JPH06329797A - Preparation of polyimide with organopolysiloxane side chain - Google Patents

Abstract

PURPOSE: To obtain the subject polyimide excellent in solvent solubility and useful for a blend with a polyimide or a polysiloxane by reacting a specified organopolysiloxane with an aromatic diamine and an aromatic tetracarboxylic dianhydride to form a specified polyimide.

CONSTITUTION: A diaminobiphenyl-containing organopolysiloxane represented by formula I [wherein Z is an organopolysiloxane represented by formula II (wherein R¹ is a divalent organic group; R² to R⁶ are each a monovalent organic group; and n is 1 or greater); and m is 0 or 1] is reacted with an aromatic diamine and an aromatic tetracarboxylic dianhydride in a solvent to synthesize a polyamic acid comprising repeating units represented by formula III (wherein A¹ is a tetravalent aromatic group; and A² is a divalent organic group represented by formula V) and formula IV (wherein A³ is a divalent aromatic group) in a molar ratio of 100/0 to 1/99, and this is imidized by heating to form a polyimide comprising repeating units represented by formulas VI and VII in a molar ratio of 100/0 to 1/99.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyimide having a novel organopolysiloxane side chain.

[0002]

Aromatic polyesters, aromatic polyamides (aramids), aromatic polyimides, and other aromatic polymers are high-performance polymer materials because of their high mechanical strength, heat resistance, and solvent resistance. It is occupying an important position [edited by The Polymer Society of Japan, high-performance aromatic polymer materials, Maruzen (199
0) etc.]. However, compared with conventional flexible polymers, these rigid linear polymers have low solubility in solvents and high melting points, and are inferior in processability. Therefore, their industrial development and use have started in recent years. Nothing more than.

As one of the methods for improving the solubility and lowering the melting point of these aromatic rigid linear polymers, it has been proposed to introduce a flexible polymer as a side chain [M.
Ballauff, Angew. Chem. Int. E
d. Engl. 28, p. 253 (1989), etc.]. For such a purpose, an aromatic polyester having an alkyl or alkyloxy side chain or having an alkyl chain introduced by an ester bond [R. W. Lenz et al., Eu
r. Polym. J. , Vol. 19, p. 1043 (19
83), M.A. Ballauff, Makromol. C
hem. , Rapid Commun. , Volume 7, 407
Page, (1986), B. R. Harkness et al.
Macromolecules, Vol. 24, p. 6759 (1991), etc.], an aromatic polyester having a polystyrene side chain [T. Heitz et al., Makromol.
Chem. , 190, 3295 pages (198
9)], an aromatic polyimide having an alkyloxy side chain [M. Ballauff et al., Makromol. Che
m. , 188, 2865 (1987)] and the like are reported. In addition, an example in which a polysiloxane side chain is introduced into a quasi-rigid aromatic polyimide for the purpose of a separation membrane material has also been reported [Nagase et al., Makromol. Ch
em. , 193, p. 1509 (1992)].

[0004]

However, an aromatic polyimide or a copolymer thereof having an organopolysiloxane side chain and a unit derived from a diamine monomer to which the side chain is bonded is a biphenyl group has not yet been known. Has not been done. The polyimide having such an organopolysiloxane side chain can be expected to have novel properties having the properties of both polyimide and polysiloxane in addition to the above-described solubility improvement and the like. It is an object of the present invention to provide a method for producing a novel polyimide having the above organopolysiloxane side chain.

[0005]

The first aspect of the present invention is as follows.
Organopolysiloxane having diaminobiphenyl group represented by the following formula I

[0006]

[Chemical 7]

[Wherein Z is an organopolysiloxane represented by the following formula II:

[0008]

[Chemical 8]

(Here, R ¹ is a divalent organic group, R ^{2 to} R ⁶
Are the same or different monovalent organic groups, and n is an integer of 1 or more. same as below. ) And m is 0 or 1. same as below. ], Aromatic diamine and aromatic tetracarboxylic dianhydride are reacted in a solvent, the repeating unit is represented by the following formula II
I and formula IV

[0010]

[Chemical 9]

[Wherein A ¹ is a tetravalent aromatic group and A ² is a divalent organic group represented by the following formula V:

[0012]

[Chemical 10]

And A ³ is a divalent aromatic group. same as below. However, A ¹ , A ³ , R ^{1 to} R ⁶ , m and n may be different for each repeating unit. same as below. ] And the molar ratio of the repeating unit represented by the formula (III) to the repeating unit represented by the formula IV is 100/0 to 1/99.
A polyamic acid having an organopolysiloxane side chain in the range of ## STR3 ## is synthesized by heating and imidized, and the repeating units have the following formulas I and II.

