymer has recurring units expressed by formula II, mesogen groups having 1000-1000000 weight-average molecular weight determined by using gel permeation chromatography as a value expressed in terms of polystyrene and is useful as a side-chain type polymer liquid crystalline material, etc.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention is directed to a polymerizable group and a mesogenic group.
are bonded via a spacer containing a siloxane bond.
A novel mesogenic group-containing polymerizable model characterized by
polymer, and the main polymers obtained by polymerizing it.
Spacer whose chain skeleton and mesogenic group contain siloxane bonds
A novel mesogen characterized by being bound via
It relates to polymers having groups. In particular, the present invention
Polymers with mesogenic groups of
In other words, it exhibits stable liquid crystallinity at room temperature or lower temperatures.
It is useful as a side-chain polymer liquid crystal. Background of the Invention and Prior Art Conventionally, mesogenic groups have been added to the side chains.
Side-chain polymer liquid crystals with
Recently, it has been used as a display element and recording material for nonlinear light.
Widely used as a functional material used in academic materials, light control glass, etc.
A wide range of applications are being considered. Conventionally known side chain type
Molecular liquid crystals are made up of molecules through chemical bonds called spacers.
It has a structure in which sogen groups are bonded to the polymer main chain skeleton.
. In that case, the main chain skeleton is polymethacrylate, polymer
Reacrylate, polyether, polyorganosiloxa
There are many known polymers such as
Many side-chain polymer liquid crystals have been proposed. (For example, small
Edited by Naoyuki De, Liquid Crystal Polymer, CMC (1987)
;R. Zentel, “Liquid Crystal
Alline Polymers”, Kem. In
d. , Volume 37, p. 355 (1988); V.
P. Shibaev, “Synthesis and
Structure of Liquid-crys
tallline side-chain polymer
s”, Pure & Appl. Chem., No. 5
Volume 7, p. 1589 (1985); T. Chun
g, ”The Recent Developments of Th
ermotropic liquid crystal
"line Polymers", Polym. Eng. Sci., Volume 26, p. 901 (198
6)) [0003] Also, it is better to use a spacer.
Since the mobility of the chain skeleton and mesogenic group becomes independent, the liquid crystal
The orientation state can be easily expressed, and the spacer can be made longer.
It is better to use a spacer with high mobility to make the liquid crystal more stable.
It is said that the phase is expressed. (Naoyuki Koide, “Polymer liquid
"Synthesis of Crystals", Kobunshi, Vol. 36, p. 98 (1987)
)) chemical bond traditionally known as that spacer
Most of them are alkylene groups and oxyalkylene groups.
It is. However, with respect to the above main chain skeleton,
If you use a spacer like
Due to the high temperature, most cases do not exhibit liquid crystallinity near room temperature.
It was. Problem to be Solved by the Invention The object of the present invention is to
In view of the drawbacks of side-chain polymer liquid crystals with spacers,
Has a highly mobile siloxane bond in the spacer
By introducing alkylene groups, relatively low temperature
In other words, stable liquid crystallinity at room temperature or lower.
An object of the present invention is to provide a side chain type polymer liquid crystal shown in FIG. [Means for Solving the Problems] The present inventors have developed a spacer
Synthesizing side-chain polymer liquid crystals with siloxane bonds in
We have given careful consideration to this matter. As a result,
to create a new monomer with a mesogenic group and a polymerizable group.
can be synthesized, and by polymerizing the monomers.
A novel side chain with a siloxane bond in the spacer
discovered that it is possible to produce polymers with sogenic groups,
We have arrived at the present invention. That is, the present invention provides the following general formula (
I) [Chemical formula 3] (wherein, R is a hydrogen atom, a halogen atom, a
alkyl group or phenyl group, R1 to R6 are the same or
may be different, an alkyl group or a phenyl group, X is a single
bond, oxygen atom, or -COO- or -OCO-
A group represented by Q is a mesogenic group, m and p are 2 to 2
An integer of 0, n is an integer of 0 to 50. ) is expressed as
Polymerizable monomers with mesogenic groups and repeating monomers
position is represented by the following general formula (II): ##STR4## where R is a hydrogen atom, a halogen atom,
alkyl group or phenyl group, R1 to R6 are the same or
may be different, an alkyl group or a phenyl group, X is a single
bond, oxygen atom, or -COO- or -OCO-
A group represented by Q is a mesogenic group, m and p are 2 to 2
An integer of 0, n is an integer of 0 or more. However, R, R1
~R6, X, Q, m, n and p are for each repeating unit
May be arbitrarily different. ), gel permeability
Polystyrene equivalent value using chromatography
The weight average molecular weight calculated as 1,000 to 1,000,000
Provides a polymer with a certain mesogenic group
. In the general formulas (I) and (II), Q represents
The mesogenic group to be dissolved is a conventionally known liquid crystalline group.
It is a giving group, and its structure is not particularly limited. mesogenic group
Examples include biphenyl, biphenyls,
ether, benzoic acid phenyl ester, benzoic acid bif
phenyl ester, benzylidene aniline, stilbene,
Azoxybenzene, azobenzene, Schiff base, cyclo
hexyl phenyl ether, cyclohexylbenzene,
Cyclohexylcarboxylic acid phenyl ester, cyclohexylcarboxylic acid phenyl ester
xylcarboxylic acid biphenyl ester, cholesterin,
Mention may be made of cholestane and their derivatives
. In addition, an alkyl group having an optically active group in the above mesogen molecule may be used.
group, alkoxy group, fluoroalkyl group, cyanoalkyl group,
Bonding polar groups such as kill groups and cyanoalkoxy groups
By this, the polymer having a mesogenic group of the present invention is strongly attracted.
It is also possible to impart special effects such as electrical properties. In the general formulas (I) and (II), R is
Hydrogen atoms, fluorine, chlorine, bromine, iodine, etc.
Gen atom, methyl group, ethyl group, propyl group, iso-
Propyl group, butyl group, t-butyl group, hexyl group, etc.
Examples include straight-chain or branched alkyl groups and phenyl groups.
can be shown. However, for ease of synthesis, it is expressed as R.
As the substituent, a halogen atom or a methyl group is more preferable.
Delicious. In addition, R1 in the general formulas (I) and (II)
The substituents represented by ~R6 include methyl group, ethyl group, etc.
thyl group, propyl group, iso-propyl group, butyl group,
iso-butyl group, t-butyl group, pentyl group, hexy
linear or branched alkyl groups such as
Examples include ru groups. However, the ease of synthesis and the present invention
In order to take advantage of the properties of polymers with mesogenic groups,
, among the above substituents, a methyl group is most preferred. Also,
The methylene chain in the general formulas (I) and (II) is
Therefore, m and p in the formula
The number of methylene groups used must be in the range of 2 to 20.
Ru. However, the ease of synthesis and the mesogenic group of the present invention
In order to take advantage of the properties of the polymer, m and p must be
More preferably, it is in the range of 3 to 10. [0014] The compound represented by the general formula (I) of the present invention
Synthesizing monomers can be produced, for example, by the synthetic route shown below.
Can be easily synthesized. In the general formula (I), n is
When the degree of polymerization of the expressed siloxane chain is 0, i.e.
If the polymerizable group and mesogenic group contain a disiloxane bond,
When synthesizing monomers bonded via a
The method shown in [Route 1] below can be applied. [0015] [0016] (In the above formula, R is a hydrogen atom, a halogen atom
, alkyl group or phenyl group, R1, R2, R5 and
and R6 may be the same or different, and
group or phenyl group, X is a single bond, oxygen atom, or
A group represented by -COO- or -OCO-, Q is a metal
The sogenic groups, m and p, are integers from 2 to 20. ) That is, represented by the above general formula (III)
A silanol compound having a mesogenic group and the general formula
Chlorosilanization having a polymerizable group represented by (IV)
The compound of the general formula (I
') can be synthesized with a monomer having a mesogenic group represented by
Wear. In addition, the cyrano represented by the general formula (III)
chlorosil compound and the chlorosilane compound represented by the general formula (IV)
Hydrogen chloride is generated when reacting with orchid compounds.
As a supplement, triethylamine, N,N-dimethyl
This is carried out in the presence of organic bases such as tylaniline and pyridine.
The reaction progresses suitably. This reaction is carried out in an organic solvent
It is preferable to carry out the reaction in
Trahydrofuran, benzene, toluene, n-hexane
, chloroform, carbon tetrachloride, etc. are preferably used. difference
Furthermore, this reaction is performed in an inert gas atmosphere such as argon or nitrogen.
It is preferable to do it below. The general formula (I
As the chlorosilane compound represented by V), 00
18 ##STR6## (In the above formula, m is an integer from 2 to 20.). Furthermore, in the general formula (I), n represents
When the degree of polymerization of the siloxane chains is 1 or more, that is, polymerization
The space between the functional group and the mesogenic group contains a polysiloxane bond.
When synthesizing monomers bound via a
The method shown in [Route 2] below can be applied. [0021] [0022] (In the above formula, R is a hydrogen atom, a halogen atom
, alkyl group or phenyl group, R1 to R6 are the same
or may be different, an alkyl group or a phenyl group,
is a single bond, an oxygen atom, or -COO- or -OC
A group represented by O-, Q is a mesogenic group, m and p are 2
-20 integer, n is an integer from 1 to 50. ) That is, represented by the above general formula (III)
Silanolate is produced by reacting the silanol compound with a base.
After making it into an anion, the compound represented by the general formula (V)
Living ring-opening polymerization of a rosiloxane compound
Reaction with a chlorosilane compound represented by general formula (IV)
By stopping the model represented by the general formula (I''),
Can synthesize Nomer. The base used here is methyl
rulithium, n-butyllithium, sec-butyllithium
um, t-butyllithium, phenyllithium, lithium
Mudiisolopyramide, bistrimethyllithiumamide
Organolithium compounds such as sodium hydride, carbon hydride, etc.
Alkali metal hydrides such as lithium, methyl iodide
sium, ethylmagnesium bromide, phenylmagnesium bromide
Examples include Grignard compounds such as sium.
Ru. These bases are usually prepared from the above general formula (I) as a starting material.
Approximately 1 equivalent to the silanol compound represented by II)
Use quantity. Reaction temperature is relatively low from -90℃ to room temperature
It is preferable to carry out the reaction at a warm temperature in order to suppress side reactions. Also,
This reaction is preferably carried out in an organic solvent.
Solvents include tetrahydrofuran, benzene, and toluene.
N-hexane, chloroform, carbon tetrachloride, etc. are suitable.
used for. Furthermore, this reaction can be carried out using argon, nitrogen, etc.
It is desirable to carry out under an inert gas atmosphere. The above general formula
As the cyclosiloxane compound represented by (V),
[0025] [0026] etc. can be exemplified. Also, this anti-
In the reaction, cyclosiloxane represented by the above general formula (V)
By adjusting the amount of the sun compound, the general formula (I
”) of the polysiloxane bond in the monomer.
The homopolymerization degree bar n can be controlled. [0027] The above [Route 1] and [Route 2]
A mesogenic group represented by the general formula (I) of the present invention shown in
In the method for producing a polymerizable monomer having
The mesogame represented by the general formula (III) used in
Examples of silanol compounds having a silan group include the following:
It can be synthesized by a manufacturing method. That is, below
General formula (IV) [Chemical formula 9] [0029] (wherein, X is a single bond, an oxygen atom, or -
A group represented by COO- or -OCO-, Q is meso
Gen group, q is an integer of 0 to 18. ) is expressed as
An alkenyl compound having a mesogenic group and the following general formula (
VII) [Chemical formula 10] [0031] (wherein R5 and R6 are the same or different
may be an alkyl group or a phenyl group, and R' is an alkyl group or a phenyl group.
It is a rukyl group. ) Alkoxysilane compound represented by
and the compound represented by the general formula (VII) is
Equimolar or more with respect to the compound represented by the general formula (VI)
Mix in such a way that the mixture is on top and react in the presence of a hydrosilylation catalyst.
By this, the following general formula (VIII) [0032] [0033] (wherein R5 and R6 are the same or different
may be an alkyl group or a phenyl group, and R' is an alkyl group or a phenyl group.
Alkyl group, X is a single bond, oxygen atom, or -COO-
or a group represented by -OCO-, Q is a mesogenic group,
p is an integer from 2 to 20. ) are combined.
and further a compound represented by the general formula (VIII)
By hydrolyzing the compound, in the general formula (III),
Manufacture silanol compounds with expressed mesogenic groups
can. In the above manufacturing method, the general formula (V
I) and the alkenyl compound represented by the general formula (VI
I) is reacted with the alkoxysilane represented by
When producing a compound represented by general formula (VIII)
The hydrosilylation catalyst used is platinum, platinum carbon,
Chloroplatinic acid and dicyclopentadienyl platinum di
The most common method is to use platinum-based catalysts such as chloride.
However, there are also other metal complexes containing palladium and rhodium.
is available. For example, (Ph3P)4Pd, (P
h3P)2PdCl2, (PhCN)2PdCl2,
(Ph3P)3RhCl, (Ph2PH)2RhCl
, (Ph3P)2(CO)RhCl, [(C2H5)3
P]2(CO)RhCl etc. can be used as a catalyst.
can. The amount of catalyst used is determined by the above general formula (VI).
Usually 1/100 to the expressed alkenyl compound
About 1/1000 equivalent is sufficient. Also complete this reaction.
In order to bind, the compound represented by the general formula (VII)
For a compound represented by the above general formula (VI)
It is necessary to mix them so that the moles are equal or more. This anti
The reaction is preferably carried out in a solvent, and the solvent is hexane.
benzene, toluene, acetone, trichloroethylene
Use chlorine, carbon tetrachloride, tetrahydrofuran, etc.
I can do it. The reaction temperature is usually in the range of 40℃ to 100℃
and under an inert gas atmosphere such as argon or nitrogen.
It is preferable to do so. Mesogen represented by the general formula (VI)
The synthesis of alkenyl compounds having groups will be shown later in reference examples.
Introducing an alkenyl group directly into the mesogenic group mentioned above, as shown in
or one step in synthesizing the aforementioned mesogenic groups.
easily by introducing an alkenyl group into
can be achieved. Represented by the general formula (VII)
Examples of the alkoxysilane compounds include: ##STR12## and some of these are
It is commercially available. Compound represented by the above general formula (VIII)
Silanolization represented by the above general formula (III) from a substance
The hydrolysis reaction carried out when producing compounds is usually carried out using a base or
The reaction proceeds smoothly by carrying out the reaction in the presence of acid.
Ru. The base or acid used here is lithium hydroxide.
aluminum, potassium hydroxide, sodium hydroxide, aluminum hydroxide
potassium carbonate, sodium carbonate, potassium acetate
, bases such as sodium acetate, or hydrochloric acid, sulfuric acid, nitric acid, vinegar
Acids, Calcium Sulfate, Calcium Nitrate, Magnesium Sulfate
Acids such as silica and the like are preferably used. In particular, the general formula (VI
II) Hydrolysis of ester bonds, etc. to the mesogenic group Q in
If a bond that is susceptible to binding is present, the above bases or
Among acids, it is preferable to use weak bases or weak acids. this
These bases or acids are represented by the above general formula (VIII).
It can be used in an amount of 0.1 to 5.0 equivalents relative to the compound to be used.
is preferable. [0040] Furthermore, this reaction can be carried out in the presence of water.
Although essential, the compound represented by the above general formula (VIII)
If the compound is insoluble in water, methanol, ethanol,
Propanol, acetone, tetrahydrofuran, acetate
By using water-soluble organic solvents such as nitrile
The reaction proceeds suitably. Room temperature is usually sufficient for the reaction temperature.
However, when the temperature is high, the dimer of the target silanol
Certain disiloxane compounds are obtained as by-products
There is. In addition, if this dimerization reaction progresses easily,
Control the reaction temperature within the range of -100℃ to 0℃.
It is necessary to [0041] The present invention obtained by the method described above
Polymerization having a mesogenic group represented by the above general formula (I)
The repeating unit is formed by the above general formula (I
Polymer having a mesogenic group of the present invention represented by I)
When synthesizing, two or more of the above general formula (I)
This is done by mixing polymerizable monomers with mesogenic groups.
Radical polymerization, anionic polymerization, cationic polymerization
Known addition polymerization methods such as polymerization can be used. However, in this case, radical polymerization
method is preferably used as the simplest method. radical
When using the polymerization method, bulk polymerization, solution polymerization, and emulsion polymerization are used.
Any known method can be used. radical polymerization
The reaction is simply initiated by heat, UV irradiation or radical initiators.
Started by addition. Radicals suitable for reaction
Initiators include dilauroyl peroxide, di-t
-butyl peroxide, benzoyl peroxide, t-
Butyl hydroperoxide, cumene hydroperoxide
organic peroxides such as α, α', -azobisisobutylene
Tyronitrile and azobiscyclohexanecarbonitrile
Examples include azo compounds such as. [0043] Also, a chain transfer agent is added during the polymerization reaction.
The molecular weight of the resulting polymer can be controlled to some extent by
can be done. The chain transfer agent used here is
Carbon chloride, bromotrichloromethane, p-benzoquinone
, chloroanil, n-butanethiol, n-dodecanethiol
Examples include oars. In this case, the radical polymerization reaction
Organic solvents that can be used include, for example, benzene, toluene,
Chlorobenzene, tetrahydrofuran, chloroform,
Methyl ethyl ketone, fluorobenzene, methanol,
Ethanol, n- or i-propanol, N,N-
Dimethylformamide, N,N-dimethylacetamide
etc., but are not limited to these.
