JPH06329805A - Organopolysiloxane with difunctional biphenyl group and its production - Google Patents

Abstract

PURPOSE: To provide a polysiloxane which contains specified difunctional biphenyl groups and reacts with various monomers to synthesize new polymers having organosiloxane side chains and a polyamide, polyimide or polyurea chain as the main chain thereof.

CONSTITUTION: There is provided an organopolysiloxane containing difunctional biphenyl groups represented by formula I (wherein Z is nitro or amino; A is an organopolysiloxane of formula II; R¹ is a divalent 2C or higher organic group; R² to R⁶ are each a monovalent organic group; n is 1 or greater; and m is 0 or 1). An organohydropolysiloxane of formula III is reacted with a dinitrobiphenyl compound of formula IV (wherein R⁷ is an organic group having a terminal ethylenic unsaturation; and m is 0 or 1) in the presence of a catalyst to obtain an organopolysiloxane of formula VI. A compound of formula V is reduced to obtain an organopolysiloxane having diaminobiphenyl groups of the formula VI. The compound of the formula VI is silylated to obtain an organopolysiloxane having trialkylsilylaminobiphenyl groups of formula VII (wherein R⁸ is an alkyl).

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel organopolysiloxane and a method for producing the same. More specifically, it relates to a novel organopolysiloxane having a bifunctional biphenyl group and a method for producing the same.

[0002]

2. Description of the Related Art A macromonomer, which has been actively researched in recent years, is a polymer (including an oligomer) having a polymerizable functional group, and by incorporating it into a graft copolymer as a branch, Graft copolymers whose length and number are controlled can be obtained [for review, edited by Yuya Yamashita, Macromonomer Chemistry and Industry, IPC (1989), Yusuke Kawakami, Polymer, 37, 2
64 pages (1988), Yoshiki Nakajo, Polymer, 39 volumes,
452 page (1990) etc.].

Most of the macromonomers known so far have a vinylphenyl group, an acryloyl group or a methacryloyl group as a terminal polymerization group, and are mainly for chain polymerization. On the other hand, macromonomers for sequential polymerization have been reported to have diols, dicarboxylic acids, dicarboxylic acid esters, diamines, phenols, etc. at their terminals [Tezuka et al., Polymer, Volume 30,
Page 553 (1989); Tezuka et al., Macromol.
ecules, 24, 122 (1991); Kawakami et al., Polym. Bull. 25, pp. 521 (1991); Okawa et al., JP-A-1-132634; Nagase et al., Makromol. Chem. , Rapi
d Commun. , Volume 11, Page 185 (199
0); Nagase et al., JP-A-1-185327, K.S.
M. Snow et al., CAP-2,025,289 (199).
1/06/23) etc.]].

[0004]

However, an organopolysiloxane having a bifunctional biphenyl group as a polymerizing group and a method for producing the same have not yet been known. If this functional group is an amino group or a trialkylsilylamino group, it is expected that a novel polymer having an organopolysiloxane side chain and having a main chain such as polyamide, polyimide or polyurea can be synthesized.

An object of the present invention is to provide a novel organopolysiloxane having a bifunctional biphenyl group, which is useful as a raw material for synthesizing the side chain type copolymer as described above, and a method for producing the same. is there.

[0006]

The above-mentioned object is achieved by the following formula I

[0007]

[Chemical 8]

Wherein Z is a nitro group or a substituted or unsubstituted amino group, and A is the following formula II

[0009]

[Chemical 9]

Organopolysiloxane (R ¹
Is a divalent organic group having 2 or more carbon atoms, R ^{2 to} R ⁶ are the same or different monovalent organic groups, and n is an integer of 1 or more,
R ⁴ and R ⁵ may be different for each repeating unit. )
Where m is 0 or 1 with an organopolysiloxane having a bifunctional biphenyl group.

Z in the formula I is a nitro group or a substituted or unsubstituted amino group, for example, acylamino such as nitro group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group and acetamide group. Group, trialkylsilylamino group and the like, preferably nitro group, amino group, trialkylsilylamino group and the like. The trialkylsilylamino group is -N
It is represented by HSi (R ⁸ ) ₃ , and examples of R ⁸ include a methyl group and an ethyl group, but a methyl group is preferable.