[0014]

[Chemical 11]

The molar ratio of the repeating unit represented by the formula VI to the repeating unit represented by the formula VII is 100/0 to
It is a method for producing a polyimide having an organopolysiloxane side chain in the range of 1/99.

The second aspect of the present invention is to prepare an organopolysiloxane having a diaminobiphenyl group represented by the above formula I and an amino group of an aromatic diamine after previously silylating with a trialkylhalosilane or a nitrogen-containing silylating agent. Reacting with an aromatic tetracarboxylic dianhydride in a solvent to give repeating units of formula VIII and formula IX

[0017]

[Chemical 12]

[In the formula, R ⁷ is an alkyl group. A silylated polyamic acid having an organopolysiloxane side chain in which the repeating unit represented by the formula VIII and the repeating unit represented by the formula IX are in a molar ratio of 100/0 to 1/99. Of which the repeating unit comprises the above formula VI and the formula VII, and the molar ratio of the repeating unit represented by the formula VI to the repeating unit represented by the formula VII is 1
A method for producing a polyimide having an organopolysiloxane side chain in the range of 00/1 to 1/99.

The tetravalent aromatic group represented by A ¹ is

[Chemical 13]

Examples thereof include, but are not limited to:

A ³ is a divalent aromatic group,

[Chemical 14]

Examples thereof include, but are not limited to.

The site where the unit represented by the formula V is bonded to the adjacent unit and the bonding position of the polysiloxane chain Z are
It may be at any of 2 to 6 positions of each benzene ring, and one polysiloxane chain Z is bonded to each benzene ring or only one benzene ring is bonded to one benzene ring.

In formula II, R¹As a divalent organic group represented by
Are alkylene groups, oxyalkylene groups, phenylene
Examples include alkylene groups and phenyleneoxyalkylene groups
However, due to the ease of availability, it is
A len group is preferred. R²~ R ⁶Is a monovalent organic group,
This includes methyl, ethyl, propyl and octyl groups.
Alkyl group such as, 2-phenylethyl group, 2-phenyl
Propyl group, 3,3,3-trifluoropropyl group, etc.
A substituted alkyl group, an aryl group such as a phenyl group, or
A substituted aryl group such as a ryl group is exemplified. Above all, R²~
R^FiveIs preferably a methyl group and a phenyl group
From an economic point of view, the methyl group is preferred.
Good R⁶For the formula, the following formula X

[0025]

[Chemical 15]

In order to easily obtain the raw material of the hydroorganopolysiloxane represented by the following formula, a methyl group, an n-butyl group,
A sec-butyl group, a tert-butyl group, and a phenyl group are preferred. n is a positive integer, preferably 1 to
5000, and more preferably 3 to 1000 are exemplified.

The polyimide having an organopolysiloxane side chain of the present invention can be produced by the method described below. That is, the following formula XI

[0028]

[Chemical 16]

A tetracarboxylic dianhydride represented by
A diaminobiphenyl group-containing organopolysiloxane represented by the formula I is reacted in an approximately equimolar amount, or a diaminobiphenyl group-containing organopolysiloxane represented by the formula V is reacted with the following formula XII.

H ₂ N--A ³ --NH ₂ XII

The reaction is carried out so that the total molar amount of the aromatic diamine compound represented by and the amount of tetracarboxylic dianhydride are equal to each other.
A polyamic acid having an organopolysiloxane side chain in which the molar ratio of the repeating unit represented by III to the repeating unit represented by formula IV is in the range of 100/0 to 1/99 is synthesized, and this is subjected to thermal imidization. Can be synthesized by
This imidization reaction can be carried out in solution with or without an imidizing agent.