There isn't. The reaction usually occurs smoothly in the range of 40℃ to 100℃.
proceed. The mesogen of the present invention thus obtained
The group-containing polymer is composed of two or more types of repeating units.
It may also be a copolymer. That is, the first general formula (I
In I), a group represented by R, R1 to R6, X, Q, and
m, n, and p may be arbitrarily different for each repeating unit.
. Also, the weight average molecular weight of this polymer is
Polystyrene conversion using cation chromatography
The calculated value must be between 1,000 and 1,000,000.
is necessary, and furthermore, it is possible to fabricate, for example, a membrane from this polymer.
When the strength is important, the weight
More preferably, the average molecular weight is 10,000 or more.
stomach. By the method described above, the general formula of the present invention can be obtained.
Polymerizable monomer having a mesogenic group represented by (I)
The repeating unit is easily derived from the general formula (I
Polymer having a mesogenic group of the present invention represented by I)
has a highly mobile siloxane bond in the spacer
Therefore, the glass transition temperature is low, around room temperature or below.
As shown in some of the examples below, relatively low temperature
That is, a wide range of temperatures from near room temperature or below.
It has become clear that liquid crystallinity is extremely stable over a range of
. Therefore, the polymer having mesogenic groups of the present invention is
Display materials, recording materials, and non-display materials in the electronics field
Linear optical materials and other materials for light control glass and separation membrane materials
It can be applied to various uses such as materials, making use of its characteristics.
Ru. [0046] The present invention will be explained below with reference examples and examples.
will be explained in more detail. However, the present invention is limited to these.
Of course, this cannot be determined. In addition, the following
In the reaction formula shown below, D3 is hexamethylcyclotrisilyl
xane, n-BuLi is n-butyllithium, AIBN
each represents azobisisobutyronitrile. [Example] Reference Example 1 Silanol having mesogenic group
Synthesis of compound 1 [Chemical formula 13] 4-cyano 4'-hydroxybiphenyl
10.0g (51.2mmol) in 100m of ethanol
reflux the solution dissolved in
15ml of an aqueous solution containing 3.7g (66.1mmol) of
1 was added dropwise. After dropping, add 13.3 ml of allyl bromide (
178 mmol) and continued stirring for about 1 hour.
A white solid precipitated out. Distill the ethanol and add water
After slurrying, the obtained solid was filtered and filtered with silica gel.
Purified by column chromatography to produce 10.0g of white
Obtained crystals. Regarding the obtained product, 1H-NMR,
Perform IR spectrum analysis and elemental analysis to identify the target product.
4-allyroxy4'-cyanobiphenyl
confirmed. (Yield: 83.0%, melting point: 81°C) 1H-NMR spectrum, δ(CDCl3
, ppm); 4.59 (dt, 2H, CH2
=CHCH2O-), 5.31 (dd, 1H,
CH2=CHCH2O-), 5.42 (dd, 1
H, CH2=CHCH2O-), 5.90-6.3
5 (m, 1H, CH2=CHCH2O-), 7.
01 (d, 2H, proton peak of phenylene group
), 7.53 (d, 2H, proto of phenylene group
peak), 7.66 (s, 4H, phenylene group
proton peak). IR spectrum (cm-1);
2950, 2880, 2230 (by C-N bond)
(Characteristic absorption of phenylene group), 1605 (Characteristic absorption of phenylene group)
), 1495, 1290, 1180, 990,
830. Elemental analysis value (%); Measured value; C: 81.29,
H: 5.61, N: 5.89
Calculated value; C: 81.67, H:
5.57, N: 5.95 [0051] Obtained here
4-allyloxy-4'-cyanobiphenyl 8.10
g (34.4 mmol) and dimethylethoxysilane 10
．． Dissolve 0ml (72.2mmol) in 60ml of toluene.
and a solution of chloroplatinic acid in isopropyl alcohol (0.
Add 0.10 ml of 1 mol/l) and create an argon gas atmosphere.
The mixture was stirred overnight at 80°C under air. After distilling off the solvent, silica
8.60g purified by Kagel column chromatography
A colorless transparent liquid was obtained. For the obtained product, 1H
-NMR, IR, Mass spectral analysis and original
Elementary analysis was performed to identify the target product, 4-(3-dimethylethoxy).
silylpropoxy)-4'-cyanobiphenyl
I confirmed that. (Yield; 73.6%) 0052
1H-NMR spectrum, δ (CDCl3, ppm);
0.15 (s, 6H, Si-CH3), 0.
53~0.83 (m, 2H, Si-CH2CH2
CH2-O), 1.20 (t, 3H, Si-O
CH2CH3), 1.66~2.00 (m, 2H
, Si-CH2CH2CH2-O), 3.69 (
q, 2H, Si-OCH2CH3), 3.99
(t, 2H, Si-CH2CH2CH2-O),
6.99 (d, 2H, proton pi of phenylene group
(d, 2H, phenylene group), 7.50 (d, 2H,
Roton Peak), 7.66 (s, 4H, Phenyl
proton peak of ren group). IR spectrum (cm
-1); 2950, 2880, 2230 (C-
(characteristic absorption due to N bond), 1605 (phenylene group
characteristic absorption), 1495, 1290, 1250
(Characteristic absorption due to Si-C bond), 1180, 11
05, 1075, 1000, 940, 890,
835. Mass spectrum (m/e); 339 (
M+), 297, 282, 103 (EtOMe
2Si+). Elemental analysis value (%); Measured value; C:
70.63, H: 7.47, N: 4.05
Calculated value; C: 70.
76, H: 7.42, N: 4.13 0053
] Next, this 4-(3-dimethylethoxysilylpropolymer)
xy)-4'-cyanobiphenyl 8.50g (25.0
mmol) in 40 ml of ethanol, and this solution
Sodium hydroxide 5.0g (125mmol) water 1
Pour into a solution dissolved in 5 ml and 40 ml of methanol.
and further add 5.0 g (1 ml) of sodium hydroxide to this solution.
An aqueous solution of 25 mmol) dissolved in 50 ml of water was added.
. After stirring at room temperature for 15 minutes, the reaction solution was diluted with phosphoric acid.
Pour into excess ice water containing 35g of potassium dihydrogen.
After extraction with chloroform, the organic phase was added to anhydrous sodium sulfate.
and dried. After distilling off the solvent, silica gel column chromatography
Purification was done by matography to obtain 4.70g of white solid.
. Regarding the obtained product, 1H-NMR, IR, M
Ass spectrum analysis and elemental analysis were performed to determine the purpose.
4-(3-dimethylhydroxysilylpropoxy)
It was confirmed that it was -4'-cyanobiphenyl. (Collection
73.6%) 1H-NMR spectrum
Le, δ (CDCl3, ppm); 0.12 (s,
6H, Si-CH3), 0.60~0.81 (m
, 2H, Si-CH2CH2CH2-O), 1.
65 (s, 1H, Si-OH), 1.70-2.
00 (m, 2H, Si-CH2CH2CH2-
O), 4.00 (t, 2H, Si-CH2CH2
CH2-O), 7.00 (d, 2H, phenylene
(Proton peak of 2H), 7.50 (d, 2H,
proton peak of phenylene group), 7.68 (s
, 4H, proton peak of phenylene group). IRs
Spectrum (cm-1); 3450 (characteristic absorption of hydroxyl group)
collection), 2945, 2880, 2225 (C-N
(characteristic absorption due to bond), 1605 (of phenylene group)
characteristic absorption), 1495, 1475, 1295,
1250 (characteristic absorption due to Si-C bond), 118
0, 1050, 1030, 1010, 825.
Mass spectrum (m/e); 311 (M+)
, 269, 254,75 (HOMe2Si+).
Elemental analysis value (%); Measured value; C: 69.25,
H: 6.72, N: 4.45
Calculated value; C: 69.42, H:
6.80, N: 4.50 Example 1
Synthesis of monomer 1 [0056] [Chemical formula 14] 4-(3-dimethylhydrogen
droxysilylpropoxy)-4'-cyanobiphenyl
4.00g (12.8mmol) in argon gas atmosphere
Dissolve in 10 ml of tetrahydrofuran and add to this solution.
Triethylamine 2.20ml (15.8mmol)
and 3-methacryloxypropyldimethylchlorosilane
Add 3.40g (15.4mmol) and stir at room temperature overnight.
did. A white salt is formed, which is mixed with diethyl ether.
After filtering and distilling off the solvent while washing with
Purified by ram chromatography to give 3.56g of colorless clear
A bright liquid was obtained. Regarding the obtained product, 1H-NMR, IR, Ma
We performed ss spectrum analysis and elemental analysis, and the above
It was confirmed that it was a monomer represented by the structure. (Collection
56.0%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.46-0.75 (m, 4H, Si-
CH2CH2CH2-Ox2), 1.53-1.87
(m, 4H, Si-CH2CH2CH2-O x
2), 1.96 (dd, 3H, CH2=C(CH
3) COO-), 4.00 (t, 2H, Si-C
H2CH2CH2-O), 4.13 (t, 2H,
Si-CH2CH2CH2-O), 5.53 (m,
1H, CH2=C(CH3)COO-), 6.6
0 (m, 1H, CH2=C(CH3)COO-)
, 6.98 (d, 2H, proton of phenylene group
peak), 7.53 (d, 2H, phenylene group
proton peak), 7.66 (s, 4H, phenylene
(proton peak of ion group). IR spectrum (cm-1)
; 2960, 2220 (characteristic absorption due to C-N bond
collection), 1715 (Characteristic absorption of carbonyl group), 1
635 (Characteristic absorption due to C=C bond), 1605 (
Characteristic absorption of phenylene group), 1495, 1475,
1400, 1320, 1295, 1250 (S
characteristic absorption due to i-C bond), 1170, 1050
(Characteristic absorption due to siloxane bond), 940, 8
20,800. Mass spectrum (m/e); 4
95 (M+), 326, 259, 217, 69
(CH2=C(CH3)CO+),41 (CH2=
C(CH3)+). Elemental analysis value (%); Measured value; C: 65.30,
H: 7.50, N: 2.68
Calculated value; C: 65.41, H:
7.52, N: 2.83 Example 2
Synthesis of Polymer 1 [0060] 1.50 g of the monomer obtained in Example 1 (
3.02 mmol) was dissolved in 15 ml of tetrahydrofuran.
Add 25 mg of azobisisobutyronitrile to this solution.
(0.152 mmol) was added. (Monomer concentration: approx. 200 mmol/l, initiator concentration
(About 10 mmol/l) Thoroughly freeze-thaw this solution.
After cooling, a polymerization reaction was carried out at 60° C. for 24 hours. anti
Pour the reaction solution into 250 ml of methanol, and the resulting precipitate
is recovered, further dissolved in tetrahydrofuran, and dissolved in methanol.
The reprecipitation was repeated twice during the process. As a result, 0.92g
A white solid polymer was obtained. (Yield; 61.0%) Regarding the obtained polymer,
1H-NMR and IR spectral analysis and elemental analysis
to confirm that the repeating unit is a polymer represented by [Chemical formula 16] [0063]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
1.18x104 and 2.11x respectively
It was 104. The glass transition temperature of this polymer was -14°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.38-0.80 (m, 4H, Si-
CH2CH2CH2-Ox2), 0.85-1.1
0 (m, 3H, -CH2C(CH3)-), 1.
45~2.28 (m, 6H, Si-CH2CH2
CH2-Ox2, -CH2C(CH3)-), 3.
98 (t, 4H, Si-CH2CH2CH2-O
x2), 7.00 (d, 2H, phenylene group
proton peak), 7.53 (d, 2H, phenyl
Proton peak of ren group), 7.65 (s, 4H,
Proton peak of phenylene group). IR spectrum (
cm-1); 2960, 2220 (C-N bond
(Characteristic absorption of carbonyl group), 1715 (Characteristic absorption of carbonyl group)
collection), 1605 (Characteristic absorption of phenylene group), 1
495, 1475, 1400, 1320, 12
95, 1250 (characteristic absorption due to Si-C bond),
1170, 1050 (characteristic absorption due to siloxane bond)
collection), 940, 820, 800. Elemental analysis value (%
); Measured value; C: 65.40, H: 7.61
, N: 2.87 calculated value; C: 65.41,
H: 7.52, N: 2.83 [0065] Implementation
Example 3 Synthesis of monomer 2 [Chemical formula 17]
Droxysilylpropoxy)-4'-cyanobiphenyl
2.00g (6.42mmol) in argon gas atmosphere
Dissolve in 20 ml of tetrahydrofuran and add this solution to
After cooling to -78°C, n-butyllithium in hexane
Solution (1.6 mol/l) 4.05 ml (6.48 mm
ol) was added and stirred for 2 hours. Add hexamethyl to this solution.
Cyclotrisiloxane 1.43g (6.43mmol)
Add a solution of 20ml of tetrahydrofuran to the chamber.
The mixture was warmed to warm temperature and further stirred overnight. Next, 3-metal
Ryloxypropyldimethylchlorosilane 2.13g (9
．． 63 mmol) was added to stop the reaction. White salt is produced
filter it while washing it with diethyl ether.
After distilling off the solvent, silica gel column chromatography
The product was purified in a vacuum cleaner to obtain 2.90 g of a colorless transparent liquid. The obtained product was analyzed by 1H-NMR and
and IR spectrum analysis, and the structure shown above is
It was confirmed that the monomer was 1H-NMR
on silicon appearing at 0.10 ppm in the spectrum
The area of the proton peak of the methyl group increased by approximately 2.4 times.
Other examples are 1H-NMR and IR spectra.
It was almost the same as the monomer obtained in 1. However, this
In this case, it is determined from the peak area ratio of the 1H-NMR spectrum.
The average degree of polymerization bar n of the polysiloxane bonds was 2.8.
It was. Example 4 Synthesis of Polymer 2 In Example 3
In the same manner as in Example 2 using 1.60 g of the obtained monomer.
Polymerization reaction and purification yielded 1.06g of colorless rubber.
A shaped polymer was obtained. (Yield; 66.2%) 0
070 Regarding the obtained polymer, 1H-NMR and
and IR spectrum analysis were performed, and the repeating unit was 00
71] Confirm that it is a polymer represented by [Chemical formula 18]
Ta. 0.10 ppm in 1H-NMR spectrum
The area of the proton peak of the methyl group on silicon that appears in
1H-NMR and IR
Both spectra are almost the same as the polymer obtained in Example 2.
Met. Determined by gel permeation chromatography
The number average molecular weight and weight average molecular weight are
The calculated values are 2.59x104 and 5.62x10 respectively.
It was 4. The glass transition temperature of this polymer is -32℃
Met. Example 5 Monomer synthesis 3 In Example 3
In the monomer synthesis described, hexamethylcyclotrisilyl
The amount of loxane was set to 2.86 g (12.9 mmol).
Except for this, 4.50 g of free
A transparent colored liquid was obtained. The obtained product was analyzed by 1H-NMR and
and IR spectrum analysis, the structure shown in Example 3 was confirmed.
It was confirmed that it was a monomer represented by the following structure. 1H-
A metal on silicon that appears at 0.10 ppm in NMR.
Since the area of the proton peak of the chill group has increased approximately 3.9 times,
Both 1H-NMR and IR spectra are from Example 3.
It was almost the same as the monomer obtained in . However, this
In the case, it was determined from the peak area ratio of the 1H-NMR spectrum.
The average degree of polymerization bar n of polysiloxane bonds was 5.8.
Ta. Example 6 Synthesis of Polymer 3 In Example 5
In the same manner as in Example 2 using 1.50 g of the obtained monomer.
Polymerization reaction and purification yielded 1.02g of colorless rubber.
A shaped polymer was obtained. (Yield; 68.0%) 00
76 Regarding the obtained polymer, 1H-NMR and
IR spectrum analysis was performed and the repeating unit was 0077
] Confirm that it is a polymer represented by [Chemical 19]
Ta. 0.10 ppm in 1H-NMR spectrum
The area of the proton peak of the methyl group on silicon that appears in
1H-NMR and IR, except that the
Both spectra are almost the same as the polymer obtained in Example 4.
Met. Determined by gel permeation chromatography
The number average molecular weight and weight average molecular weight are
The calculated values are 2.82x104 and 6.05x10 respectively.
It was 4. The glass transition temperature of this polymer is -54℃
Met. Reference Example 2 Silano having a mesogenic group
Synthesis of compound 2 [0080] p-hydroxybenzaldehyde 25.0
g (205 mmol), allyl bromide 30 ml (347 m
mol) and tetrabutylammonium hydrogen sulfate6.
5g (19.1mmol) in 60ml of tetrahydrofuran
16.5 g of sodium hydroxide is dissolved in this solution.
17 ml of an aqueous solution containing the mixture was added. Stirred at room temperature for 2 hours.
Afterwards, pour this reaction solution into an excess amount of water and add diethyl
After extraction with ether, the organic phase was dried over anhydrous sodium sulfate.
did. After distilling off the solvent, silica gel column chromatography
Purification was performed using Raffy to obtain 28.0 g of yellow solid. Obtained
1H-NMR spectrum analysis was performed on the obtained product.
No, the target product is p-allyloxybenzaldehyde.