Examples of the divalent organic group represented by R ¹ in the formula II include an alkylene group, an oxyalkylene group, a phenylenealkylene group, a phenyleneoxyalkylene group and the like. Alkylene groups are preferred. R ^{2 to} R ⁶ are monovalent organic groups, which include alkyl groups such as methyl group, ethyl group, propyl group and octyl group, 2-phenylethyl group, 2-phenylpropyl group, 3,3,3. Examples thereof include substituted alkyl groups such as trifluoropropyl group, aryl groups such as phenyl group, and substituted aryl groups such as tolyl group. Above all, R ^{2 to} R
⁵ is preferably a methyl group or a phenyl group, more preferably a methyl group from an economical point of view. As for R ⁶ , a methyl group, n and n are used because of easy availability of the raw material for the hydroorganopolysiloxane represented by the formula III.
-Butyl group, sec-butyl group, tert-butyl group,
And phenyl groups are preferred. n is a positive integer, preferably 1 to 5000, more preferably 3 to 1000.
Is exemplified.

The substituent Z in the formula I is attached to each benzene ring one by one, and the polysiloxane chain A is attached to each benzene ring one by one or only to one benzene ring. is doing. Both Z and A may be bonded to any position from the 2-position to the 6-position of each benzene ring.

The organopolysiloxane of the present invention can be produced by the method described below. That is, the following formula V

[0015]

[Chemical 10]

[Wherein A and m have the same meanings as described in formula I]. ] An organopolysiloxane having a dinitrobiphenyl group represented by the following formula III

[0017]

[Chemical 11]

[Wherein R ^{1 to} R ⁶ and n have the same meanings as described in the formula II. ] A terminal hydroorganopolysiloxane represented by the following formula IV

[0019]

[Chemical 12]

[In the formula, R ⁷ is an organic group having an ethylenically unsaturated group at the terminal, and m is 0 or 1. ] The compound which has terminal olefin shown by these can be synthesize | combined by carrying out hydrosilylation reaction in presence of a catalyst. Formula VI below

[0021]

[Chemical 13]

[In the formula, A and m have the same meanings as described in the formula I. ] The polyorganosiloxane having a diaminobiphenyl group represented by the following is obtained by reducing the nitro group of the above-mentioned organopolysiloxane having a dinitrobiphenyl group. Further, in the formula I, the organopolysiloxane in which Z is a substituted amino group can be obtained by, for example, alkylating, arylating or acetylating the amino group of the organopolysiloxane having a diaminobiphenyl group represented by the formula VI. Furthermore, the following formula VII

[0023]

[Chemical 14]

[Wherein A and m have the same meanings as described in formula I, and R ⁸ represents an alkyl group. ] The organopolysiloxane having a trialkylsilylaminobiphenyl group represented by the following] is obtained by silylating the above amino group.

The organopolysiloxane having a bifunctional biphenyl group of the present invention has a starting material, a dinitrobiphenyl compound represented by the formula IV, which has one organic group having an ethylenically unsaturated bond at the terminal. That is, when m = 0 in the formula IV, A (organopolysiloxane) bonded to the compound represented by the formula I is formed.
Will be one. In the case where the dinitrobiphenyl compound represented by the other formula IV has two organic groups having an ethylenically unsaturated bond at the end, that is, m =
In the case of 1, the number of A (organopolysiloxane) bonded to the compound represented by the formula I is two.

The terminal hydroorganopolysiloxane of formula III can be prepared by known methods.

Dinitrobiphenyl compound of formula IV
Has one nitro group attached to each benzene ring
And an organic group R having an ethylenically unsaturated bond at the end⁷
Is one attached to each benzene ring, or
One is bonded only to one benzene ring. Nitro group,
R⁷Are both positions 2 to 6 of each benzene ring
It may be connected to the device. R⁷As -CH = CH
₂, -CH₂CH = CH₂, -CH₂CH₂CH = CH
₂, -CH (CH₃) CH = CH₂,-(CH ₂)₆C
H = CH₂, -OCH = CH₂, -OCH₂CH = CH
₂, -OCH₂CH₂CH = CH₂, -OCH (C
H₃) CH = CH₂, -O (CH₂)₆CH = CH₂etc
Is exemplified, but because of easy availability of raw materials, -OCH = C
H₂, -OCH₂CH = CH₂, -OCH₂CH₂CH
= CH₂, -OCH (CH₃) CH = CH₂, -O (C
H₂)₆CH = CH₂Etc. are preferred. These compounds are
Generally not on the market, but shown later as an example
It can be synthesized by a method or the like.