Further, the organopolysiloxane having the diaminobiphenyl group represented by the formula I and the aromatic diamine compound represented by the formula XII are silylated, and then the aromatic tetracarboxylic acid dianhydride represented by the formula XI is used in a solvent. And the repeating unit comprises the above formula VIII and formula IX, and the molar ratio of the repeating unit represented by formula VIII and the repeating unit represented by formula IX is in the range of 100/0 to 1/99. It can also be produced by synthesizing silylated polyamic acid having an organopolysiloxane side chain and subjecting this to thermal imidization.

Examples of the aromatic tetracarboxylic dianhydride represented by the formula XI include pyromellitic dianhydride, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride, 2,
3,3 ′, 4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′ , 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3
3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-
Dicarboxyphenyl) sulfone dianhydride, 2,3
6,7-naphthalenetetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3, Examples include, but are not limited to, 4,9,10-perylenetetracarboxylic dianhydride, 2,3,5,6-pyrazinetetracarboxylic dianhydride, and mixtures thereof. It can also be used.

As the aromatic diamine compound represented by the formula XII, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,6-diaminonaphthalene, 1 , 5
-Diaminonaphthalene, 2,6-diaminoanthracene, 2,7-diaminoanthracene, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,
3'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone,
2,2-bis (4-diaminophenyl) propane, 1,
Examples include 1,1,3,3,3-hexafluoro-2,2-bis (4-diaminophenyl) propane and 4,4′-diaminodiphenylsulfone, but the invention is not limited thereto. It is also possible to use a mixture of these.

The organopolysiloxane having a diaminobiphenyl group represented by the formula I includes a terminal hydroorganopolysiloxane represented by the formula X and the following formula XIII.

[0036]

[Chemical 17]

[In the formula, R ⁸ is an organic group having an ethylenically unsaturated bond at the terminal. And a compound having a terminal olefin represented by the following formula XIV

[0038]

[Chemical 18] Can be synthesized by synthesizing an organopolysiloxane having a dinitrobiphenyl group represented by and further reducing the nitro group.

The terminal hydroorganopolysiloxane represented by the formula X can be produced by a known method.

A dinitrobiphenyl compound of formula XIII
The product has one nitro group attached to each benzene ring
And an organic group R having an ethylenically unsaturated bond at the end
⁸Is attached to each benzene ring one by one
Is bonded to only one benzene ring. Nitro
Group, R⁸Both of the 2- to 6-positions of each benzene ring
It may be attached to a position. R⁸As, -CH = C
H₂, -CH₂CH = CH₂, -CH₂CH₂CH = C
H₂, -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.
As an example, since the raw materials are easily available, -OCH = CH
₂, -OCH₂CH = CH₂, -OCH₂CH₂CH =
CH₂, -OCH (CH₃) CH = CH ₂, -O (CH
₂)₆CH = CH₂Etc. are preferred. These compounds are generally
Although not commercially available in the market,
Can be synthesized by.

The terminal hydroorganopolysiloxane of the formula X
Hydride of roxane with olefin compound of formula XIII
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 1/10²Molar level is sufficient. 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.

As a method for reducing the nitro group of the organopolysiloxane having a dinitrobiphenyl group represented by the formula XIV to an amino group, platinum, Raney nickel, platinum carbon, palladium carbon, rhodium-alumina, platinum sulfide carbon or the like is used as a catalyst. The catalytic reduction method with hydrogen used is exemplified. 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 synthesis of the polyamic acid is preferably carried out under a dry, inert atmosphere. The reaction can be carried out without a solvent, but it is preferably carried out in a solvent, and examples of the solvent include the above-mentioned various solvents and mixtures thereof. The reaction temperature is preferably -50 ° C to 100 ° C, more preferably 0 ° C to 50 ° C.

The heat imidization of the polyamic acid is carried out by removing the solvent and then heating at 100 ° C. to 400 ° C., preferably 150 ° C. to 350 ° C. At this time, the atmosphere may be air, an inert gas, or a reduced pressure. Further, imidization in a solution is carried out in the above various solvents, for example, at a reaction temperature of about 50 ° C. to 150 ° C. using acetic anhydride and a base such as amine as an imidizing agent,
Alternatively, the imidizing agent may be used at a temperature of about 150 ° C. to 200 ° C. without using an imidizing agent, but the imidization method in a solution is not limited thereto. In the imidization in a solution, the imidization rate is 10 depending on the reaction conditions.
Although it can be made smaller than 0%, further imidization can be completed by post-heating under the above heating imidization conditions.