It was confirmed. (Yield: 84.2%, melting point: 22
℃) 1H-NMR spectrum, δ(CD
Cl3, ppm); 4.65 (dt, 2H,
CH2=CHCH2O-), 5.32 (dd, 1H
, CH2=CHCH2O-), 5.45 (dd,
1H, CH2=CHCH2O-), 5.88-6
．． 30 (m, 1H, CH2=CHCH2O-),
7.00 (d, 2H, proton pi of phenylene group
(d, 2H, phenylene group), 7.83 (d, 2H, phenylene group)
roton peak), 9.86 (s, aldehyde group peak), 9.86 (s,
Roton Peak). p-Nitrophenylacetic acid
30.8g (170mmol) under argon gas atmosphere
Add 17 ml (172 mmol) of piperidine dropwise at room temperature.
In addition, 16.0 g of p-allyloxybenzaldehyde
(98.7 mmol) and then heated at 100℃ for 2 hours.
Stir for a while. When stirring was continued for another 3 hours at 130°C, the reaction solution
A brown solid was formed in the liquid. This reaction solution was heated to about 1 mm.
Piperidine and
Other by-products are distilled off, and the resulting solid is purified using silica gel.
Purified by column chromatography to yield 19.2g of yellow
A solid was obtained. 1H-NMR, IR spectrum of the obtained product
4-aryloyl and elemental analyzes of the target product were performed.
It was confirmed that it was C4'nitrostilbene. (
Yield: 69.2%, melting point: 114°C) 0
1H-NMR spectrum, δ(CDCl3,
ppm); 4.62 (dt, 2H, CH2=C
HCH2O-), 5.33 (dd, 1H, CH
2=CHCH2O-), 5.46 (dd, 1H,
CH2=CHCH2O-), 5.91-6.30
(m, 1H, CH2=CHCH2O-), 6.90
~7.25 (m, 4H, proton of phenylene group
peak), 7.41~7.70 (m, 4H, Fe
Proton peak of nylene group), 8.24 (d, 2H
, proton peak of vinylene group). IR spectrum
(cm-1); 2850, 2730, 1595
(characteristic absorption of phenylene group), 1510 (of nitro group)
(characteristic absorption), 1340 (characteristic absorption of nitro group),
1270, 1160, 995, 930, 830.
Elemental analysis value (%); Measured value; C: 72.61,
H: 5.33, N: 4.90
Calculated value; C: 72.58, H:
5.38, N: 4.98 Obtained 4
- Allyloxy 4' nitrostilbene 5.0 g (17
．． Toluene was added by adding 1.5 g of 5% platinum carbon to 8 mmol).
Dissolve in 30 ml of dimethyl ether under argon gas atmosphere.
Add 10.0ml (72.2mmol) of toxisilane
, and stirred at 50°C for 3 hours. Add diethyl ether to this solution.
After filtration, the solvent was distilled off, and silica gel column chromatography was performed.
Purification was done by matography to obtain 4.80g of yellow solid.
. Regarding the obtained product, 1H-NMR, IR, M
Ass spectrum analysis and elemental analysis were performed to determine the purpose.
4-(3-dimethylethoxysilylpropoxy)-
It was confirmed that it was 4'nitrostilbene. (Yield: 70.0%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.15 (s, 6H, Si-CH
3), 0.63~0.82 (m, 2H, Si-
CH2CH2CH2-O), 1.20 (t, 3H
, Si-OCH2CH3), 1.66-2.00
(m, 2H, Si-CH2CH2CH2-O),
3.69 (q, 2H, Si-OCH2CH3),
3.97 (t, 2H, Si-CH2CH2C
H2-O), 6.86-7.16 (m, 4H, F
Proton peak of henylene group), 7.43-7.63
(m, 4H, proton peak of phenylene group), 8
．． 20 (d, 2H, proton peak of vinylene group)
．． IR spectrum (cm-1); 2950, 288
0, 1590 (characteristic absorption of phenylene group), 151
0 (characteristic absorption of nitro group), 1340 (nitro group
(Characteristic absorption due to Si-C bond), 1250 (Characteristic due to Si-C bond)
absorption), 1175, 1110, 1030, 94
0, 890, 835. Mass spectrum (m/e
); 385 (M+), 343, 328, 10
3 (EtOMe2Si+). Elemental analysis value (%);
Fixed value; C: 65.32, H: 6.96, N:
3.74 Calculated value; C: 65.42, H: 7
．． 06, N: 3.63 [0087] The obtained 4-(
3-dimethylethoxysilylpropoxy)-4'nito
Add 2.40 g (62.0 mmol) of rostilbene to ethanol.
Dissolve in 15 ml of alcohol and 6 ml of tetrahydrofuran.
, this solution was mixed with 2.0 g (50 mmol) of sodium hydroxide.
) in 2 ml of water and 15 ml of methanol
and add 2.0 ml of sodium hydroxide to this solution.
Add an aqueous solution of g (50 mmol) dissolved in 10 ml of water.
I got it. After stirring at room temperature for 10 minutes, the reaction solution was
Pour into an excess amount of ice water containing 6.8 g of potassium dihydrogen phosphate.
After extracting with chloroform, the organic phase was diluted with anhydrous sodium sulfate.
It was dried in a humidifier. After distilling off the solvent, silica gel
1.50g of yellow solid purified by muchromatography
I got it. Regarding the obtained product, 1H-NMR, IR
, Mass spectrum analysis and elemental analysis
, the target product 4-(3-dimethylhydroxysilylpropo)
-4'-nitrostilbene
Ta. (Yield; 67.7%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.18 (s, 6H, Si-CH
3), 0.66-0.84 (m, 2H, Si-
CH2CH2CH2-O), 1.69 (s, 1H
, Si-OH), 1.81~2.00 (m, 2H
, Si-CH2CH2CH2-O), 4.00 (
t, 2H, Si-CH2CH2CH2-O), 6
．． 87-7.16 (m, 4H, phenylene group
Roton Peak), 7.44-7.64 (m, 4H
, proton peak of phenylene group), 8.20 (
d, 2H, proton peak of vinylene group). IRs
Spectrum (cm-1); 3280 (characteristic absorption of hydroxyl group)
collection), 2950, 2880, 1590 (Phenic
1510 (characteristic absorption of nitro group), 1510 (characteristic absorption of nitro group)
collection), 1340 (characteristic absorption of nitro group), 1250
(Characteristic absorption due to Si-C bond), 1180, 1
105, 1030, 970, 870, 840. M
ass spectrum (m/e); 357 (M+),
315, 300, 75 (HOMe2Si+). Former
Elementary analysis value (%); Measured value; C: 63.90, H
: 6.38, N: 3.90
Calculated value; C: 63.84, H: 6
．． 49, N: 3.92 Example 7
Synthesis of Monomer 4 [0090] [Chemical 21] 4-(3-dimethylhydrogen obtained in Reference Example 2)
Droxysilylpropoxy)-4'-nitrostilbene
2.00g (5.60mmol) in argon gas atmosphere
Dissolve the solution in 10 ml of tetrahydrofuran, and add the solution to this solution.
1.56 ml (11.2 mmol) of ethylamine and
and 3-methacryloxypropyldimethylchlorosilane 1
．． Add 24g (5.62mmol) and stir at room temperature overnight.
Ta. A white salt is formed, which is mixed with diethyl ether.
After filtering and distilling off the solvent while washing, silica gel
2.40g of yellow solid purified by mucochromatography
I got it. Regarding the obtained product, 1H-NMR, IR
, Mass spectrum analysis and elemental analysis
, confirm that it is a monomer represented by the above structure.
Ta. (Yield: 79.1%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.35-0.70 (m, 4H, Si-
CH2CH2CH2-Ox2), 1.52-1.93
(m, 4H, Si-CH2CH2CH2-O x
2), 1.94 (dd, 3H, CH2=C(CH
3) COO-), 3.96 (t, 2H, Si-C
H2CH2CH2-O), 4.10 (t, 2H,
Si-CH2CH2CH2-O), 5.54 (m,
1H, CH2=C(CH3)COO-), 6.1
0 (m, 1H, CH2=C(CH3)COO-)
, 6.89-7.15 (m, 4H, phenylene group
proton peak), 7.48-7.68 (m, 4
H, proton peak of phenylene group), 8.27 (
d, 2H, proton peak of vinylene group). IRs
Spectrum (cm-1); 2950, 2890, 1
770 (characteristic absorption of carbonyl group), 1635 (C
= characteristic absorption due to C bond), 1590 (phenylene
(characteristic absorption of nitro group), 1510 (characteristic absorption of nitro group),
1340 (characteristic absorption of nitro group), 1250 (
Characteristic absorption due to Si-C bond), 1175, 111
0, 1050 (characteristic absorption due to siloxane bond),
970, 840, 800. Mass spectrum
(m/e); 541 (M+), 248, 217
, 69 (CH2=C(CH3)CO+),41 (
CH2=C(CH3)+). Elemental analysis value (%); Measurement
Value; C: 62.01, H: 7.22, N:
2.55 Calculated value;
C: 62.07, H: 7.26, N: 2.5
9 Example 8 Polymer synthesis 4 00
94 [Image Omitted] 2.04 g of the monomer obtained in Example 7 (
Polymerization reaction was carried out in the same manner as in Example 2 using 3.76 mmol).
After purification, 1.45 g of yellow solid polymer was obtained.
- was obtained. (Yield: 71.1%) Obtained polymer
1H-NMR, IR spectrum analysis and
We conducted elemental analysis and confirmed that the repeating unit was a polymer represented by [Chemical formula 23] [0097]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
4.05x104 and 8.91x respectively
It was 104. The glass transition temperature of this polymer was 61°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.50-0.80 (m, 4H, Si-
CH2CH2CH2-O x2), 0.85-1.10
(m, 3H, -CH2C(CH3)-), 1.4
8-2.15 (m, 6H, Si-CH2CH2C
H2-O x2 and -CH2C(CH3)-),4
．． 00 (t, 2H, Si-CH2CH2CH2-
O), 4.15 (t, 2H, Si-CH2CH
2CH2-O), 6.85-7.16 (m, 4H,
proton peak of phenylene group), 7.46-7.
65 (m, 4H, proton peak of phenylene group
), 8.20 (d, 2H, proton of vinylene group
peak). IR spectrum (cm-1); 2950,
2880, 1715 (characteristic absorption of carbonyl group)
, 1590 (Characteristic absorption of phenylene group), 15
10 (characteristic absorption of nitro group), 1340 (nitro group
(Characteristic absorption due to Si-C bond), 1250 (Characteristic due to Si-C bond)
absorption), 1175, 1110, 1050 (siloki
characteristic absorption due to Sun coupling), 970, 840, 8
00. Elemental analysis value (%); Measured value; C: 61.
98, H: 7.34, N: 2.51 Calculated value;
C: 62.07, H: 7.26, N: 2.5
9 Reference Example 3 Sila having a mesogenic group
Synthesis of Nol Compound 3 [0100] [0101] Methyl p-hydroxybenzoate 15.0 g
(98.6 mmol), potassium carbonate 13.0 g (94
．． A solution of 1 mmol) mixed in 150 ml of acetone
Add 13 ml (150 mmol) of allyl bromide to the alkaline solution.
The mixture was stirred at 80° C. for 2 hours under a gas atmosphere. in this solution
After adding water and extracting with ethyl acetate, the organic phase was extracted with 5% hydroxy acid.
The mixture was washed with an aqueous sodium chloride solution and a saturated saline solution. solvent
After distilling off, it was subjected to silica gel column chromatography.
This was purified to obtain 18.6 g of a colorless transparent liquid. raw obtained
Regarding the product, 1H-NMR, IR, Mass spec.
The target product, p-allyloxybenzoic acid, was analyzed by
I confirmed that it was chill. (Yield; 96.6%) [
1H-NMR spectrum, δ(CDCl3,
ppm); 3.88 (s, 3H, -COOCH
3), 4.58 (dt, 2H, CH2=CHCH
2O−), 5.32(dd, 1H, CH2=CH
CH2O−), 5.43 (dd, 1H, CH2=
CHCH2O-), 5.86-6.22 (m, 1
H, CH2=CHCH2O-), 6.92 (d, 2
H, proton peak of phenylene group), 7.98 (d
, 2H, proton peak of phenylene group). IR
Spectrum (cm-1); 2960, 1720 (cm-1)
(Characteristic absorption of carbonyl group), 1610 (Characteristic absorption of phenylene group)
sexual absorption), 1510, 1435, 1280, 1
255, 1170, 1110, 1020, 845
, 770. Mass spectrum (m/e); 19
2 (M+), 161, 41 (CH2=CHCH2
+). [0103] The p-allyloxybenzoic acid compound obtained here
Chill 18.0g (93.6mmol) and ethanol 60g
0 ml, and this solution was added with 12.0 ml of sodium hydroxide.
g (300 mmol) in 80 ml of water and 1 methanol
Pour into the solution dissolved in 0.00ml and further heat at 80°C.
It was refluxed for 2 hours. The white solid obtained by distilling off the solvent was dissolved in water.
When dissolved in water and added with hydrochloric acid until it becomes acidic, a white precipitate is produced.
It was. This was extracted with methylene chloride, and the organic phase was saturated with
After washing with salt water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off and subjected to silica gel column chromatography.
Purification was performed to obtain 14.7 g of white solid. the product obtained
1H-NMR, IR, Mass spectrum for
Analysis was conducted and the target product was p-allyloxybenzoic acid.
It was confirmed. (Yield; 88.1%) 0104
]1H-NMR spectrum, δ(CDCl3, ppm
); 4.56 (dt, 2H, CH2=CHCH
2O-), 5.27 (dd, 1H, CH2=C
HCH2O-), 5.43 (dd, 1H, CH
2=CHCH2O-), 5.84-6.28 (m,
1H, CH2=CHCH2O-), 6.90 (d
, 2H, proton peak of phenylene group), 7.9
5 (d, 2H, proton peak of phenylene group)
．． IR spectrum (cm-1); 2450-3000
(Characteristic absorption of -OH group of carboxylic acid), 1680 (
Characteristic absorption of carbonyl group), 1600 (phenylene
characteristic absorption of groups), 1550, 1430, 1350,
1250, 1180, 1010, 1000,
930, 850, 770. Mass spectrum (m
/e); 178 (M+), 41 (CH2=CH
CH2+). [0105] Add chlorine to 90 g of phosphorus pentoxide.
100ml loform and 200ml diethyl ether
was added and refluxed for 2 days at 60°C under an argon gas atmosphere.
After that, the solvent is distilled off, and polyphosphoric acid ester (hereinafter referred to as PP
(abbreviated as E) was obtained as a viscous colorless liquid.
. 30.0 g of this PPE and 5.0 g of p-allyloxybenzoic acid.
00g (28.1 mmol) and p-propoxif
Add 4.40 g (28.9 mmol) of phenol to argon gas.
Dissolve in 100 ml of chloroform under a gas atmosphere and store at room temperature.
Stir overnight. Add water and extract with methylene chloride to extract organic
After drying the phase with anhydrous sodium sulfate and distilling off the solvent,
Purified by silica gel column chromatography 8.3
Obtained 0 g of white solid. For the obtained product, 1H
-NMR, IR, Mass spectral analysis and original
Perform elemental analysis to determine the target p-propoxyphenyl p-
It was confirmed that it was allyloxybenzoate. (yield
; 94.6%, melting point; 71°C) 1H
-NMR spectrum, δ (CDCl3, ppm);
1.05(t, 3H, -OCH2CH2CH3),
1.70~1.94 (m, 2H, -OCH2CH
2CH3), 3.93 (t, 2H, -OCH2
CH2CH3), 4.63 (dt, 2H, CH2
=CHCH2O-), 5.36 (dd, 1H,
CH2=CHCH20-), 5.43 (dd, 1H
, CH2=CHCH2O-), 5.88-6.13
(m, 1H, CH2=CHCH2O-)6.85
~7.16 (m, 6H, proton of phenylene group
peak), 8.14 (d, 2H, phenylene group
proton peak). IR spectrum (cm-1); 2
950, 1725 (characteristic absorption of carbonyl group), 1
605 (characteristic absorption of phenylene group), 1515,
1480, 1460, 1430, 1320, 1
310, 1280, 1260, 1170, 10
80, 1020, 940, 850, 800, 7
60. Mass spectrum (m/e); 312 (M
+), 279, 161, 41 (CH2=CHC
H2+). Elemental analysis value (%); Measured value; C: 7
3.04, H: 6.41 Calculated value; C: 73.
06, H: 6.45 [0107] The obtained p-propylene
Ropoxyphenyl p-allyloxybenzoate 3.50
g (11.2 mmol) and dimethylethoxysilane7.
0 ml (50.9 mmol) in tetrahydrofuran 12
Dissolve dicyclopentadienyl platinum di
Chloride methylene chloride solution (0.1 mol/l) 0.
Add 10ml and leave at 50℃ under argon gas atmosphere overnight.
Stirred. After distilling off the solvent, silica gel column chroma
Purified by chromatography to obtain 3.51g of colorless transparent liquid.