The terminal hydroorganopolyol of formula III
Hydride of siloxane with olefin compound of formula IV
The rosilylation reaction is carried out in the presence of a catalyst, preferably in a solvent.
Done in. As the catalyst, chloroplatinic acid, platinum-dibi
Nyltetramethyldisiloxane complex, platinum such as platinum carbon
It is most common to use a system catalyst, but (Ph ₃
P)₃RhCl, (Ph₂PH)₃RhCl, (Ph₃
P)₃(CO) RhH, and further Co (I), Pd (I
It is also possible to use transition metal catalysts such as I) and Ru (II).
Wear. The amount of catalyst is usually 1 mole of carbon-carbon double bond.
Then 1/10^FourFrom 1/10²It may be about g equivalent. solvent
As, aromatic carbon such as benzene, toluene, xylene
Solvents such as hydrogen fluoride, aliphatic hydrocarbons such as hexane and heptane
Medium, diethyl ether, tetrahydrofuran, etc.
Solvent such as methanol, ethanol, propanol, etc.
Alcohol solvents, acetone, methyl ethyl ketone, etc.
Ketone type solvent, ester type such as ethyl acetate, butyl acetate
Solvent, chloroform, trichlorethylene, carbon tetrachloride
Halogenated hydrocarbon solvents such as
Muamide, dimethylacetamide, dimethylsulfoxy
Do and the like are exemplified. The reaction temperature is 0 to 200 ° C, preferably
At 40-110 ° C in a dry, inert atmosphere
However, it is desirable to add a small amount of oxygen depending on the catalyst.

The diaminobiphenyl group-containing organopolysiloxane represented by the formula VI can be synthesized by reducing the nitro group of the dinitrobiphenyl group-containing organopolysiloxane represented by the formula V to an amino group. Examples of the reduction method include a catalytic reduction method with hydrogen using platinum, Raney nickel, platinum carbon, palladium carbon, rhodium-alumina, platinum sulfide carbon or the like as a catalyst. The reaction is preferably carried out in a solvent, and examples of the solvent include the above-mentioned various solvents and mixed solvents thereof. The reaction temperature is preferably in the range of room temperature to the reflux temperature of the solvent. The reduction method is not limited to the above method.

The organopolysiloxane in which Z is a substituted amino group in formula I is obtained, for example, by alkylating, arylating or acetylating the amino group of the organopolysiloxane having a diaminobiphenyl group represented by formula VI. . Specifically, an alkyl halide, an aryl halide, acetyl chloride, or the like is used.

Organopolysiloxanes having a trialkylsilylaminobiphenyl group of formula VII have the formula
It is obtained by silylating an amino group of an organopolysiloxane having a diaminobiphenyl group represented by VI. Examples of silylating agents include trialkylhalosilanes such as trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, and methyldiethylbromosilane, and hexamethyldisilazane, N, N-diethylaminotrimethylsilane, N, O-bis (trimethylsilyl) carbamate. , N-trimethylsilylimidazole and other nitrogen-containing silylating agents are exemplified. When a trialkylhalosilane is used, it is preferable to coexist with a base to neutralize by-produced hydrogen halide. When using a nitrogen-containing silylating agent, a catalyst such as trimethylchlorosilane or ammonium sulfate may be added. The silylation reaction can be carried out in the above various solvents other than the alcohol solvent, but the solvent can be omitted. Reaction temperature is 0-20
The temperature is 0 ° C, preferably 20 to 140 ° C.

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1) (Synthesis of 2- (3-butenyloxy) -4,4'-dinitrobiphenyl) In a beaker, 13.0 g of 4,4'-dinitro-2-aminobiphenyl and 15.0 ml of water were added. After adding a mixture of concentrated sulfuric acid (11.0 ml) and stirring for 2 hours while heating, 26.5 g of crushed ice was added, and an aqueous solution of 3.51 g of sodium nitrite was added dropwise to this in an ice bath for 10 minutes. Stir,
It was left for a few more minutes. A solution prepared by adding 33.4 ml of concentrated sulfuric acid to 25 ml of water was boiled, the above reaction mixture was slowly added dropwise thereto, and the mixture was boiled for 5 minutes, and then poured into a beaker in an ice bath. This is suction filtered and the filter cake is purified by column chromatography to give 4,4 '
10.9 g (yield 83.9%) of dinitro-2-hydroxybiphenyl was obtained as a tan powder. Melting point, 22
0-222 ° C.