Silylation of the organopolysiloxane having a diaminobiphenyl group represented by the formula I and the aromatic diamine compound represented by the formula XII is carried out with a silylating agent. As the silylating agent, trimethylchlorosilane,
Triethylchlorosilane, triphenylchlorosilane,
Examples are trialkylhalosilanes such as methyldiethylbromosilane, and nitrogen-containing silylating agents such as hexamethyldisilazane, N, N-diethylaminotrimethylsilane, N, O-bis (trimethylsilyl) carbamate, and N-trimethylsilylimidazole. . 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.

The silylated polyamic acid is synthesized using these silylated diamines in the same manner as the above polyamic acid. Further, a polyimide is obtained by heating the silylated polyamic acid in the same manner as above. Of course, since the usual polyamic acid can be obtained by hydrolyzing the silyl ester, this can also be imidized in the same manner as above by heating or in a solution.

[0047]

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

Reference Example 1 (Synthesis of 2- (3-butenyloxy) -4,4'-dinitrobiphenyl) 4,3'-dinitro-2-aminobiphenyl (13.0 g), water (15.0 ml) and concentrated sulfuric acid. After adding 11.0 ml of the mixture and stirring for 2 hours while heating, 26.5 g of crushed ice was added. An aqueous solution of 3.51 g of sodium nitrite was added dropwise to this in an ice bath, and the mixture was stirred for 10 minutes and left for a few minutes. Concentrated sulfuric acid 33.4 in 25 ml of water
The mixture to which ml was added was boiled, the above-mentioned reaction mixture was slowly added dropwise thereto, and after boiling for 5 minutes, the mixture was poured into a beaker in an ice bath. It is suction filtered and the filter cake is purified by column chromatography,
4'-dinitro-2-hydroxybiphenyl 10.9 g
(Yield 83.9%) was obtained as a tan powder.

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.

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

[0051]

[Chemical 19]

The 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%).

Reference Examples 3 and 4 In the same manner as in Reference Example 2, polysiloxanes having 4,4′-dinitrobiphenyl groups having different polymerization degrees as shown in Table 1 were synthesized.

[0054]

[Table 1]

Reference Example 5 (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, and hydrogen was passed through. 4,4'-synthesized in Reference Example 2
A solution prepared by dissolving 3.21 g of a polysiloxane having a dinitrobiphenyl group (average value of n: 14.4) 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 3.0
0 g, 97.7%).

Reference Examples 6 and 7 By the same method as in Reference Example 5, polysiloxanes having 4,4′-diaminobiphenyl groups having different degrees of polymerization as shown in Table 2 were synthesized.

[0057]

[Table 2]

Example 1 (Synthesis 1 of Polyamic Acid Having Polysiloxane Side Chain)
Polysiloxane synthesized in Reference Example 5 having 4,4′-diaminobiphenyl group (average value of n: 14.4) 0.74
5 g was dissolved in 4 ml of tetrahydrofuran, 0.114 g of pyromellitic dianhydride was added, and the mixture was stirred at room temperature. The generated polyamic acid solution was applied onto a glass plate, and the solvent was removed under reduced pressure at 30 ° C. to obtain a polyamic acid film.

The intrinsic viscosity of the resulting polyamic acid having a polysiloxane side chain is 25 ° C. in tetrahydrofuran.
Was 0.17 dL / g.

IR spectrum (cm ^-1 ): 2961
(S), 1713 (m), 1669 (m), 1599
(S), 1522 (s), 1497 (m), 1400
(S), 1256 (vs), 1076 (sh), 105
9 (sh), 1007 (vs), 789 (vs) (33
N—H around 00 and aromatic C—H around 3050 had low strength and could not be identified. s is strong absorption, vs is very strong absorption, m is medium absorption, sh refers to what appears as a shoulder for other absorptions. )

Examples 2 and 3 (Synthesis of Polyamic Acid Having Polysiloxane Side Chains 2,
3) By the same method as in Example 1, polyamic acids having different polysiloxane polymerization degrees as shown in Table 3 were synthesized. Were obtained similar IR spectrum as in Example 1, Example 2,3 N-H in the vicinity of both 3290cm ^-1, 3050cm ^-1
Aromatic CH was observed in the vicinity.