Ta. Regarding the obtained product, 1H-NMR, IR,
Mass spectrum analysis and elemental analysis were performed, and the eye
p-propoxyphenyl p-(3-dimethyleth)
Confirmed to be xysilylpropoxy)benzoate
did. (Yield; 75.2%) 1H-N
MR spectrum, δ (CDCl3, ppm); 0.1
5 (s, 6H, Si-CH3), 0.64~0
．． 93 (m, 2H, Si-CH2CH2CH2-
O), 1.04 (t, 3H, -OCH2CH2
CH3), 1.20 (t, 3H, Si-OCH2
CH3), 1.70-2.16 (m, 4H, Si-
CH2CH2CH2-O, -OCH2CH2CH3)
,3.69 (q, 2H, Si-OCH2CH3)
, 3.93 (t, 2H, Si-CH2CH2C
H2-O), 4.12 (t, 2H, -OCH2
CH2CH3), 6.86-7.16 (m, 6H,
proton peak of phenylene group), 8.12 (d,
2H, proton peak of phenylene group). IR spec
vector (cm-1); 2950, 2880, 17
30 (Characteristic absorption of carbonyl group), 1610 (Fe
Characteristic absorption of nylene group), 1580, 1480, 14
00, 1320, 1260 (due to Si-C bond
characteristic absorption), 1190, 1010, 980, 9
50, 850, 800, 770. Mass Spec
Tor (m/e); 416 (M+), 265, 1
61, 145, 103 (EtOMe2Si+),
59 (CH3CH2CH2O+). 0109 Here
p-propoxyphenyl p-(3-dimethyl
(ethoxysilylpropoxy)benzoate 3.50g
(8.40 mmol) was dissolved in 100 ml of acetone,
This solution was heated to 3.5 g (25.3 m
mol) in 30 ml of water and 100 ml of acetone.
Add potassium carbonate to this solution.
Dissolve 3.5g (25.3mmol) in 100ml of water
Aqueous solution was added. After stirring at 0°C for 2 hours, this reaction
The reaction solution was added to an excess of potassium dihydrogen phosphate containing 8.0 g.
Pour into ice water, extract with methylene chloride, and dry the organic phase.
It was dried with sodium sulfate. After distilling off the solvent, silica
2.68g purified by Kagel column chromatography
A white solid was obtained. Regarding the obtained product, 1H-N
MR, IR, Mass spectrum analysis and elemental content
The target product p-propoxyphenyl p-(
3-dimethylhydroxysilylpropoxy)benzoate
It was confirmed that the (Yield; 82.2%) 0
110] 1H-NMR spectrum, δ(CDCl3, p
pm); 0.19 (s, 6H, Si-CH3)
,0.66~0.85 (m, 2H, Si-CH2
CH2CH2-O), 1.04 (t, 3H, -
OCH2CH2CH3), 1.64 (s, 1H,
Si-OH), 1.66-2.00 (m, 4H,
Si-CH2CH2CH2-O, -OCH2CH2C
H3), 3.93 (t, 2H, Si-CH2CH
2CH2-O), 4.03 (t, 2H, -OC
H2CH2CH3), 6.85-7.16 (m, 6H
, proton peak of phenylene group), 8.13 (d
, 2H, proton peak of phenylene group). IR spec
(cm-1); 3450 (Characteristic absorption of hydroxyl group
), 2980, 2900, 1720 (carboni
(Characteristic absorption of phenylene group), 1650 (Characteristic absorption of phenylene group)
absorption), 1440, 1320, 1280, 126
0 (characteristic absorption due to Si-C bond), 1200,
1170, 1110, 1080, 1010, 90
0,850. Mass spectrum (m/e); 3
88 (M+), 237, 195, 121,75
(HOMe2Si+). Example 9 Monomer synthesis 5
] [Chemical formula 25] p-propoxyphenylene obtained in Reference Example 3
p-(3-dimethylhydroxysilylpropoxy)
1.50 g (3.86 mmol) of benzoate was added to Argo.
Dissolved in 10 ml of tetrahydrofuran under a gas atmosphere,
Add 0.65ml (4.66ml) of triethylamine to this solution.
mol) and 3-methacryloxypropyldimethylchloride
Add 1.00g (4.53mmol) of Rorosilane and leave at room temperature.
The mixture was stirred overnight. A white salt will be produced, which should be diethylized.
After filtering and distilling off the solvent while washing with ether, the
Purified by silica gel column chromatography to 2.00
g of pale yellow liquid was obtained. For the obtained product, 1H
-NMR, IR, Mass spectral analysis and original
We performed elementary analysis and determined that the monomer represented by the above structure is
I was sure that. (Yield: 90.5%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.47-0.75 (m, 4H, Si-
CH2CH2CH2-O x2), 1.04 (t,
3H, -OCH2CH2CH3), 1.57-1.
96 (m, 9H, Si-CH2CH2CH2-O
x2, -OCH2CH2CH3, CH2=C(C
H3) COO-), 3.93 (t, 4H, Si-
CH2CH2CH2-O x2), 4.05 (t,
2H, -OCH2CH2CH3), 5.54 (m
, 1H, CH2=C(CH3)COO-)6.10
(m, 1H, CH2=C(CH3)COO-),
6.85-7.16 (m, 6H, phenylene group
proton peak), 8.12 (d, 2H, phenyl
proton peak of ren group). IR spectrum (cm-
1); 2990, 2900, 1740 (carbo
(characteristic absorption of phenylene group), 1650 (characteristic absorption of phenylene group)
absorption), 1615 (characteristic absorption due to C=C bond),
1520 (characteristic absorption of phenylene group), 1260
(Characteristic absorption due to Si-C bond), 1170, 108
0, 1055 (characteristic absorption due to siloxane bond),
850, 800. Mass spectrum (m/e);
572 (M+), 421, 279, 217,
69 (CH2=C(CH3)CO+), 41 (
CH2=C(CH3)+). Example 10
Synthesis of Polymer 5 [0116] 1.90 g of the monomer obtained in Example 9 (
Polymerization reaction was carried out in the same manner as in Example 2 using 3.32 mmol).
After purification, 1.51g of white polymer was obtained.
It was done. (Yield: 79.5%) The obtained polymer
1H-NMR, IR spectrum analysis and elemental
Analysis was conducted and it was confirmed that the repeating unit was a polymer represented by [Chemical formula 27] [0119]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
4.26x104 and 1.06x respectively
It was 105. The glass transition temperature of this polymer was 25°C. this
The glass transition temperature of the polymer was -3°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.45-0.80 (m, 4H, Si-
CH2CH2CH2-O x2), 0.85-1.10
(m, 6H, -CH2C(CH3)-, -OC
H2CH2CH3), 1.48-2.15 (m,
8H, Si-CH2CH2CH2-O x2, -O
CH2CH2CH3, -CH2C(CH3)-),3
．． 94 (t, 4H, Si-CH2CH2CH2-
O x2), 4.05 (t, 2H, -OCH2C
H2CH3), 6.85-7.16 (m, 6H,
proton peak of phenylene group), 8.12 (d,
2H, proton peak of phenylene group). IR spec
Torr (cm-1); 2990, 2900, 173
0 (Characteristic absorption of carbonyl group), 1650 (Phenyl group)
1520 (characteristic absorption of phenylene group), 1520 (characteristic absorption of phenylene group)
(Characteristic absorption), 1250 (Characteristic absorption due to Si-C bond)
, 1170, 1080, 1055 (siloxane bond)
(Characteristic absorption due to combination), 850, 800. 0121
]Reference Example 4 Silanol compound having mesogenic group
Synthesis 4 [0122] [Chemical formula 28] 30.0 g of PPE and p-allyloxybenzoin
5.00 g (28.1 mmol) of acid and 4-cyano
4'-hydroxybiphenyl 5.60g (28.7mm
ol) in 120 ml of chloroform under an argon gas atmosphere.
and stirred overnight at room temperature. Add water and methylene chloride
The organic phase was extracted with anhydrous sodium sulfate.
After distilling off the solvent, silica gel column chromatography
The product was purified in a vacuum to obtain 9.00 g of white solid. raw obtained
Regarding the product, 1H-NMR, IR, Mass spec.
Torr analysis and elemental analysis were performed to determine the target product's 4-(4
'-cyanobiphenyl) p-allyloxybenzoate
It was confirmed that (Yield: 92.1%) 1H-NMR spectrum, δ(CDCl3
, ppm); 4.65 (dt, 2H, CH2
=CHCH2O-), 5.35 (dd, 1H, C
H2=CHCH2O-), 5.45 (dd, 1H
, CH2=CHCH2O-), 5.85-6.30
(m, 1H, CH2=CHCH2O-), 7.0
1 (d, 2H, proton peak of phenylene group)
,7.32 (d, 2H, proton of phenylene group
peak), 7.64 (d, 2H, phenylene group
proton peak), 7.71 (d, 4H, phenyl
Proton peak of ren group), 8.17 (d, 2H,
proton peak of phenylene group), IR spectrum (
cm-1); 2960, 2240 (for C-N bond
(Characteristic absorption of carbonyl group), 1725 (Characteristic absorption of carbonyl group)
), 1600 (characteristic absorption of phenylene group), 15
80, 1510, 1500, 1420, 1320
, 1260, 1210, 1170, 1070,
1000, 950, 825, 765. Mass
Spectrum (m/e); 355 (M+), 161
, 41 (CH2=CHCH2+). Elemental analysis value (%
); Measured value; C: 77.69, H: 4.79
, N: 3.91
Calculated value; C: 77.73, H: 7.82, N
: 3.94 [0125] The obtained 4-(4'-sia)
p-allyloxybenzoate 2.00
g (5.63 mmol) and dimethylethoxysilane3.
0 ml (21.8 mmol) in tetrahydrofuran 60
Dissolve dicyclopentadienyl platinum in ml
Loride methylene chloride solution (0.1 mol/l) 0.2
Add 0ml and heat at 50℃ under argon gas atmosphere for 3 hours.
Stirred. After distilling off the solvent, the target product 4-(4'-shi)
p-(3-dimethylethoxysilyl)
Propoxy)benzoate was obtained as a crude product. the
The structure was confirmed by 1H-NMR, but it is an unstable compound.
Because of this, it was used in the next reaction as it was. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.15 (s, 6H, Si-CH
3), 0.64-0.93 (m, 2H, Si-
CH2CH2CH2-O), 1.20 (t, 3H
, Si-OCH2CH3), 1.68~2.00 (
m, 2H, Si-CH2CH2CH2-O), 3
．． 70 (q, 2H, Si-OCH2CH3),3
．． 95 (t, 2H, Si-CH2CH2CH2-
O), 7.00 (d, 2H, phenylene group
Roton peak), 7.32 (d, 2H, phenylene
(proton peak of
6H, proton peak of phenylene group), 8.17
(d, 2H, proton peak of phenylene group). [0127] 2.10 g of the crude product obtained here was
Dissolved in 20ml of ton and 30ml of tetrahydrofuran
and add 3.5 g (25.5 g) of potassium carbonate to this solution at room temperature.
3 mmol) in 20 ml of water and 60 ml of acetone.
Add potassium carbonate to this solution.
3.5g (25.3mmol) was dissolved in 70ml of water.
Aqueous solution was added. After stirring for 2 hours at room temperature, the reaction
Pour the solution into an excess of ice containing 8.0 g of potassium dihydrogen phosphate.
Pour into water, extract with methylene chloride, and remove the organic phase with anhydrous sulfur.
It was dried with sodium chloride. After distilling off the solvent, the silica
Purified by gel column chromatography and 1.35g of
A white solid was obtained. Regarding the obtained product, 1H-NM
R, IR, Mass spectrum analysis and elemental analysis
The target product 4-(4'-cyanobiphenyl)
p-(3-dimethylhydroxysilylpropoxy)ben
It was confirmed that it was Zoate. (Yield: 5 in 2 steps
5.5%) 1H-NMR spectrum, δ(
CDCl3, ppm); 0.19 (s, 6H,
Si-CH3), 0.67-0.86 (m, 2H,
Si-CH2CH2CH2-O), 1.65 (s
, 1H, Si-OH) 1.84-1.94 (m,
2H, Si-CH2CH2CH2-O), 4.0
6 (t, 2H, Si-CH2CH2CH2-O)
,7.00 (d, 2H, proton of phenylene group
peak), 7.32 (d, 2H, phenylene group
proton peak), 7.60-7.77 (m, 6H
, phenylene group proton peak), 8.16 (d
, 2H, proton peak of phenylene group). IRs
Spectrum (cm-1); 3350 (characteristic absorption of hydroxyl group)
collection), 2970, 2900, 2240 (C-N bond
1730 (characteristic absorption due to carbonyl group), 1730 (characteristic absorption due to carbonyl group)
(characteristic absorption of phenylene group), 1610 (characteristic absorption of phenylene group),
1510, 1270 (Characteristic absorption due to Si-C bond
), 1215, 1175, 1080, 1005,
900, 880, 850, 810. Mass
Spectrum (m/e); 431 (M+), 416 (
M+-Me), 237, 195, 121, 75
(HOMe2Si+). Elemental analysis value (%); Measured value
; C: 69.46, H: 5.69, N: 3
．． 38 Calculated value; C
: 69.58, H: 5.84, N: 3.25
Example 11 Monomer synthesis 6 01
30 [Image Omitted] [0131] 4-(4'-cyanobi) obtained in Reference Example 4
(phenyl) p-(3-dimethylhydroxysilylpro
poxy)benzoate 2.70g (6.26mmol)
into 10 ml of tetrahydrofuran under argon gas atmosphere.
Dissolve and add 1.30 ml (9 ml) of triethylamine to this solution.
．． 32 mmol) and 3-methacryloxypropyl di
1.80g (8.16mmol) of methylchlorosilane
The mixture was added and stirred overnight at room temperature. Since white salt is produced, it
was filtered while washing with diethyl ether, and the solvent was distilled off.
After that, it was purified by silica gel column chromatography.
3.10 g of white solid was obtained. About the product obtained
, 1H-NMR, IR, Mass spectrum analysis
We conducted elemental analysis to identify the monomer represented by the above structure.
It was confirmed that the (Yield: 80.4%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.48-0.80 (m, 4H, Si-
CH2CH2CH2-O x2), 1.59-1.90
(m, 4H, Si-CH2CH2CH2-Ox
2), 1.97 (dd, 3H, CH2=C(CH
3) COO-), 4.00 (t, 2H, Si-C
H2CH2CH2-O), 4.09 (t, 2H,
Si-CH2CH2CH2-O), 5.57 (m,
1H, CH2=C(CH3)COO-), 6.1
3 (m, 1H, CH2=C(CH3)COO-)
,7.00 (d, 2H, proton of phenylene group
peak), 7.32 (d, 2H, phenylene group
proton peak), 7.60-7.77 (m, 6H
, phenylene group proton peak), 8.16 (d
, 2H, proton peak of phenylene group). IR spec
vector (cm-1); 2970, 2900, 22
40 (Characteristic absorption due to C-N bond), 1730 (Ka
Characteristic absorption of carbonyl group), 1625, 1610 (
Characteristic absorption of phenylene group), 1510, 1260 (
Characteristic absorption due to Si-C bond), 1170, 108
0,1060 (characteristic absorption due to siloxane bond),
850, 800. Mass spectrum (m/e);
600 (M+-Me), 516, 421, 21
7, 121,69 (CH2=C(CH3)COO+
), 41 (CH2=C(CH3)+). Elemental analysis value
(%); Measured value; C: 66.36, H: 6.
79, N: 2.29
Calculated value; C: 66.31, H: 6.71,
N: 2.27 Example 12 Polymer
Synthesis 6 of - [0134] [Chemical formula 30] 0.50 g of the monomer obtained in Example 11
(0.35 mmol) in the same manner as in Example 2.
After reaction and purification, 0.35g of white solid poly
Mar was obtained. (Yield; 70.0%) Regarding the obtained polymer,
1H-NMR, IR spectrum analysis and elemental analysis
No, confirm that the repeating unit is a polymer represented by [Chemical formula 31] [0137]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
2.08x104 and 3.68x respectively
It was 104. The glass transition temperature of this polymer was 22°C. Also
, DSC measurement and polarized light microscopy observation revealed that this polymer
- can be used in a wide temperature range from 28℃ to 230℃
It showed a tic liquid crystal phase. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.45-0.70 (m, 4H, Si-
CH2CH2CH2-Ox2), 0.75-1.1
0(m, 3H, -CH2C(CH3)-), 1.4
8~2.00(m, 6H, Si-CH2CH2CH
2-O x2, -CH2C(CH3)-), 3.92
(m, 4H, Si-CH2CH2CH2-Ox
2), 7.00 (d, 2H, phenylene group pro-
ton peak), 7.32 (d, 2H, phenylene
proton peak), 7.60-7.77 (m,
6H, proton peak of phenylene group), 8.16
(d, 2H, proton peak of phenylene group). I
R spectrum (cm-1); 2970, 2900,
2240 (Characteristic absorption due to C-N bond), 1730
(Characteristic absorption of carbonyl group), 1610 (Phenyl group)
characteristic absorption of ren group), 1510, 1260 (Si-
Characteristic absorption due to C bond), 1170, 1080, 10
60 (characteristic absorption due to siloxane bond), 850,
800. Elemental analysis value (%); Measured value; C: 66.13,
H: 6.73, N: 2.22
Calculated value; C: 66.31, H:
6.71, N: 2.27 Example
13 Synthesis of Polymer 7 [0140] 0.40 g of the monomer obtained in Example 1 (
0.76 mmol) and the monomer obtained in Example 11
Example 2 using -0.47g (0.76mmol)
Polymerization reaction and purification were carried out in the same manner, and 0.37 g of white
A solid polymer was obtained. (Yield; 42.5%)
The obtained polymer was analyzed by 1H-NMR and IR spectrum.
vector analysis and elemental analysis, it was confirmed that the repeating unit was a copolymer represented by [Chemical 33] [0143] and [Chemical 34]
Ta. Here, the former repeating unit and the latter repeating unit
The molar ratio of 1H-NMR spectrum and elemental analysis is
The result was 48/52 (mol%). gelper
Number average content determined by migration chromatography
Molecular weight and weight average molecular weight are polystyrene equivalent values.