Next, the obtained 4,4'-dinitro-2-
Acetone dried with 10.4 g of hydroxybiphenyl 9
Dissolve in 5 ml, potassium carbonate 5.52 g, 4-bromo-
7.56 g of 1-butene was added, and the mixture was refluxed for 71 hours. Purified by a conventional method, 2- (3-butenyloxy) -4,4 '
-5.20 g (yield 41.4%) of dinitrobiphenyl was obtained as a pale yellow powder. Melting point 146-147 [deg.] C.

Example 2 (Synthesis of Polysiloxane Having 4,4'-Dinitrobiphenyl Group) 2.52 g of 2- (3-butenyloxy) -4,4'-dinitrobiphenyl synthesized in Example 1 was dried. After dissolving in 80 ml of toluene and adding 100 μl of 3% isopropyl alcohol solution of chloroplatinic acid,

[0036]

[Chemical 15]

A terminal hydropolysiloxane (n
The average value of 14.4) 7.88 g dissolved in 20 ml of dry toluene was added dropwise, and stirring was continued at 100 ° C. for 4 hours. Purified by column chromatography, 8.68
g of a polysiloxane having 4,4'-dinitrobiphenyl groups was obtained as a pale yellow waxy solid (yield 8
7.1%). Only the terminal (β) adduct was obtained.

¹ H NMR spectrum (in CDCl ₃ )
δ (ppm): 8.27 (d, 2H), 7.90 (d,
1H), 7.83 (s, 1H), 7.68 (d, 2)
H), 7.46 (d, 1H), 4.08 (t, 2H),
1.78 (m, 2H), 1.42 (m, 2H), 1.2
9 (m, 4H), 0.86 (t, 3H), 0.53
(M, 4H), 0.24 to -0.01 (m, 92.4)
H).

(Examples 3 to 5) In the same manner as in Example 2, polysiloxanes having 4,4'-dinitrobiphenyl groups having different degrees of polymerization as shown in Table 1 were synthesized. An example using a platinum-divinyltetramethyldisiloxane complex instead of chloroplatinic acid as a catalyst is also shown. O-Si
The same N except that the relative amount of (CH ₃ ) ₂ —O groups is different.
An MR spectrum was obtained.

[0040]

[Table 1]

(Example 6) (Synthesis of polysiloxane having 4,4'-diaminobiphenyl group) 270 mg of palladium carbon (5% Pd) was suspended in 14 ml of a 1: 1 mixed solvent of ethanol and benzene,
While passing through hydrogen, 3.21 g of the polysiloxane having the 4,4'-dinitrobiphenyl group synthesized in Example 2 (average value of n: 14.4) dissolved in 14 ml of the same mixed solvent was added. After continuing hydrogen blowing for 3 hours with stirring, the catalyst was filtered off and the solvent was distilled off under reduced pressure to obtain a polysiloxane having 4,4′-diaminobiphenyl group as a yellow viscous liquid ( Yield 3.00
g, 97.7%).

¹ H NMR spectrum (in CDCl ₃ )
δ (ppm): 7.29 (d, 2H), 7.07 (d,
1H), 6.66 (d, 2H), 6.30 (d, 1
H), 6.29 (s, 1H), 3.87 (t, 2H),
3.61 (d, 4H), 1.74 (m, 2H), 1.4
4 (m, 2H), 1.30 (m, 4H), 0.86
(T, 3H), 0.54 (m, 4H), 0.05-0.
01 (m, 92.4H).

(Examples 7 and 8) In the same manner as in Example 6, polysiloxanes having 4,4'-diaminobiphenyl groups having different polymerization degrees as shown in Table 2 were synthesized. O
Except that the relative amounts of -Si (CH _{3) 2} -O groups are different, similar NMR spectrum was obtained.

[0044]

[Table 2]

(Example 9) (Synthesis of polysiloxane having 4,4'-bis (trimethylsilylamino) biphenyl group) Polysiloxane having a diamino group synthesized in Example 7 (average value of n: 2)
6.7) 1.18 g was dissolved in 10 ml of dried benzene and 0.158 g of dried triethylamine was added.
To this, 0.041 g of trimethylchlorosilane was slowly added, and the mixture was stirred at room temperature for 1 hour, further at 60 ° C. for 2 hours and at 80 ° C. for 38 hours in an oil bath. The salt was filtered off under an argon atmosphere and the solvent and the like were removed under reduced pressure to obtain a polysiloxane having 4,4'-bis (trimethylsilylamino) biphenyl group as a brown viscous liquid (yield 1.04 g,
83.1%).