[0062]

[Table 3]

Example 4 (Synthesis 1 of Polyimide Having Polysiloxane Side Chain) The polyamic acid film obtained in Example 1 was heated at 60 ° C. for 20 minutes, 100 ° C. for 20 minutes, and 200 ° C. under an argon atmosphere. After heating for 2 hours, a polyimide film having a polysiloxane side chain was obtained.

IR spectrum (cm ^-1 ): 2961
(S), 1782 (m), 1726 (vs), 1605
(S), 1499 (s), 1377 (s), 1258
(Vs), 1177 (m), 1069 (sh), 100
7 (vs), 785 (vs), 723 (s)

Examples 5 and 6 (Synthesis of Polyimide Having Polysiloxane Side Chain 2,
3) In the same manner as in Example 4, as shown in Table 4, Example 2
The polyamic acid obtained in and 3 was imidized.

[0066]

[Table 4]

(Example 7) (Synthesis 4 of Polyimide Having Polysiloxane Side Chain) In the same manner as in Example 1, polysiloxane having 4,4'-diaminobiphenyl group (average value of n was 14.4). 735
g and pyromellitic dianhydride 0.112 g were reacted in 4 ml of tetrahydrofuran and 0.434 g of triethylamine and 0.44 of acetic anhydride were added to the obtained polyamic acid solution.
0 g of the mixture was added dropwise and reacted in an oil bath at 70 ° C for 1 hour. IR of polyimide obtained as a yellow transparent gel
The spectrum was as follows, and the imidization ratio was 47%.

IR spectrum (cm ^-1 ): 2961
(S), 1779 (m), 1730 (s), 1601
(M), 1520 (w), 1499 (s), 1375
(S), 1260 (vs), 1094 (sh), 102
2 (vs), 801 (vs), 720 (m) (w indicates weak absorption)

When this polyimide was heated in the same manner as in Example 4, imidization was completed.

Reference Example 8 (Synthesis of Polysiloxane Having 4,4′-Bis (trimethylsilylamino) biphenyl Group) The polysiloxane having a diamino group synthesized in Reference Example 6 (average value of n: 2)
6.7) 1.18 g was dissolved in 10 ml of benzene, and 0.158 g of 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 stirred in an oil bath at 60 ° C for 2 hours, and at 80 ° C for 38 hours. After removing the salt by filtration, the solvent and the like are removed under reduced pressure.
A polysiloxane having 4'-bis (trimethylsilylamino) biphenyl groups was obtained (yield 1.04 g, 83.
1%).

(Example 8) (Synthesis of silylated polyamic acid having a polysiloxane side chain) All reactions were carried out in a glove bag in which argon was substituted. In a water bath at 10 ° C., 1.00 g of the polysiloxane having 4,4′-bis (trimethylsilylamino) biphenyl group synthesized in Reference Example 8 was dissolved in 4 ml of tetrahydrofuran, and pyromellitic dianhydride prepared in advance. A tetrahydrofuran solution of the product was added dropwise in such an amount that the amount of pyromellitic dianhydride became 0.087 g. After 1 hour, the water bath was replaced with an oil bath and heated at 35 ° C. overnight. The produced polymer solution was applied on a glass plate in a glove bag and the solvent was removed to obtain a silylated polyamic acid film.

IR spectrum (cm ^-1 ): 2961
(S), 1703 (m), 1655 (m), 1608
(M), 1534 (m), 1495 (s), 1408
(M), 1256 (vs), 1209 (s), 1009
(Vs), 823 (s), 788 (vs)

The intrinsic viscosity of polyamic acid obtained by desilylating this silylated polyamic acid in methanol is 0.24 dL.
/ G.

(Example 9) (Synthesis 5 of Polyimide Having Polysiloxane Side Chain) The silylated polyamic acid film obtained in the glove bag in Example 8 was heated and imidized in the same manner as in Example 4. did.