They are 1.06x104 and 1.78x104, respectively.
Ta. The glass transition temperature of this polymer was 9°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, Si-CH3), 0
．． 45~0.70 (m, Si-CH2CH2CH2
-O), 0.75-1.10 (m, -CH2C(
CH3)-)1.45~2.00 (m, Si-CH
2CH2CH2-O, -CH2C(CH3)-),3
．． 65~4.00 (m, Si-CH2CH2CH2
-O), 7.00 (d, proton pi of phenylene group
), 7.32 (d, proton pi of phenylene group
), 7.60-7.80 (m, phenylene group
proton peak), 8.16 (d, 2H, phenyl
proton peak of ren group). IR spectrum (cm-1
); 2970, 2900, 2240 (C-N bond
(Characteristic absorption due to combination), 1730 (Characteristics of carbonyl group
absorption), 1610 (characteristic absorption of phenylene group),
1510, 1260 (Characteristic absorption due to Si-C bond)
, 1170, 1080, 1060 (siloxane bond)
(characteristic absorption due to combination), 850, 800. Elemental analysis value (
%); Measured value; C: 65.88, H: 7.3
1, N: 2.51 [0147] Example 14 Po
Synthesis of Limer 8 0.40 g of monomer obtained in Example 1
(0.76 mmol) and the monomer obtained in Example 11
Example 2 using 1.41 g (2.29 mmol) of
Polymerization reaction and purification were carried out in the same manner as above, and 0.58 g of white
A colored solid polymer was obtained. (Yield; 32.0%
) Regarding the obtained polymer, 1H-NMR, IR spectrum
Perform spectral analysis and elemental analysis to identify repeating units.
It is a copolymer similar to the polymer obtained in Example 13.
It was confirmed. Here, the former repeating unit shown in Example 13 and the latter
The molar ratio of repeating units of
From the results of elemental analysis, it was 33/67 (mol%).
It was. In addition, in the 1H-NMR spectrum, phenyl
1H-NMR and
and IR spectrum were similar to those of Example 13.
. Determined by gel permeation chromatography
The number average molecular weight and weight average molecular weight of polystyrene
Converted values are 7.15x104 and 1.47x1, respectively.
It was 05. The glass transition temperature of this polymer is 16℃
Met. In addition, DSC measurements and polarized light microscopy observations
This polymer can withstand a wide range of temperatures from 45°C to 148°C.
It exhibited a nematic liquid crystal phase in the degree range. Elemental analysis value (%); Measured value; C: 66.05, H
: 7.19, N: 2.43 [0148] Example
15 Synthesis of Polymer 9 Monomer obtained in Example 1
0.10 g (0.19 mmol) and obtained in Example 11
Using 2.22 g (3.61 mmol) of the monomer obtained
Polymerization reaction and purification were carried out in the same manner as in Example 2, and 1.
29 g of white solid polymer was obtained. (yield;
55.6%) Regarding the obtained polymer, 1H-NM
Perform R, IR spectrum analysis and elemental analysis, and repeat
A copolymer whose return unit is similar to that of the polymer obtained in Example 13
I confirmed that it was a combination. Here, as shown in Example 13,
molar ratio of the former repeating unit to the latter repeating unit
is based on the results of 1H-NMR spectrum and elemental analysis.
It was 4/96 (mol%). In addition, 1H-NMR spectrum
The peak intensities derived from phenylene groups are different in the spectrum.
1H-NMR and IR spectra are as in Example
It was the same as in case 13. gel permeation black
Number average molecular weight and weight average determined by matography
The average molecular weight is 1.41x in terms of polystyrene.
104 and 2.40x104. The glass transition temperature of this polymer was 18°C. Also
, DSC measurement and polarized light microscopy observation revealed that this polymer
- is nematic in a wide temperature range from 25℃ to 170℃
It showed a liquid crystal phase. Elemental analysis value (%); Measured value; C: 66.28, H
: 6.88, N: 2.30 [0149] Reference example
5 Synthesis of silanol compound having mesogenic group 5 [Chemical formula 35] 15.0 g of PPE and p-allyloxybenzoin
4.00 g (22.4 mmol) of acid and p-cyanof
Add 2.66 g (22.3 mmol) of phenol to argon gas.
Dissolve in 100 ml of chloroform under a gas atmosphere and store at room temperature.
Stir overnight. Add water and extract with methylene chloride to extract organic
After drying the phase with anhydrous sodium sulfate and distilling off the solvent,
Purified by silica gel column chromatography 4.8
Obtained 0 g of white solid. For the obtained product, 1H
- Perform NMR, IR, Mass spectrum analysis,
p-cyanophenyl p-allyloxybenzoate
It was confirmed that the (Yield; 76.7%) [
1H-NMR spectrum, δ(CDCl3,
ppm); 4.63 (dt, 2H, CH2=
CHCH2O-), 5.36 (dd, 1H, CH
2=CHCH2O-), 5.45 (dd, 1H,
CH2=CHCH2O-), 5.88-6.24
(m, 1H, CH2=CHCH2O-), 7.01
(d, 2H, proton peak of phenylene group),
7.34 (d, 2H, proton pi of phenylene group
(d, 2H, phenylene group), 7.73 (d, 2H, phenylene group)
Roton peak), 8.13 (d, 2H, phenylene
(proton peak of ion group), IR spectrum (cm-1)
; 2960, 2230 (characteristic absorption due to C-N bond
collection), 1720 (characteristic absorption of carbonyl group), 16
00 (characteristic absorption of phenylene group), 1580,15
00, 1450, 1420, 1325, 131
0, 1260, 1200, 1180, 1060
, 990, 920, 880, 840, 755
．． Mass spectrum (m/e); 279 (M+)
, 161, 41 (CH2=CHCH2+). 0
153] Obtained p-cyanophenyl p-allyloxy
Benzoate 1.90g (5.72mmol) and dimethylene
2.50 ml (18.2 mmol) of ethoxysilane
Dissolve dicyclopenta in 30 ml of tetrahydrofuran.
Dienylplatinum dichloride solution in methylene chloride (0
．． Add 0.20 ml of 1 mol/l) and place in an argon gas atmosphere.
The mixture was stirred for 3 hours at 50°C under ambient air. After distilling off the solvent,
Purified by silica gel column chromatography to 1.8
0 g of a colorless transparent liquid was obtained. Regarding the obtained product,
1H-NMR, IR, Mass spectrum analysis
p-cyanophenyl p-(3-dimethyl
Ethoxysilylpropoxy) benzoate
confirmed. (Yield: 72.9%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.14 (s, 6H, Si-CH
3), 0.63~0.82 (m, 2H, Si-
CH2CH2CH2-O), 1.19 (t, 3H
, Si-OCH2CH3), 1.60~1.98 (
m, 2H, Si-CH2CH2CH2-O), 3
．． 68 (q, 2H, Si-OCH2CH3),4
．． 03 (t, 2H, Si-CH2CH2CH2-
O), 6.97 (d, 2H, phenylene group
Roton peak), 7.34 (d, 2H, phenylene
(proton peak of ion group). 7.72 (d, 2H,
proton peak of phenylene group), 8.12 (d,
2H, proton peak of phenylene group). IR spec
Torr (cm-1); 3000, 2960, 289
0,2200 (Characteristic absorption due to C-N bond), 173
0 (Characteristic absorption of carbonyl group), 1600 (Fe
Characteristic absorption of nylene group), 1580, 1510, 14
75, 1420, 1410, 1390, 126
0 (characteristic absorption due to Si-C bond), 1200,
1150, 1040, 990, 940, 880
, 840, 800, 770, 750. Mass
Spectrum (m/e); 368 (M+-Me),
326, 265, 145, 121, 103 (
EtOMe2Si+), [0155] The obtained p-cyanophenyl p-(3-
Dimethylethoxysilylpropoxy)benzoate 1.
Dissolve 75 g in 35 ml of acetone and bring this solution to room temperature.
Add 1.5g (10.9mmol) of potassium carbonate to 25g of water.
ml and a solution dissolved in 60 ml of acetone.
, further add 1.5 g (10.9 m
An aqueous solution prepared by dissolving mol) in 45 ml of water was added. room temperature
After stirring for 2 hours, the reaction solution was added with dihydrogen phosphate solution.
Pour into an excess amount of ice water containing 5.0 g of chloride.
After extraction with methylene, the organic phase was dried over anhydrous sodium sulfate.
did. After distilling off the solvent, silica gel column chromatography
Purification was performed using Raffy to obtain 1.40 g of white solid. Obtained
1H-NMR, IR, Mass
Perform spectral analysis to identify the target p-cyanophenyl
p-(3-dimethylhydroxysilylpropoxy) base
It was confirmed that the substance was inzoate. (Yield; 86.4
%)0156 1H-NMR spectrum, δ(CDC
l3, ppm); 0.19 (s, 6H, Si-
CH3), 0.67-0.89 (m, 2H, Si
-CH2CH2CH2-O), 1.70 (s, 1
H, Si-OH) 1.83~2.02 (m, 2H
, Si-CH2CH2CH2-O), 3.67 (
t, 2H, Si-CH2CH2CH2-O), 6.
98 (d, 2H, proton peak of phenylene group
), 7.35 (d, 2H, proto of phenylene group
peak), 7.73 (d, 2H, phenylene group
proton peak), 8.12 (d, 2H, phenyl
proton peak of ren group). IR spectrum (cm-1
); 3500 (characteristic absorption of hydroxyl group), 2950,
2880, 2240 (characteristic absorption due to C-N bond),
1930, 1720 (Characteristic absorption of carbonyl group)
, 1600 (characteristic absorption of phenylene group), 1510
,, 1470, 1410, 1390, 1320
, 1250 (characteristic absorption due to Si-C bond), 12
00, 1150, 1040, 1000, 870
, 820, 760. Mass spectrum (m/e)
; 355 (M+), 340 (M+-Me), 2
37, 195, 121, 75 (HOMe2Si
+). Example 16 Monomer synthesis 7 [
embedded image p-cyanophenyl obtained in Reference Example 5
p-(3-dimethylhydroxysilylpropoxy)ben
1.25g (3.52mmol) of zoate was added to argon gas.
Dissolve in 15 ml of tetrahydrofuran under gas atmosphere.
Add 1.00 ml of triethylamine (7.17 mmo
l) and 3-methacryloxypropyldimethylchloro
Add 0.93g (4.22mmol) of silane and let stand at room temperature.
It was stirred overnight. A white salt will be produced, which can be mixed with diethyl ethyl ethyl ethyl ethyl ethyl ether.
After filtering and distilling off the solvent while washing with
Purified by gel column chromatography and 1.72g of
A white solid was obtained. Regarding the obtained product, 1H-NM
R, IR, Mass spectrum analysis was performed, and the above
It was confirmed that it was a monomer represented by the structure. (Collection
90.5%) 1H-NMR spectrum
Torr, δ (CDCl3, ppm); 0.10 (s,
12H, Si-CH3), 0.53-0.75 (
m, 4H, Si-CH2CH2CH2-O x2)
, 1.61~1.96 (m, 4H, Si-CH2
CH2CH2-O x2), 1.94 (dd, 3
H, CH2=C(CH3)COO-), 4.03 (t
, 2H, Si-CH2CH2CH2-O), 4.
31 (t, 2H, Si-CH2CH2CH2-O
), 5.53 (m, 1H, CH2=C(CH3)
COO-), 6.10 (m, 1H, CH2=
C(CH3)COO-), 6.98 (d, 2H,
proton peak of phenylene group), 7.35 (d, 2
H, proton peak of phenylene group), 7.73 (
d, 2H, proton peak of phenylene group), 8.1
2 (d, 2H, proton peak of phenylene group)
．． IR spectrum (cm-1); 2950, 290
0, 2250 (Characteristic absorption due to C-N bond), 17
40 (Characteristic absorption of carbonyl group), 1720, 1
600 (characteristic absorption of phenylene group), 1510, 1
320, 1300, 1255 (due to Si-C bond)
characteristic absorption), 1210, 1160, 1060 (
characteristic absorption due to siloxane bonds), 1000, 84
0,800. Mass spectrum (m/e); 52
4 (M+-Me), 482, 440, 421,
217, 121,69 (CH2=C(CH3)C
OO+), 41 (CH2=C(CH3)+). Example 17 Polymer synthesis 10 01
62 [Image Omitted] 1.49 g of monomer obtained in Example 16
(2.76 mmol) in the same manner as in Example 2.
After reaction and purification, 1.10 g of white solid poly
Mar was obtained. (Yield: 73.8%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 38] [0165]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
3.49x104 and 6.40x respectively
It was 104. The glass transition temperature of this polymer was 7°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.08 (s, 12H, Si-C
H3), 0.39-0.55 (m, 4H, Si-
CH2CH2CH2-Ox2), 0.70-1.2
0(m, 3H, -CH2C(CH3)-), 1.3
8~1.84 (m, 6H, Si-CH2CH2C
H2-O x2, -CH2C(CH3)-), 3.9
4 (m, 4H, Si-CH2CH2CH2-O
x2), 6.93 (d, 2H, phenylene group
Roton peak), 7.30 (d, 2H, phenylene
Proton peak of 2H group), 7.67 (d, 2H,
proton peak of phenylene group), 8.07 (d,
2H, proton peak of phenylene group). IR spec
Torr (cm-1); 3010, 2950, 288
0, 2210 (Characteristic absorption due to C-N bond), 17
25 (characteristic absorption of carbonyl group), 1600 (characteristic absorption of carbonyl group)
characteristic absorption of phenylene group), 1510, 1250 (S
characteristic absorption due to i-C bond), 1200, 1160,
1055 (characteristic absorption due to siloxane bond), 10
00, 840, 790. Elemental analysis value (%); Measurement
Value; C: 62.24, H: 7.10, N:
2.38 Calculated value; C
: 62.31, H: 6.91, N: 2.59
Reference Example 6 Silano having a mesogenic group
Synthesis of compound 6 [Chemical formula 39] 15.0 g of PPE and p-allyloxybenzoin
4.00 g (22.4 mmol) of acid and p-hexyl
4.40g (22.6mmol) of xyphenol
Dissolve in 100 ml of chloroform under a gas atmosphere and store in a room.
Stir overnight at warm temperature. Add water and extract with methylene chloride.
The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off.
After that, it was purified by silica gel column chromatography.
6.10 g of white solid was obtained. About the product obtained
, 1H-NMR, IR, Mass spectrum analysis
No, the target p-hexyloxyphenyl p-allylo
It was confirmed that it was cibenzoate. (Yield; 76
．． 8%) 1H-NMR spectrum, δ(
CDCl3, ppm); 0.92 (t, 3H,
-OCH2(CH2)4CH3), 1.23-1.8
3 (m, 8H, -OCH2(CH2)4CH3)
, 3.96 (t, 2H, -OCH2(CH2)
4CH3), 4.63 (dt, 2H, CH2=C
HCH2O-), 5.35 (dd, 1H, CH
2=CHCH2O−), 5.43 (dd, 1H,
CH2=CHCH2O-), 5.90-6.25 (
m, 1H, CH2=CHCH2O-), 6.90
(d, 2H, proton peak of phenylene group), 6.
98 (d, 2H, proton peak of phenylene group)
,7.10 (d, 2H, proton of phenylene group
peak), 8.13 (d, 2H, phenylene group
Proton peak), IR spectrum (cm-1); 2
960, 2940, 2860, 1720 (Cal
(Characteristic absorption of phenylene group), 1600 (Characteristic absorption of phenylene group)
sexual absorption), 1580, 1510, 1470, 14
50, 1420, 1390, 1315, 1300
, 1270, 1250, 1190, 1160,
1070, 1000, 985, 920, 870
, 840, 800, 770. Mass spectrum
(m/e); 354 (M+), 161, 41
(CH2=CHCH2+). [0171] The obtained p-
Hexyloxyphenyl p-allyloxybenzoate 4
．． 00g (11.3mmol) and dimethylethoxysila
Add 3.0 ml (21.8 mmol) of water to tetrahydrofurane.
Dissolve dicyclopentadienyl platinum in 50 ml of
Mudichloride methylene chloride solution (0.1 mol/l)
Add 0.20ml and heat at 50℃ under argon gas atmosphere.
Stirred for 3 hours. After distilling off the solvent, the target product p-hex
Siloxyphenyl p-(3-dimethylethoxysilyl
Propoxy)benzoate was obtained as a crude product. [0172] The crude product obtained here was mixed with 70 m of acetone.
3.0 g of potassium carbonate at room temperature.
(21.7 mmol) in 50 ml of water and 10 ml of acetone.
Pour into the solution dissolved in 0 ml, and add charcoal to this solution.
3.0g (21.7mmol) of potassium acid in 80ml of water
An aqueous solution dissolved in was added. After stirring at room temperature for 4 hours
, this reaction solution containing 8.0 g of potassium dihydrogen phosphate
After pouring into excess ice water and extracting with methylene chloride, the organic
The phase was dried over anhydrous sodium sulfate. the solvent was distilled off
After that, it was purified by silica gel column chromatography.