¹ H NMR spectrum (in CDCl ₃ )
δ (ppm): 7.30 (d, 2H), 7.07 (d,
1H), 6.60 (d, 2H), 6.31 (d, 1)
H), 6.29 (s, 1H), 3.87 (t, 2H),
3.27 (s, 2H), 1.72 (m, 2H), 1.4
2 (m, 2H), 1.30 (m, 4H), 0.86
(T, 3H), 0.54 (m, 4H), 0.25-0.
01 (m, 184.2H).

[0047]

Since the organopolysiloxane of the present invention has a diaminobiphenyl group and a trialkylsilylaminobiphenyl group which have sequential polymerization reactivity, the organopolysiloxane side chain can be obtained by reacting with a suitable monomer. It is possible to synthesize a novel polymer having a main chain of polyamide, polyimide, polyurea or the like.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 2, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

The terminal hydroorganopolyol of formula III
Hydride of siloxane with olefin compound of formula IV
The rosilylation reaction is carried out in the presence of a catalyst, preferably in a solvent.
Done in. As the catalyst, chloroplatinic acid, platinum-dibi
Nyltetramethyldisiloxane complex, platinum such as platinum carbon
It is most common to use a system catalyst, but (Ph ₃
P)₃RhCl, (Ph₂PH)₃RhCl, (Ph₃
P)₃(CO) RhH, and further Co (I), Pd (I
It is also possible to use transition metal catalysts such as I) and Ru (II).
Wear. The amount of catalyst is usually 1 mole of carbon-carbon double bond.
Then 1/10^FourFrom 1/10 ² molThe degree is enough. With solvent
For aromatic carbonization of benzene, toluene, xylene, etc.
Hydrogen solvent, hexane, heptane, etc.
Medium, diethyl ether, tetrahydrofuran, etc.
Solvent such as methanol, ethanol, propanol, etc.
Alcohol solvents, acetone, methyl ethyl ketone, etc.
Ketone type solvent, ester type such as ethyl acetate, butyl acetate
Solvent, chloroform, trichlorethylene, carbon tetrachloride
Halogenated hydrocarbon solvents such as
Muamide, dimethylacetamide, dimethylsulfoxy
Do and the like are exemplified. The reaction temperature is 0 to 200 ° C, preferably
At 40-110 ° C in a dry, inert atmosphere
However, it is desirable to add a small amount of oxygen depending on the catalyst.

Claims (7)

[Claims] 1. The following formula I: [In the formula, Z is a nitro group or a substituted or unsubstituted amino group, and A is the following formula II: (Wherein R ¹ is a divalent organic group having 2 or more carbon atoms, R ^{2 to} R ⁶ are the same or different monovalent organic groups, n is an integer of 1 or more, and R ^{4 is} , R ⁵
May be different for each repeating unit. ) And m is 0 or 1. ] The organopolysiloxane which has a bifunctional biphenyl group shown by these. 2. An organopolysiloxane having a bifunctional biphenyl group of formula I, wherein m is 0. 3. The substituent 2 according to claim 1 or 2, wherein the substituent Z is a nitro group, an amino group or a trialkylsilylamino group.
An organopolysiloxane having a functional biphenyl group. 4. The organopolysiloxane having a bifunctional biphenyl group according to claim 1, wherein R ^{2 to} R ⁵ in the formula II are methyl groups. 5. The following formula III: [In the formula, R ^{2 to} R ⁶ and n have the same meanings as described in claim 1. ] And an organohydropolysiloxane represented by the following formula IV: [In the formula, R ⁷ is an organic group having an ethylenically unsaturated bond at the terminal, and m is 0 or 1. ] A dinitrobiphenyl compound represented by the following formula V is reacted in the presence of a catalyst. [In the formula, A and m have the same meanings as described in claim 1. ] The manufacturing method of the organopolysiloxane which has a dinitro biphenyl group shown by these. 6. An organopolysiloxane having a dinitrobiphenyl group represented by the formula V according to claim 5 is reduced in the presence of a catalyst. [In the formula, A and m have the same meanings as described in claim 1. ] The manufacturing method of the organopolysiloxane which has a diamino biphenyl group shown by these. 7. An organopolysiloxane having a diaminobiphenyl group represented by the formula VI according to claim 6 is silylated with a trialkylhalosilane or a nitrogen-containing silylating agent. [Wherein R ⁸ is an alkyl group, and A and m have the same meanings as described in claim 1. ] The manufacturing method of the organopolysiloxane which has a trialkyl silyl amino biphenyl group shown by these.