IR spectrum (cm ^-1 ): 2961
(S), 1782 (m), 1730 (vs), 1602
(S), 1500 (s), 1377 (s), 1257
(Vs), 1177 (m), 1068 (sh), 100
7 (vs), 785 (vs), 723 (s)

(Example 10) (Synthesis 4 of polyamic acid having a polysiloxane side chain)
Polysiloxane having 4,4'-diaminobiphenyl group synthesized in Reference Example 5 (average value of n: 14.4) 0.20
Polysiloxane having 1 g and 4,4′-diaminobiphenyl group synthesized in Reference Example 7 (average value of n: 46.2)
0.496 g was dissolved in 5 ml of tetrahydrofuran, 0.062 g of pyromellitic dianhydride was added, and the mixture was stirred at room temperature. Apply the resulting polyamic acid solution on a glass plate,
The solvent was removed at 30 ° C. under reduced pressure to obtain an amic acid copolymer film having two kinds of side chains with different lengths (ratio of two kinds of units: 1: 1).

The polyamic acid having a polysiloxane side chain thus obtained has an intrinsic viscosity of 25 ° C. in tetrahydrofuran.
Was 0.17 dL / g.

IR spectrum (cm ^-1 ): 3291 (w,
b), 2963 (s), 1713 (m), 1669
(M), 1601 (s), 1526 (s), 1497
(M), 1402 (s), 1258 (vs), 1080
(Sh), 1011 (vs), 785 (vs) (b indicates wide absorption).

Example 11 (Synthesis 6 of Polyimide Having Polysiloxane Side Chain) The polyamic acid film obtained in Example 10 was used in Example 4
Is imidized by heating in the same manner as in (2), and an imide copolymer having two kinds of side chains with different lengths (ratio of two kinds of units is 1:
1) was obtained.

IR spectrum (cm ^-1 ): 2963
(S), 1784 (m), 1730 (vs), 1605
(S), 1499 (s), 1377 (s), 1258
(Vs), 1177 (w), 1073 (sh), 100
7 (vs), 785 (vs), 723 (s)

(Example 12) (Synthesis 5 of polyamic acid having a polysiloxane side chain)
Polysiloxane having 4,4'-diaminobiphenyl group synthesized in Reference Example 6 (average value of n: 26.7) 0.85
3 g and 0.040 g of p-phenylenediamine were dissolved in 14 ml of a 1: 1 mixed solvent of tetrahydrofuran and N, N-dimethylacetamide to give pyromellitic dianhydride 0.1
59 g was added, and the mixture was stirred at room temperature. The resulting polyamic acid solution was applied onto a glass plate, and the solvent was removed under reduced pressure at 30 ° C. to prepare a unit containing a biphenyl group having a polysiloxane side chain and a unit containing a p-phenylene group having no side chain. An amic acid copolymer film with a ratio of 1: 1 was obtained.

The intrinsic viscosity of the obtained polyamic acid having a polysiloxane side chain is tetrahydrofuran and N, N-
It was 0.39 dL / g at 30 ° C. in a 1: 1 mixed solvent of dimethylacetamide.

IR spectrum (cm ^-1 ): 3320 (w,
b), 2963 (s), 1717 (m), 1676
(M), 1601 (s), 1516 (s), 1402
(S), 1258 (vs), 1074 (sh), 100
9 (vs), 785 (vs)

Example 13 (Synthesis 7 of Polyimide Having Polysiloxane Side Chain) The polyamic acid film obtained in Example 12 was used in Example 4
By heat imidation in the same manner as in (1), an imide copolymer having a ratio of the unit containing a biphenyl group having a polysiloxane side chain to the unit containing a p-phenylene group having no side chain of 1: 1 was obtained.

IR spectrum (cm ^-1 ): 2961
(S), 1780 (m), 1728 (vs), 1605
(S), 1516 (s), 1499 (m), 1364
(S), 1258 (vs), 1179 (w), 1078
(Sh), 1007 (vs), 785 (vs), 723
(S)

[0086]

INDUSTRIAL APPLICABILITY In the polyimide having a polysiloxane side chain of the present invention, since the side chain length, number, etc. can be freely designed in terms of molecular weight, in addition to lowering the melting point and improving the solubility of the polyimide, It is possible to provide new properties that combine the properties of polysiloxane. It can also be used as a blend with polyimide or polysiloxane, or as a compatibilizer.