．． 81 g of white solid was obtained. Regarding the obtained product,
1H-NMR, IR, Mass spectrum analysis
p-hexyloxyphenyl p-(3-dimethyl)
hydroxysilylpropoxy)benzoate
It was confirmed. (Yield: 57.7% in 2 steps) 0
173] 1H-NMR spectrum, δ(CDCl3,p
pm); 0.19 (s, 6H, Si-CH3)
,0.66~0.76 (m, 2H, Si-CH2
CH2CH2-O), 0.93 (t, 3H, -
OCH2(CH2)4CH3), 1.22-2.06
(m, 11H, -OCH2(CH2)4CH3,
Si-OH, Si-CH2CH2CH2-O), 3.
96 (t, 2H, -OCH2(CH2)4CH3
), 4.04 (t, 2H, Si-CH2CH2
CH2-O), 6.90 (d,2H, phenylene group
proton peak), 6.96 (d, 2H, phenyl
Proton peak of ren group), 7.11 (d, 2H,
proton peak of phenylene group), 8.13 (d,
2H, proton peak of phenylene group). IR spec
(cm-1); 3250 (Characteristic absorption of hydroxyl group
), 2950, 2880, 1720 (carbonyl
(Characteristic absorption of phenylene group), 1600 (Characteristic absorption of phenylene group)
collection), 1500, 1470, 1420, 1380
, 1310, 1280 (Characteristics due to Si-C bond
absorption), 1220, 1180, 1160, 107
0, 1030, 1000, 880, 840,
810,760. Mass spectrum (m/e); 4
30 (M+), 237, 195, 121, 7
5 (HOMe2Si+). Example 18
Monomer synthesis 8 [Chemical formula 40] p-hexyloxyphene obtained in Reference example 6
p-(3-dimethylhydroxysilylpropoxy)
) 2.20 g (5.11 mmol) of benzoate was added to the alkaline
Dissolve in 20ml of tetrahydrofuran under gas atmosphere.
, 1.40 ml (10.0 ml) of triethylamine was added to this solution.
mmol) and 3-methacryloxypropyldimethyl
Add 1.30 g (5.89 mmol) of chlorosilane to the chamber.
Stir overnight at warm temperature. A white salt will be generated, so remove it from the die.
After filtering and distilling off the solvent while washing with methyl ether,
Purified by silica gel column chromatography 2.8
Obtained 0 g of white solid. For the obtained product, 1H
- Perform NMR, IR, Mass spectrum analysis,
It was confirmed that the monomer is represented by the structure above.
. (Yield: 89.1%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.47-0.75 (m, 4H, Si-
CH2CH2CH2-O x2), 0.91 (t,
3H, -OCH2(CH2)4CH3), 1.25
~1.90 (m, 12H, Si-CH2CH2C
H2-O x2, -OCH2(CH2)4CH3),
1.95 (dd, 3H, CH2=C(CH3)C
OO-), 3.96 (t, 2H, -OCH2(
CH2)4CH3),4.01 (t, 2H, Si
-CH2CH2CH2-O), 4.11 (t, 2
H, Si-CH2CH2CH2-O), 5.54 (
m, 1H, CH2=C(CH3)COO-), 6
．． 10 (m, 1H, CH2=C(CH3)CO
O-), 6.90 (d, 2H, phenylene group pro-
peak), 6.96 (d, 2H, phenylene group
proton peak), 7.11 (d, 2H, phenyl
Proton peak of ren group), 8.13 (d, 2H,
Proton peak of phenylene group). IR spectrum (
cm-1); 2950, 2870, 1720 (
Characteristic absorption of carbonyl group), 1610 (phenylene
characteristic absorption of the group), 1510, 1250 (Si-C
characteristic absorption due to bonding), 1190, 1160, 10
70, 1050 (characteristic absorption due to siloxane bond)
, 1000, 840, 800. Mass Spect
Le (m/e); 614 (M+), 515, 42
1, 217, 69 (CH2=C(CH3)COO
+), 41 (CH2=C(CH3)+). 0178
Example 19 Synthesis of Polymer 11 [Chemical Formula 41] 2.00 g of the monomer obtained in Example 18
(3.25 mmol) in the same manner as in Example 2.
After reaction and purification, 1.20 g of white solid poly
Mar was obtained. (Yield: 60.0%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 42] [0182]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
4.69x104 and 9.28x respectively
It was 104. The glass transition temperature of this polymer was -1°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.08 (s, 12H, Si-C
H3), 0.30~0.65 (m, 4H, Si-
CH2CH2CH2-O x2), 0.75-1.20
(m, 6H, -CH2C(CH3)-, -OCH
2(CH2)4CH3), 1.28-2.00(m,
14H, Si-CH2CH2CH2-Ox2, -
CH2C(CH3)-, -OCH2(CH2)4CH
3), 3.84-3.97 (m, 6H, Si-C
H2CH2CH2-O x2, -OCH2(CH2)
4CH3), 6.86 (d, 2H, phenylene group
proton peak), 6.90 (d, 2H, Fe
proton peak of nylene group), 7.06 (d, 2H
, proton peak of phenylene group), 8.08 (d,
2H, proton peak of phenylene group). IR spec
vector (cm-1); 2950, 2900, 28
50, 1730 (Characteristic absorption of carbonyl group), 16
00 (characteristic absorption of phenylene group), 1575, 1
500, 1460, 1415, 1385, 125
0 (characteristic absorption due to Si-C bond), 1190,
1160, 1050 (characteristic absorption due to siloxane bond)
), 1000, 885, 830, 780. 0
184] Reference Example 7 Silanolization with mesogenic group
Synthesis of compound 7 [0185] [Chemical formula 43] 15.0 g of PPE and p-allyloxybenzoin
4.00 g (22.4 mmol) of acid and p-hexyl
4.00g (22.4mmol) of phenol in argon
Dissolve in 100 ml of chloroform under gas atmosphere and bring to room temperature.
The mixture was stirred overnight. Add water and extract with methylene chloride.
After drying the organic phase with anhydrous sodium sulfate and distilling off the solvent
6. Purified by silica gel column chromatography.
Obtained 50 g of white solid. For the product obtained, 1
Perform H-NMR, IR, and Mass spectrum analysis
, target p-hexylphenyl p-allyloxyben
It was confirmed that it was Zoate. (Yield; 85.7%
) 1H-NMR spectrum, δ(CDC
l3, ppm); 0.92 (t, 3H, -C
H2(CH2)4CH3), 1.25-1.85 (m
, 8H, -OCH2(CH2)4CH3), 2.
62 (t, 2H, -OCH2(CH2)4CH3
)4.62 (dt, 2H, CH2=CHCH2O
-), 5.36 (dd, 1H, CH2=CHC
H2O-), 5.43 (dd, 1H, CH2=C
HCH2O-), 5.88-6.30 (m, 1H,
CH2=CHCH2O-), 6.98 (d, 2H
, proton peak of phenylene group), 7.15 (d
, 4H, proton peak of phenylene group), 8.1
4 (d, 2H, proton peak of phenylene group)
, IR spectrum (cm-1); 2960, 294
0, 2850, 1720 (characteristic absorption of carbonyl group)
collection), 1610 (characteristic absorption of phenylene group), 15
80, 1510, 1450, 1420, 141
0, 1280, 1260, 1200, 1160,
1100, 1070, 1010, 1000,
915, 880, 840, 810, 760. M
ass spectrum (m/e); 338 (M+),
161, 41 (CH2=CHCH2+). 018
8] Obtained p-hexylphenyl p-allyloxybe
4.00g (11.8mmol) and dimethyl
Add 2.50 ml (18.2 mmol) of ethoxysilane to the
Dissolve dicyclopentadi in 50 ml of trahydrofuran.
Enylplatinum dichloride in methylene chloride solution (0.
Add 0.20 ml of 1 mol/l) and create an argon gas atmosphere.
The mixture was stirred for 3 hours at 50°C under air. After distilling off the solvent,
p-hexylphenyl p-(3-dimethyleth)
xysilylpropoxy)benzoate as crude product
Obtained. [0189] The crude product obtained here was mixed with 70 m of acetone.
3.0 g of potassium carbonate at room temperature.
(21.7 mmol) in 50 ml of water and 10 ml of acetone.
Pour into the solution dissolved in 0 ml, and add charcoal to this solution.
3.0g (21.7mmol) of potassium acid in 80ml of water
An aqueous solution dissolved in was added. After stirring at room temperature for 2 hours
, this reaction solution containing 8.0 g of potassium dihydrogen phosphate
After pouring into excess ice water and extracting with methylene chloride, the organic
The phase was dried over anhydrous sodium sulfate. the solvent was distilled off
After that, it was purified by silica gel column chromatography.
．． 20g of white solid was obtained. Regarding the obtained product,
1H-NMR, IR, Mass spectrum analysis
p-hexylphenyl p-(3-dimethylphenyl)
hydroxysilylpropoxy) benzoate.
I confirmed that. (Yield: 45.0% in 2 steps) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.20 (s, 6H, Si-CH
3), 0.67~0.78 (m, 2H, Si-C
H2CH2CH2-O), 0.95 (t, 3H,
-CH2(CH2)4CH3), 1.22-1.83
(m, 11H, -CH2(CH2)4CH3,
Si-OH, Si-CH2CH2CH2-O), 2.
64 (t, 2H, -CH2(CH2)4CH3)
, 4.05 (t, 2H, Si-CH2CH2C
H2-O), 6.97 (d, 2H, phenylene group
proton peak), 7.16 (d, 4H, Fe
proton peak of nylene group), 8.15 (d, 2H
, proton peak of phenylene group). IR spectrum
(cm-1); 3200 (characteristic absorption of hydroxyl group),
2960, 2930, 2850, 1720 (Cal
(characteristic absorption of phenylene group), 1600 (characteristic absorption of phenylene group), 1600 (characteristic absorption of phenylene group)
characteristic absorption), 1580, 1510, 1470, 1
420, 1260 (Characteristic absorption due to Si-C bond)
, 1200, 1180, 1060, 1040,
1015, 995, 900, 860, 840,
760. Mass spectrum (m/e); 414
(M+), 397 (M+-OH), 237, 1
95, 121,75 (HOMe2Si+). 01
91 Example 20 Synthesis of Monomer 9 [Chemical Formula 44] p-hexylphenyl obtained in Reference Example 7
p-(3-dimethylhydroxysilylpropoxy) base
1.65g (3.98mmol) of nizoate was added to
Dissolve in 15 ml of tetrahydrofuran under gas atmosphere.
Add 1.20 ml of triethylamine (8.62 mm
ol) and 3-methacryloxypropyldimethylchloro
Add 1.05g (4.76mmol) of Rosilan and let it cool at room temperature.
Stir overnight. A white salt is produced, which can be converted into diethyl
After filtering and distilling off the solvent while washing with ether,
Purified by Kagel column chromatography, 2.26g
A white solid was obtained. Regarding the obtained product, 1H-N
MR, IR, and Mass spectrum analysis were performed, and the above
It was confirmed that the monomer has the structure: (Yield; 94.8%) 1H-NMR spectrum, δ
(CDCl3, ppm); 0.10 (s, 12
H, Si-CH3), 0.56-0.75 (m,
4H, Si-CH2CH2CH2-O x2), 0
．． 92 (t, 3H, -CH2(CH2)4CH3
), 1.21~1.95 (m, 12H, Si-C
H2CH2CH2-O x2, -CH2(CH2)4C
H3), 1.94 (dd, 3H, CH2=C(C
H3)COO-), 2.58 (t,2H, -CH
2(CH2)4CH3), 4.01 (t, 2H,
Si-CH2CH2CH2-O), 4.11 (t,
2H, Si-CH2CH2CH2-O), 5.53
(m, 1H, CH2=C(CH3)COO-),
6.10 (m, 1H, CH2=C(CH3)
COO-), 6.90 (d, 2H, phenylene group
proton peak), 7.20 (d, 4H, Fe
Proton peak of nylene group), 8.13 (d, 2H,
Proton peak of phenylene group). IR spectrum (
cm-1); 2955, 2950, 2870,
1720 (characteristic absorption of carbonyl group), 1610 (
Characteristic absorption of phenylene group), 1510, 1320,
1300, 1255 (Characteristic absorption due to Si-C bond
), 1200, 1160, 1070, 1050
(Characteristic absorption due to siloxane bond), 1010,
840, 800. Mass spectrum (m/e);
598 (M+), 583 (M+-Me), 54
1, 499, 421, 217, 121,69
(CH2=C(CH3)COO+), 41 (CH2
=C(CH3)+). Example 21 Poly
Synthesis of Monomer 12 [0195] 1.60 g of monomer obtained in Example 20
(2.67 mmol) in the same manner as in Example 2.
After reaction and purification, 1.10 g of viscous liquid poly
Mar was obtained. (Yield: 68.8%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 46] [0198]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
3.52x104 and 7.19x respectively
It was 104. The glass transition temperature of this polymer was -18°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.08 (s, 12H, Si-C
H3), 0.40~0.65 (m, 4H, Si-
CH2CH2CH2-O x2), 0.75-1.20
(m, 6H, -CH2C(CH3)-, -CH2
(CH2)4CH3), 1.25-1.90 (m, 1
4H, Si-CH2CH2CH2-Ox2, -C
H2C(CH3)-, -CH2(CH2)4CH3)
,2.54 (t, 2H, -CH2(CH2)4C
H3), 3.95 (t,4H, Si-CH2CH
2CH2-O x2), 6.90 (d, 2H, F
proton peak of phenylene group), 7.10 (d, 4
H, proton peak of phenylene group), 8.10 (
d, 2H, proton peak of phenylene group). IR
Spectrum (cm-1); 2950, 2930,
2860, 2850, 1730 (characteristics of carbonyl group)
(characteristic absorption of phenylene group), 1605 (characteristic absorption of phenylene group),
1580, 1510, 1470, 1420, 1
315, 1250 (Characteristic absorption due to Si-C bond)
, 1190, 1160, 1060 (siloxane bond)
characteristic absorption), 840, 795, 760,
690. Reference Example 8 Having a mesogenic group
Synthesis of silanol compound 8 [Chemical formula 47] 15.0 g of PPE and p-allyloxybenzoin
3.67 g (20.6 mmol) of acid and p-phenyl
3.50g (20.6mmol) of phenol in argon
Dissolve in 100 ml of chloroform under gas atmosphere and bring to room temperature.
The mixture was stirred overnight. Add water and extract with methylene chloride.
After drying the organic phase with anhydrous sodium sulfate and distilling off the solvent
, purified by silica gel column chromatography, and
Further recrystallization from ethyl acetate yielded 4.45 g of white solid.
Ta. Regarding the obtained product, 1H-NMR, IR,
Mass spectrum analysis was performed to identify the target 4-biphene.
Confirmed that it is p-allyloxybenzoate.
Ta. (Yield; 65.4%) 1H-NMR spectrum, δ(CDCl3
, ppm); 4.63 (dt, 2H, CH2
=CHCH2O-), 5.35 (dd, 1H, C
H2=CHCH2O-), 5.44 (dd, 1H
, CH2=CHCH2O-), 5.76-6.24
(m, 1H, CH2=CHCH2O-), 7.0
1 (d, 2H, proton peak of phenylene group)
,7.22~7.68 (m, 9H, phenylene group
proton peak), 8.17 (d, 2H, Fe
Proton peak of nylene group), IR spectrum (cm-
1); 3070, 2900, 1725 (carbo
(characteristic absorption of phenylene group), 1605 (characteristic absorption of phenylene group)
absorption), 1580, 1510, 1485, 14
50, 1420, 1405, 1380, 1310
, 1250, 1210, 1180, 1160,
1105, 1060, 980, 920, 88
0, 840, 760, 690. Mass spectrum
(m/e); 330 (M+), 161, 41
(CH2=CHCH2+). Obtained 4-biphenyl p-allyloxy
Benzoate 4.10g (12.4mmol) and dimethylene
2.40 ml (17.4 mmol) of ethoxysilane
Dissolve dicyclopenta in 50 ml of tetrahydrofuran.
Dienylplatinum dichloride solution in methylene chloride (0
．． Add 0.20 ml of 1 mol/l) and place in an argon gas atmosphere.
The mixture was stirred for 3 hours at 50°C under ambient air. After distilling off the solvent,
Target product 4-biphenyl p-(3-dimethylethoxy
Silylpropoxy)benzoate was obtained as crude product.
. [0205] The crude product obtained here was diluted with 100% acetone.
ml of potassium carbonate, and the solution was heated to 2.0 ml of potassium carbonate at room temperature.
g (14.5 mmol) in 40 ml of water and 1 acetone.
Pour into the solution dissolved in 00ml, and then add to this solution.
2.0g (14.5mmol) of potassium carbonate in 80ml of water
An aqueous solution of 1 ml was added. Stirred at room temperature for 2 hours.
After that, this reaction solution was added containing 8.0 g of potassium dihydrogen phosphate.
Pour into excess ice water and extract with methylene chloride.
The organic phase was dried over anhydrous sodium sulfate. distill off the solvent
After that, it was purified by silica gel column chromatography.