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[Procedure amendment]

[Submission date] November 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] [Wherein Z is an organopolysiloxane represented by the following formula II:

[Chemical 2] (Wherein R ¹ is a divalent organic group, R ^{2 to} R ⁶ are the same or different monovalent organic groups, n is an integer of 1 or more. The same applies hereinafter), and m is 0 or 1. . same as below. ], An aromatic diamine and an aromatic tetracarboxylic acid dianhydride are reacted in a solvent, and the repeating units have the following formulas III and IV:

[Chemical 3] [Wherein A ¹ is a tetravalent aromatic group and A ² is a divalent organic group represented by the following formula V:

[Chemical 4] And A ³ is a divalent aromatic group. same as below. However, A ¹ , A ³ , R ^{1 to} R ⁶ , m and n may be different for each repeating unit. same as below. And a polyamic acid having an organopolysiloxane side chain in which the molar ratio of the repeating unit represented by the formula III to the repeating unit represented by the formula IV is in the range of 100/0 to 1/99,
This is heated and imidized to give repeating units of the following formulas VI and VII.

[Chemical 5] A process for producing a polyimide having an organopolysiloxane side chain, which comprises a repeating unit represented by the formula VI and a repeating unit represented by the formula VII in a molar ratio of 100/0 to 1/99.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

And A ³ is a divalent aromatic group. same as below. However, A ¹ , A ³ , R ^{1 to} R ⁶ , m and n may be different for each repeating unit. same as below. ] And a polyamic acid having an organopolysiloxane side chain in which the molar ratio of the repeating unit represented by the formula III and the repeating unit represented by the formula IV is in the range of 100/0 to 1/99 is synthesized. Upon heat imidization, the repeating units have the following formulas VI and VII

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[In the formula, R ⁷ is an alkyl group. A silylated polyamic acid having an organopolysiloxane side chain in which the repeating unit represented by the formula VIII and the repeating unit represented by the formula IX are in a molar ratio of 100/0 to 1/99. Of which the repeating unit comprises the above formula VI and the formula VII, and the molar ratio of the repeating unit represented by the formula VI to the repeating unit represented by the formula VII is 1
00/0 is a method for producing a polyimide having organopolysiloxane side chains in ~ 1/99 range.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

A tetracarboxylic dianhydride represented by
Either by equimolar reaction of organopolysiloxane having diaminobiphenyl group of the formula I, or formula I
An organopolysiloxane having a diaminobiphenyl group represented by the following formula XII

Claims (3)

[Claims] 1. An organopolysiloxane having a diaminobiphenyl group represented by the following formula I: ## STR1 ## [In the formula, Z is an organopolysiloxane represented by the following formula II: (Wherein R ¹ is a divalent organic group, R ^{2 to} R ⁶ are the same or different monovalent organic groups, n is an integer of 1 or more. The same applies hereinafter), and m is 0 or 1. . same as below. ], An aromatic diamine and an aromatic tetracarboxylic acid dianhydride are reacted in a solvent, and the repeating units are represented by the following formulas III and IV: [Wherein A ¹ is a tetravalent aromatic group, and A ² is a divalent organic group represented by the following formula V: And A ³ is a divalent aromatic group. same as below. However, A ¹ , A ³ , R ^{1 to} R ⁶ , m and n may be different for each repeating unit. same as below. ] And has the formula (III)
And a polyamic acid having an organopolysiloxane side chain in which the molar ratio of the repeating unit represented by the formula IV to the repeating unit represented by the formula IV is in the range of 100/0 to 1/99 is synthesized, and this is subjected to thermal imidization and repeated. The unit is the following formula I
And formula II A process for producing a polyimide having an organopolysiloxane side chain, which comprises a repeating unit represented by the formula VI and a repeating unit represented by the formula VII in a molar ratio of 100/0 to 1/99. 2. The organopolysiloxane having a diaminobiphenyl group represented by the formula I and the amino group of an aromatic diamine are previously silylated with a trialkylhalosilane or a nitrogen-containing silylating agent, and then the aromatic tetracarboxylic acid diamine is added. Reaction with an anhydride in a solvent yields repeating units of formula VIII and IX [In the formula, R ⁷ is an alkyl group. A silylated polyamic acid having an organopolysiloxane side chain in which the repeating unit represented by the formula VIII and the repeating unit represented by the formula IX are in a molar ratio of 100/0 to 1/99. The method for producing a polyimide having an organopolysiloxane side chain according to claim 1, wherein the polyimide is heated and imidized. 3. The imidization of the polyamic acid having an organopolysiloxane side chain according to claim 1 in a solution or, if necessary, further post-heating to complete the imidization. A method for producing a polyimide having an organopolysiloxane side chain.