2.50 g of white solid was obtained. About the product obtained
, 1H-NMR, IR, Mass spectrum analysis
4-biphenyl p-(3-dimethylhydrogen)
Droxysilylpropoxy) benzoate
confirmed. (Yield: 49.6% in two steps) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.20 (s, 6H, Si-CH
3), 0.67~0.86 (m, 2H, Si-C
H2CH2CH2-O), 1.64 (s, 1H,
Si-OH) 1.74-2.12 (m, 4H,
Si-CH2CH2CH2-O), 4.06 (t,
2H, Si-CH2CH2CH2-O), 6.99
(d, 2H, proton peak of phenylene group),
7.23-7.68 (m, 9H, phenylene group
proton peak), 8.17 (d, 2H, phenyl
proton peak of ren group). IR spectrum (cm-1
); 3400, 3200 (characteristic absorption of hydroxyl group),
3060, 2950, 2850, 1720 (Ka
characteristic absorption of carbonyl group), 1700, 1600 (
characteristic absorption of phenylene group), 1580, 1510,
1485, 1420, 1320, 1260 (S
characteristic absorption due to i-C bond), 1220, 1160,
1070, 1000, 880, 840, 7
50. Mass spectrum (m/e); 406 (M
+), 349, 311, 237, 195, 1
21, 75 (HOMe2Si+). 0207] Fruit
Example 22 Synthesis of Monomer 10 4-biphenyl p- obtained in Reference Example 8
(3-dimethylhydroxysilylpropoxy)benzoe
2.00 g (4.92 mmol) of
Dissolve in 20 ml of tetrahydrofuran under ambient atmosphere, and add this solution.
and triethylamine 1.00ml (7.17mmol)
and 3-methacryloxypropyldimethylchlorosila
Add 1.30 g (5.89 mmol) of water and stir overnight at room temperature.
Stirred. A white salt is formed, which is treated with diethyl ether.
After filtering and distilling off the solvent while washing with a silica gel
Purified by column chromatography to give 1.44g of colorless
A viscous liquid was obtained. Regarding the obtained product, 1H-NM
R, IR, Mass spectrum analysis was performed, and the above
It was confirmed that it was a monomer represented by the structure. (Yield: 49.5%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.08 (s, 12H, Si-C
H3), 0.43 to 0.76 (m, 4H, Si-
CH2CH2CH2-Ox2), 1.53-1.96
(m, 4H, Si-CH2CH2CH2-O x
2), 1.92 (dd, 3H, CH2=C(CH
3) COO-), 3.99 (t, 2H, Si-C
H2CH2CH2-O), 4.09 (t, 2H,
Si-CH2CH2CH2-O), 5.51 (m,
1H, CH2=C(CH3)COO-)), 6.
07 (m, 1H, CH2=C(CH3)COO-
), 6.95 (d, 2H, proto of phenylene group
peak), 7.20 to 7.65 (m, 9H, peak
Proton peak of phenylene group), 8.10 (d, 2H
, proton peak of phenylene group). IR spectrum
(cm-1); 2950, 2870, 1730
(characteristic absorption of carbonyl group), 1605 (phenylene
characteristic absorption of groups), 1510, 1485, 1320
, 1290, 1250 (characteristic absorption due to Si-C bond)
collection), 1200, 1160, 1065 (Shiroki
characteristic absorption due to Sun coupling), 1000, 840,
790, 755. Mass spectrum (m/e);
590 (M+), 533, 491, 421,
217, 170,69 (CH2=C(CH3)CO
O+), 41 (CH2=C(CH3)+). 02
11] Example 23 Polymer synthesis 13 [Chemical formula 49] 1.20 g of monomer obtained in Example 22
(2.00 mmol) in the same manner as in Example 2.
After reaction and purification, 0.68 g of white solid poly
Mar was obtained. (Yield: 57.6%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 50] [0215]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
1.41x104 and 2.55x respectively
It was 104. The glass transition temperature of this polymer was 25°C. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.12 (s, 12H, Si-C
H3), 0.44-0.70 (m, 4H, Si-
CH2CH2CH2-Ox2), 0.75-1.1
0(m, 3H, -CH2C(CH3)-), 1.4
5-2.03 (m, 6H, Si-CH2CH2C
H2-O x2 and -CH2C(CH3)-),
3.89~4.05 (m, 4H, Si-CH2C
H2CH2-O x2), 6.95 (d, 2H,
proton peak of phenylene group), 7.19-7.64
(m, 9H, proton peak of phenylene group),
8.14 (d, 2H, proton pi of phenylene group
). IR spectrum (cm-1); 3020,
2950, 1730 (characteristic absorption of carbonyl group),
1605 (characteristic absorption of phenylene group), 1510,
1485, 1250 (Characteristic absorption due to Si-C bond
), 1200, 1160, 1065 (siloxane
characteristic absorption due to bonding), 1000, 840, 79
0, 755, 690. Reference example 9
Synthesis of silanol compound having sogenic group 9 [Chemical formula 51] 20.0 g of PPE and p-allyloxybenzoin
4.86 g (27.3 mmol) of acid and 4-butoxy
-4'-hydroxybiphenyl 6.60g (27.3m
mol) in 100 m of chloroform under an argon gas atmosphere.
1 and stirred overnight at room temperature. Add water and add methane chloride.
Extracted with water and dried the organic phase with anhydrous sodium sulfate.
After distilling off the solvent, silica gel column chromatography
The product was purified in a vacuum cleaner to obtain 9.15 g of white solid. obtained
Regarding the product, 1H-NMR, IR, Mass spectrum
4-(
4'-butoxybiphenyl) p-allyloxybenzoe
It was confirmed that the (Yield; 83.4%)
1H-NMR spectrum, δ(CDCl3
, ppm); 0.98 (t, 3H, -OCH
2(CH2)2CH3), 1.38-1.89 (m,
4H, -OCH2(CH2)2CH3), 4.0
1 (t, 2H, -OCH2(CH2)2CH3)
,4.64 (dt, 2H, CH2=CHCH2O
-), 5.38 (dd, 1H, CH2=CHC
H2O-), 5.55 (dd, 1H, CH2=C
HCH2O-), 5.94-6.13 (m, 1H
, CH2=CHCH2O-),6.96 (d,2H
, proton peak of phenylene group), 7.00 (d
, 2H, proton peak of phenylene group), 7.24
(d, 2H, proton peak of phenylene group),
7.50 (d, 2H, proton pi of phenylene group
(d, 2H, phenylene group), 7.58 (d, 2H,
Roton peak), 8.16 (d, 2H, phenylene
(proton peak of ion group), IR spectrum (cm-1)
; 2960, 2940, 2880, 1720
(characteristic absorption of carbonyl group), 1600 (phenylene
characteristic absorption of groups), 1510, 1470, 1320
, 1245, 1210, 1160, 1070, 1
040, 940, 840, 810, 760. M
ass spectrum (m/e); 402 (M+),
161, 41 (CH2=CHCH2+). 02
21] Obtained 4-(4'-butoxybiphenyl) p
- Allyloxybenzoate 8.75 g (21.0 mmo
l) and 7.30 ml (53.0 ml) of dimethylethoxysilane
mmol) in 100 ml of tetrahydrofuran,
Dicyclopentadienylplatinum dichloride chloride
Add 0.50 ml of tyrene solution (0.1 mol/l),
The mixture was stirred at 50° C. for 3 hours under an argon gas atmosphere. solvent
After distilling off, the target product 4-(4'-butoxybiphenylene)
p-(3-dimethylethoxysilylpropoxy)
Benzoate was obtained as crude product. [0222] The crude product obtained here was mixed with 35m of acetone.
1 and 50 ml of tetrahydrofuran.
9.0 g (65.1 mmol) of potassium carbonate was added to the solution at room temperature.
) in 15 ml of water and 45 ml of acetone
and then add 9.0 g of potassium carbonate (
Add an aqueous solution of 65.1 mmol) dissolved in 45 ml of water.
I got it. After stirring at room temperature for 8 hours, the reaction solution was phosphorized.
Pour into excess ice water containing 30g of potassium dihydrogen acid.
After extraction with methylene chloride, the organic phase was extracted with anhydrous sodium sulfate.
It was dried. After distilling off the solvent, silica gel column
Purified by chromatography to obtain 4.38g of white solid.
Ta. Regarding the obtained product, 1H-NMR, IR,
Mass spectrum analysis and elemental analysis were performed, and the eye
4-(4'-butoxybiphenyl) p-(3-
dimethylhydroxysilylpropoxy)benzoate
I confirmed that there is. (Yield: 42.2% in 2 steps)
1H-NMR spectrum, δ(CDCl3
, ppm); 0.12 (s, 6H, Si-CH
3), 0.52~0.82 (m, 2H, Si-C
H2CH2CH2-O), 0.98 (t, 3H,
-OCH2(CH2)2CH3), 1.12-1.9
2 (m, 7H, -OCH2(CH2)2CH3,
Si-OH, Si-CH2CH2CH2-O), 3
．． 97 (t, 2H, -OCH2(CH2)2CH
3), 4.00 (t, 2H, Si-CH2CH2
CH2-O), 6.92 (d, 4H, phenylene
proton peak), 7.20 (d, 2H,
proton peak of phenylene group), 7.84 (d, 2
H, proton peak of phenylene group), 7.92 (
d, 2H, proton peak of phenylene group), 8.
10 (d, 2H, proton peak of phenylene group
). IR spectrum (cm-1); 3400 (hydroxy acid
characteristic absorption of groups), 2960, 2940, 2880
, 1740 (Characteristic absorption of carbonyl group), 172
0, 1620 (characteristic absorption of phenylene group), 151
0, 1490, 1440, 1410, 1260
(Characteristic absorption due to Si-C bond), 1220, 1
175, 1090, 1060, 1010, 990
, 900, 840, 820, 780. Mass
Spectrum (m/e); 478 (M+), 416
, 362, 242, 186, 121, 75
(HOMe2Si+). Example 24
Synthesis of Nomer 11 [0225] 4-(4'-butoxy obtained in Reference Example 9)
biphenyl) p-(3-dimethylhydroxysilylp)
Ropoxy)benzoate 3.90g (8.15mmol
) in 30 ml of tetrahydrofuran under argon gas atmosphere.
3.27 ml of triethylamine (
23.7 mmol) and 3-methacryloxypropyl
Dimethylchlorosilane 2.10g (9.46mmol)
was added and stirred at room temperature overnight. White salt is generated, so avoid
Filter it while washing with diethyl ether and distill off the solvent.
After that, it was purified by silica gel column chromatography.
3.00 g of white solid was obtained. Regarding the obtained product
For 1H-NMR, IR, Mass spectrum analysis,
We conducted elemental analysis to identify the monomer represented by the above structure.
It was confirmed that the (Yield: 55.5%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.54-0.86 (m, 4H, Si-
CH2CH2CH2-O x2), 1.00 (t,
3H, -OCH2(CH2)2CH3) 1.20~
1.90 (m, 4H, Si-CH2CH2CH2
-Ox2, -OCH2(CH2)2CH3), 1.
94 (dd, 3H, CH2=C(CH3)COO
-), 4.02 (t, 4H, Si-CH2CH
2CH2-O, -OCH2(CH2)2CH3),4
．． 11 (t, 2H, Si-CH2CH2CH2-
O), 5.54 (m, 1H, CH2=C(CH
3) COO-), 6.10 (m, 1H, CH2=
C(CH3)COO-), 6.97 (d, 4H,
proton peak of phenylene group), 7.27 (d,
2H, proton peak of phenylene group), 7.51
(d, 2H, proton peak of phenylene group), 7
．． 58 (d, 2H, proton py of phenylene group
h), 8.16 (d, 2H, phenylene group pro-
Ton Peak). IR spectrum (cm-1); 296
0, 2940, 2880, 1730 (carboni
(Characteristic absorption of phenylene group), 1605 (Characteristic absorption of phenylene group)
collection), 1500, 1470, 1320, 129
0,1250 (Characteristic absorption due to Si-C bond), 1
215, 1170, 1070 (due to siloxane bond)
characteristic absorption), 1040, 1010, 970,
900, 840, 810. Mass spectrum (
m/e); 662 (M+), 493, 421,
379, 337, 242, 217, 121,
69 (CH2=C(CH3)COO+), 41 (
CH2=C(CH3)+). Example 25 Polymer synthesis 14 02
29] [0230] 2.00 g of monomer obtained in Example 24
(2.86 mmol) in the same manner as in Example 2.
After reaction and purification, 1.40 g of white solid poly
Mar was obtained. (Yield: 70.0%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 54] [0232]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
2.12x104 and 4.44x respectively
It was 104. The glass transition temperature of this polymer was 21°C. Also
, DSC measurement and polarized light microscopy observation revealed that this polymer
- can be used in a wide temperature range from 55℃ to 156℃
It showed a tic liquid crystal phase. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.54-0.62 (m, 4H, Si-
CH2CH2CH2-O x2), 0.88-1.43
(m, 6H, -CH2C(CH3)-, -OC
H2(CH2)2CH3), 1.58-1.83 (m
, 10H, Si-CH2CH2CH2-Ox2,
-CH2C(CH3)-, -OCH2(CH2)2C
H3), 3.96 (m, 6H, Si-CH2CH
2CH2-O x2, -OCH2(CH2)2CH3
), 6.97 (d, 4H, proton of phenylene group
peak), 7.27 (d, 2H, phenylene group
proton peak), 7.54 (d, 2H, phenyl
Proton peak of ren group), 7.60 (d, 2H,
proton peak of phenylene group), 8.16 (d,
2H, proton peak of phenylene group). IR spec
vector (cm-1); 2960, 2880, 17
30 (Characteristic absorption of carbonyl group), 1605 (Fe
Characteristic absorption of nylene group), 1510, 1500, 1
470, 1250 (characteristic absorption due to Si-C bond),
1210, 1165, 1070 (for siloxane bond)
characteristic absorption), 1040, 1000, 840,
800, 760. Reference Example 10 Cyrano having a mesogenic group
Synthesis of Mol Compound 10 [Chemical Formula 55] 23.4 g of PPE and p-allyloxybenzoin
3.83 g (21.5 mmol) of acid and 4-(S-2
-methylbutoxy)-4'-hydroxybiphenyl5.
50g (21.5mmol) was heated under an argon gas atmosphere.
Dissolve in 120 ml of loloform and stir overnight at room temperature.
Ta. Add water, extract with methylene chloride, and extract the organic phase with anhydrous sulfur.
After drying with sodium chloride and distilling off the solvent, silica gel
Purified by column chromatography to yield 7.28g of white
A solid was obtained. Regarding the obtained product, 1H-NMR,
Performed IR, mass spectrum analysis and elemental analysis.
No, target product 4-(4'-(S-2-methylbutoxy)
) biphenyl) p-allyloxybenzoate
I confirmed that. (Yield: 81.5%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.98 (t, 3H, -OCH
2CH(CH3)CH2CH3), 1.04 (d,
3H, -OCH2CH(CH3)CH2CH3),1
．． 09-1.45 (m, 1H, -OCH2CH(C
H3) CH2CH3), 1.69-1.90 (m,
2H, -OCH2CH(CH3)CH2CH3),
3.83 (dd, 2H, -OCH2CH(CH
3) CH2CH3), 4.64 (dt, 2H,
CH2=CHCH2O-), 5.37 (dd, 1H
, CH2=CHCH2O-), 5.44 (dd,
1H, CH2=CHCH2O-), 5.85-6
．． 25 (m, 1H, CH2=CHCH2O-),
6.97 (d, 2H, proton pi of phenylene group
(d, 2H, phenylene group), 7.00 (d, 2H,
Roton peak), 7.24 (d, 2H, phenylene
proton peak of fluorine group), 7.51 (d, 2H, fluorophore group)
proton peak of phenylene group), 7.58 (d, 2
H, proton peak of phenylene group), 8.17 (
d, 2H, proton peak of phenylene group). IR
Spectrum (cm-1); 3060, 3000,
2970, 1770 (characteristic absorption of carbonyl group),
1650, 1620 (characteristic absorption of phenylene group),
1545, 1510, 1490, 1450, 1
445, 1420, 1330, 1300, 12
65, 1220, 1150, 1125, 108
0, 1040, 950, 910, 880,84
5, 800, 720, 690. Mass Spect
Le (m/e); 416 (M+), 356, 25
6, 186, 161, 105, 41 (CH2
=CHCH2+). The obtained 4-(4'-
(S-2-methylbutoxy)biphenyl) p-arylo
7.00 g (16.8 mmol) of xybenzoate and
Methylethoxysilane 5.90ml (44.3mmol
) in 50 ml of tetrahydrofuran and dicyclopetrope.
Methylene chloride solution of ntadienylplatinum dichloride
(0.1 mol/l) and add 0.50 ml of argon gas.
The mixture was stirred at 50° C. for 3 hours under a gas atmosphere. After distilling off the solvent, the target product 4-(4'-(S-2-method)
(methylbutoxy)biphenyl) p-(3-dimethyleth)
xysilylpropoxy)benzoate as crude product
Obtained. [0239] The crude product obtained here was mixed with 45 m of acetone.
1 and 30 ml of tetrahydrofuran.
9.0 g (65.1 mmol) of potassium carbonate was added to the solution at room temperature.
) in 15 ml of water and 45 ml of acetone
and then add 9.0 g of potassium carbonate (
Add an aqueous solution of 65.1 mmol) dissolved in 45 ml of water.
I got it. After stirring at room temperature for 2 hours, the reaction solution was phosphorized.
Pour into excess ice water containing 20g of potassium dihydrogen acid.
After extraction with methylene chloride, the organic phase was extracted with anhydrous sodium sulfate.
It was dried. After distilling off the solvent, silica gel column
Purified by chromatography to obtain 4.13g of white solid.
Ta. Regarding the obtained product, 1H-NMR, IR,
Mass spectrum analysis and elemental analysis were performed, and the eye
4-(4'-(S-2-methylbutoxy)biphetamine)
p-(3-dimethylhydroxysilylpropyl)
c) It was confirmed that it was benzoate. (Yield; 2
49.9% in stages) 1H-NMR spectrum
Le, δ(CDCl3, ppm); 0.10 (s,
6H, Si-CH3), 0.59-0.89 (m,
2H, Si-CH2CH2CH2-O), 0.9
6 (t, 3H, -OCH2CH(CH3)CH2
CH3), 1.04 (d, 3H, -OCH2CH
(CH3)CH2CH3), 1.09-1.49 (m
, 1H, -OCH2CH(CH3)CH2CH3)
, 1.60-2.19 (s, 5H, Si-OH,
Si-CH2CH2CH2-O, -OCH2CH(
CH3) CH2CH3), 3.83 (dd, 2H,
-OCH2CH(CH3)CH2CH3), 4.0
5 (t, 2H, Si-CH2CH2CH2-O)
, 6.97 (d, 4H, proton of phenylene group
peak), 7.24 (d, 2H, phenylene group
proton peak), 7.51 (d, 2H, phenyl
Proton peak of ren group), 7.58 (d, 2H,
proton peak of phenylene group), 8.16 (d,
2H, proton peak of phenylene group). IR spec
(cm-1); 3400 (Characteristic absorption of hydroxyl group
), 2960, 2930, 2870, 1730
(Characteristic absorption of carbonyl group), 1700, 1605
(Characteristic absorption of phenylene group), 1495, 1470
, 1250 (Characteristic absorption due to Si-C bond), 1
210, 1165, 1070, 1040,100
5, 990, 840, 800, 760. Mas
s spectrum (m/e); 492 (M+), 23
7, 195, 121, 75 (HOMe2Si+
). Example 26 Monomer synthesis 12 [
##STR56## 4-(4'-(S-) obtained in Reference Example 10
2-methylbutoxy)biphenyl) p-(3-dimethy
hydroxysilylpropoxy)benzoate 3.90
g (7.92 mmol) under argon gas atmosphere
Dissolve in 25 ml of hydrofuran and add triethyl to this solution.
3.28 ml (23.8 mmol) of amine and
2.10g of tacryloxypropyldimethylchlorosilane
(9.46 mmol) was added and stirred overnight at room temperature. White
Salts will form, so do not wash them with diethyl ether.
After filtering and distilling off the solvent, silica gel column chroma
The product was purified by tography to obtain 3.81 g of white solid. Regarding the obtained product, 1H-NMR, IR, Ma
We performed ss spectrum analysis and elemental analysis, and the above
It was confirmed that it was a monomer represented by the structure. (Collection
rate; 71.1%) 1H-NMR spectrum
Torr, δ (CDCl3, ppm); 0.10 (s,
12H, Si-CH3), 0.40~0.80 (
m, 4H, Si-CH2CH2CH2-O x2)
,0.98 (t, 3H, -OCH2CH(CH3
)CH2CH3), 1.04 (t, 3H, -O
CH2CH(CH3)CH2CH3), 1.10-1.
49 (m, 1H, -OCH2CH(CH3)CH
2CH3), 1.60~1.90 (m, 6H, S
i-CH2CH2CH2-O x2, -OCH2CH
(CH3)CH2CH3), 1.97 (dd, 3H
, CH2=C(CH3)COO-), 3.81 (
d, 2H, -OCH2CH(CH3)CH2CH3
), 4.02 (t, 2H, Si-CH2CH2C
H2-O), 4.12 (t, 2H, Si-CH
2CH2CH2-O), 5.54 (m, 1H, C
H2=C(CH3)COO-)), 6.10 (m,
1H, CH2=C(CH3)COO-), 6.97
(d, 4H, proton peak of phenylene group), 7
．． 24 (d, 2H, proton peak of phenylene group
), 7.51 (d, 2H, proton of phenylene group
peak), 7.58 (d, 2H, phenylene group
proton peak), 8.16 (d, 2H, phenyl
proton peak of ren group). IR spectrum (cm-1
); 2990, 2950, 2900, 1730
(Characteristic absorption of carbonyl group), 1640, 1610
(Characteristic absorption of phenylene group), 1585, 1515
, 1505, 1470, 1420, 1390,
1320, 1300, 1250 (for Si-C bond
characteristic absorption), 1210, 1170, 1070 (
Characteristic absorption due to siloxane bonds), 1010, 85
0, 810, 770. Mass spectrum (m/e
); 677 (M+), 507, 421, 37
9, 337, 256, 217, 121,69
(CH2=C(CH3)COO+), 41 (CH2
=C(CH3)+). Example 27 Poly
Synthesis of monomer 15 [Chemical formula 57] 3.60 g of monomer obtained in Example 26
(5.32 mmol) in the same manner as in Example 2.
After reaction and purification, 1.96 g of white solid poly
Mar was obtained. (Yield: 54.5%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 58] [0249]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
4.77x104 and 7.96x respectively
It was 104. The glass transition temperature of this polymer was 20°C. Also
, DSC measurement and polarized light microscopy observation revealed that this polymer
- is chiral over a wide temperature range from 45℃ to 127℃
It exhibited a smectic liquid crystal phase. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.40-0.80 (m, 4H, Si-
CH2CH2CH2-Ox2), 0.95-1.38
(m, 10H, -OCH2CH(CH3)CH2
CH3, -OCH2CH(CH3)CH2CH3,-
OCH2CH(CH3)CH2CH3, -CH2C(
CH3)-), 1.40-1.90 (m, 8H,
Si-CH2CH2CH2-O x2, -CH2C(
CH3)-, -OCH2CH(CH3)CH2CH3
), 3.80 (d, 2H, -OCH2CH(CH
3) CH2CH3), 4.06 (t, 4H, S
i-CH2CH2CH2-O x2), 6.97 (d
, 4H, proton peak of phenylene group), 7.2
4 (d, 2H, proton peak of phenylene group)
,7.51 (d, 2H, proton of phenylene group
peak), 7.58 (d, 2H, phenylene group
proton peak), 8.16 (d, 2H, phenyle
(proton peak of ion group). IR spectrum (cm-1)
; 2950, 2880, 1730 (carbonyl
(Characteristic absorption of phenylene group), 1610 (Characteristic absorption of phenylene group)
), 1510, 1500, 1470, 1310
, 1250 (Characteristic absorption due to Si-C bond), 1
210, 1170, 1070 (due to siloxane bond)
characteristic absorption), 1010, 995, 850, 8
00. Reference Example 11 Having a mesogenic group
Synthesis of silanol compound 11 [0252] [Chemical formula 59] 15.0 g of PPE and p-allyloxybenzoin
2.65 g (15.2 mmol) of acid and 4-octyl
4.50 g of xy-4'-hydroxybiphenyl (13.
4 mmol) in chloroform under an argon gas atmosphere.
The solution was dissolved in 0 ml and stirred at room temperature overnight. Add water and chloride
Extract with methylene and extract the organic phase with anhydrous sodium sulfate.
After drying and distilling off the solvent, silica gel column chromatography
It was purified using Raffy to obtain 5.30 g of white solid. Obtained
1H-NMR, IR, Mass
Perform spectral analysis to identify the 4-(4'-octyl) of the target.
(oxybiphenyl) p-allyloxybenzoate
I was sure that. (Yield: 86.2%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.73 (t, 3H, -OCH
2(CH2)6CH3), 1.00-1.85 (m,
12H, -OCH2(CH2)6CH3), 3.
96 (t, 2H, -OCH2(CH2)6CH3)
,4.60 (dt, 2H, CH2=CHCH2O
-), 5.36 (dd, 1H, CH2=CHC
H2O-), 5.43 (dd, 1H, CH2=C
HCH2O-), 5.85-6.23 (m, 1H
, CH2=CHCH2O-), 6.93 (d, 2H
, proton peak of phenylene group), 6.97 (d
, 2H, proton peak of phenylene group), 7.20
(d, 2H, proton peak of phenylene group),
7.47 (d, 2H, proton pi of phenylene group
(d, 2H, phenylene group), 7.55 (d, 2H,
Roton peak), 8.13 (d, 2H, phenylene
(proton peak of ion group). IR spectrum (cm-1)
; 2960, 2930, 2850, 1725
(characteristic absorption of carbonyl group), 1610 (phenylene
characteristic absorption of the group), 1500, 1470, 1310
,1290, 1250, 1215,1165, 1
080, 1010, 995, 930, 880,
840, 800, 760, 690. Mass
Spectrum (m/e); 458 (M+), 298,
161, 41 (CH2=CHCH2+). The obtained 4-(4'-octyloxybife)
p-allyloxybenzoate 5.00g (10
．． 9 mmol) and 2.5 ml of dimethylethoxysilane (
18.2 mmol) was dissolved in 50 ml of tetrahydrofuran.
and dicyclopentadienyl platinum dichloride.
0.20 ml of methylene chloride solution (0.1 mol/l)
and stirred for 3 hours at 50°C under an argon gas atmosphere.
. After distilling off the solvent, the target product 4-(4'-octyloxy)
(sibiphenyl) p-(3-dimethylethoxysilylp)
Ropoxy)benzoate was obtained as a crude product. [0256] The crude product obtained here was mixed with 40 m of acetone.
1 and 60 ml of tetrahydrofuran.
3.5 g (25.3 mmol) of potassium carbonate was added to the solution at room temperature.
) in 50 ml of water and 120 ml of tetrahydrofuran.
Pour into the dissolved solution, and add potassium carbonate to this solution.
Dissolve 3.5g (25.3mmol) of Mu in 100ml of water.
Added the aqueous solution. After stirring at room temperature for 2 hours, this
The reaction solution was added to an excess amount containing 12 g of potassium dihydrogen phosphate.
Pour into ice water, extract with methylene chloride, and dry the organic phase.
It was dried with sodium sulfate. After distilling off the solvent, silica
4.01g purified by Kagel column chromatography
A white solid was obtained. Regarding the obtained product, 1H-N
Perform MR, IR, and Mass spectrum analysis to determine the purpose.
4-(4'-octyloxybiphenyl) p-(3
-dimethylhydroxysilylpropoxy)benzoate
It was confirmed that (Yield: 68.8% in 2 steps
) 1H-NMR spectrum, δ(CDCl
3, ppm); 0.20 (s, 6H, Si-C
H3), 0.58-0.70 (m, 2H, Si-
CH2CH2CH2-O), 0.75 (t, 3H
, -OCH2(CH2)6CH3), 1.20-2.
10 (m, 15H, Si-OH, Si-CH2
CH2CH2-O, -OCH2(CH2)6CH3)
,4.01 (t, 2H, -OCH2(CH2)
6CH3), 4.06 (t, 2H, Si-CH
2CH2CH2-O), 6.98 (d, 4H, F
proton peak of phenylene group), 7.25 (d, 2
H, proton peak of phenylene group), 7.52 (
d, 2H, proton peak of phenylene group), 7.
59 (d, 2H, proton peak of phenylene group
), 8.17 (d, 2H, proto of phenylene group
peak). IR spectrum (cm-1); 3280
(characteristic absorption of hydroxyl groups), 2960, 2940,
2860, 1740 (characteristic absorption of carbonyl group),
1610 (characteristic absorption of phenylene group), 1510,
1500, 1470, 1400, 1250 (S
characteristic absorption due to i-C bond), 1220, 1160
, 1075, 1040, 1000, 890, 8
60, 840, 800, 760, 680. Ma
ss spectrum (m/e); 534 (M+), 4
18, 298, 237, 195, 121, 7
5 (HOMe2Si+). Example 28
Synthesis of Monomer 13 [Chemical Formula 60] 4-(4'-octyl
p-(3-dimethylhydroxybiphenyl)
3.60 g (6.73 m
mol) in tetrahydrofuran 2 under an argon gas atmosphere.
Dissolve 2.00 mL of triethylamine in this solution.
ml (14.3 mmol) and 3-methacryloxyp
Lopyldimethylchlorosilane 1.48g (6.71mm
ol) was added and stirred at room temperature overnight. white salt is produced
Then, filter it while washing with diethyl ether and remove the solvent.
After distilling off, it was subjected to silica gel column chromatography.
Purification was performed to obtain 2.01 g of white solid. the product obtained
1H-NMR, IR, Mass spectrum for
The analysis revealed that the monomer has the structure shown above.
It was confirmed. (Yield: 38.2%) 1H-NMR spectrum, δ(CDCl3
, ppm); 0.11 (s, 12H, Si-C
H3), 0.32 to 0.65 (m, 4H, Si-
CH2CH2CH2-O x2), 0.75 (t,
3H, -OCH2(CH2)6CH3), 1.10
~1.90 (m, 16H, Si-CH2CH2C
H2-O x2, -OCH2(CH2)6CH3),
1.95 (s, 3H, CH2=C(CH3)CO
O-), 4.02 (t, 2H, -OCH2(C
H2)6CH3),4.07 (t, 2H, Si-
CH2CH2CH2-O), 4.12 (t, 2H
, Si-CH2CH2CH2-O), 5.54 (m
, 1H, CH2=C(CH3)COO-)), 6
．． 11 (m, 1H, CH2=C(CH3)CO
O-), 6.97 (d, 4H, phenylene group pro-
peak), 7.24 (d, 2H, phenylene group
proton peak), 7.51 (d, 2H, phenyl
proton peak of ren group), 7.59 (d, 2H,
proton peak of phenylene group), 8.16 (d,
2H, proton peak of phenylene group). IR spec
vector (cm-1); 3000, 2950, 29
00, 1730 (Characteristic absorption of carbonyl group), 16
10 (characteristic absorption of phenylene group), 1510, 1
500, 1260 (characteristic absorption due to Si-C bond),
1210, 1170, 1070, 1070 (Shi
characteristic absorption due to loxane bonds), 900, 840,
820, 770. Mass spectrum (m/e);
719 (M+), 549, 421, 379,
298, 217, 121,69 (CH2=C(
CH3)COO+),41 (CH2=C(CH3)+
). Example 29 Polymer synthesis 16 [
[0263] 1.20 g of monomer obtained in Example 28
(1.67 mmol) in the same manner as in Example 2.
After reaction and purification, 0.78 g of white solid poly
Mar was obtained. (Yield: 65.0%) Regarding the obtained polymer, 1
Performed H-NMR, IR spectrum analysis and elemental analysis.
Confirm that the repeating unit is a polymer represented by [Chemical formula 62] [0266]
Ta. Determined by gel permeation chromatography
The calculated number average molecular weight and weight average molecular weight are
2.37x104 and 4.38x respectively
It was 104. The glass transition temperature of this polymer was 19°C. Also
, DSC measurement and polarized light microscopy observation revealed that this polymer
- can be used in a wide temperature range from 45℃ to 164℃
It showed a tic liquid crystal phase. 1H-NMR spectrum, δ(CDCl3
, ppm); 0.10 (s, 12H, Si-C
H3), 0.33-0.70 (m, 4H, Si-
CH2CH2CH2-Ox2), 0.72-1.35
(m, 6H, -CH2C(CH3)-, -OCH
2(CH2)6CH3), 1.45-1.98(m,
18H, Si-CH2CH2CH2-Ox2, -
CH2C(CH3)-, -OCH2(CH2)6CH
3), 3.94 (m, 6H, Si-CH2CH2
CH2-O x2, -OCH2(CH2)6CH3)
, 6.91 (d, 4H, proton of phenylene group
peak), 7.20 (d, 2H, phenylene group
proton peak), 7.48 (d, 2H, phenyl
proton peak of ren group), 7.59 (d, 2H,
proton peak of phenylene group), 8.13 (d,
2H, proton peak of phenylene group). IR spec
vector (cm-1); 2970, 2950, 28
90, 1735 (Characteristic absorption of carbonyl group), 16
10 (characteristic absorption of phenylene group), 1510, 1
500, 1480, 1255 (due to Si-C bond
characteristic absorption), 1210, 1165, 1060 (characteristic absorption)
characteristic absorption due to loxane bonds), 910, 840,
800, 760.

Claims (2)

[Claims] Claim 1: The following general formula (I) [Formula 1] (wherein R is a hydrogen atom, a halogen atom, an alkyl group or a phenyl group, R1 to R6 may be the same or different, and an alkyl group or a phenyl group, X is a single bond, an oxygen atom, or a group represented by -COO- or -OCO-, Q is a mesogenic group, m and p are integers of 2 to 20, n
is an integer from 0 to 50. ) A polymerizable monomer having a mesogenic group represented by: [Claim 2] The repeating unit is represented by the following general formula (II)
[Formula 2] (wherein, R is a hydrogen atom, a halogen atom, an alkyl group, or a phenyl group, R1 to R6 may be the same or different, and an alkyl group or a phenyl group, and X is a single bond, an oxygen atom, or -COO - or -OCO-, Q is a mesogenic group, m and p are integers of 2 to 20, n
is an integer from 0 to 50. However, R, R1 to R6,
, Q, m, n and p may be arbitrarily different for each repeating unit. ) and has a mesogenic group and has a weight average molecular weight of 1,000 to 1,000,000, determined as a polystyrene equivalent value using gel permeation chromatography.