JPH06329796A - Polyimide with organopolysiloxane side chain - Google Patents

Abstract

PURPOSE: To obtain the subject polyimide excellent in solvent solubility and useful in preparing a blend with a polyimide or a polysiloxane by selecting for use a polyimide comprising a plurality of types of specified repeating units and having a specified ratio from among the plurality of types of the repeating units.

CONSTITUTION: There is provided a polyimide comprising repeating units represented by formula I {wherein A¹ is a tetravalent aromatic group; A² is a group represented by formula III [wherein Z is a group represented by formula IV (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]} and formula II (wherein A³ is a divalent aromatic group) and having a molar ratio of the repeating units represented by the formula I to the repeating units represented by the formula II of 100/0 to 1/99.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to 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.Ba.
Llauff, Angew.Chem.Int.Ed.Engl., 28, 253 (1989), etc.]. For this purpose, alkyl,
Aromatic polyester having an alkyloxy side chain or introducing an alkyl chain with an ester bond [RW Lenz et al.
Eur. Polym. J., 19: 1043 (1983), M.
Ballauff, Makromol. Chem., Rapid Commun., Volume 7, 407
Page (1986), BR Harkness et al., Macromolecule
s, Vol. 24, p. 6759 (1991), etc.], aromatic polyesters having polystyrene side chains [T. Heitz et al., Ma.
kromol.Chem., 190, 3295 (1989)],
Aromatic polyimides with alkyloxy side chains [M. Ballau
ff et al., Makromol. Chem., 188, 2865 (198).
7)] etc. have been reported. In addition, an example of introducing a polysiloxane side chain into a quasi-rigid aromatic polyimide for the purpose of a separation membrane material has also been reported [Nagase et al., Makromol.
hem., 193, 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. An object of the present invention is to provide a novel polyimide having the above organopolysiloxane side chain.

[0005]

Means for Solving the Problems The above-mentioned object is to provide repeating units of the following formulas I and II:

[0006]

[Chemical 4]

[In the formula, A ¹ is a tetravalent aromatic group,
² is the following formula III

[0008]

[Chemical 5]

Is a divalent organic group represented by the formula:

[0010]

[Chemical 6]

An organopolysiloxane group represented by:
(In the formula, R¹Is a divalent organic group, R²~ R ⁶Are the same or
Different monovalent organic groups, n is an integer of 1 or more. )so,
m is 0 or 1, and A³Is a divalent aromatic group.
(However, A¹, A³, R¹~ R ⁶, M, n are repeated
It may be different for each unit. same as below. )] Consists of
Repeating units of formula I and repeating units of formula II
The molar ratio of the sushi unit is in the range of 100/0 to 1/99
With a polyimide having an organopolysiloxane side chain
To be achieved.

In formulas I and II, the tetravalent aromatic group represented by A ¹ is

[0013]

[Chemical 7]

Examples thereof include, but are not limited to:

A ³ in the formula II is a divalent aromatic group,

[0016]

[Chemical 8]

Examples thereof include, but are not limited to.

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

In formula IV, 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 R⁶Is the raw material of formula V

[0020]

[Chemical 9]

In view of easy availability of raw materials for the hydroorganopolysiloxane represented by the formula (R ^{2 to} R ⁶ have the same meanings as above), a methyl group, an n-butyl group, a sec-butyl group and a tert-butyl group are used. , And a phenyl group are preferred. n is a positive integer, preferably 1 to 5000, more preferably 3 to 1000 is exemplified.

The polyimide having an organopolysiloxane side chain of the present invention can be produced by the method described below. That is, a tetracarboxylic acid dianhydride represented by the following formula VI (wherein A ¹ has the same meaning as described in formula I) and the following formula VII (wherein Z and m are formula III
Which has the same meaning as described above) or is reacted in an equimolar amount with an organopolysiloxane having a diaminobiphenyl group represented by

[0023]

[Chemical 10]

Alternatively, an organopolysiloxane having a diaminobiphenyl group represented by the formula VII and the following formula VIII

H ₂ N--A ³ --NH ₂ VIII

The reaction is carried out so that the total molar amount of the aromatic diamine compound represented by and the tetracarboxylic dianhydride becomes equal to that of the repeating unit represented by the following formula IX and the following formula X: Repeating unit (in the formula, A ^{1 to} A ³
Represents the same meaning as described in formulas I and II)

[0027]

[Chemical 11]

A polyamic acid having an organopolysiloxane side chain having a molar ratio of 100/0 to 1/99 is synthesized, and this can be synthesized by heating and imidizing. This imidization reaction can be carried out in solution with or without an imidizing agent. Also, formula VII
The organopolysiloxane having a diaminobiphenyl group represented by and an aromatic diamine compound represented by the above formula VIII are silylated, and then reacted with an aromatic tetracarboxylic dianhydride in a solvent to give a repeating unit of the following formula XI: and
XII (wherein A ^{1 to} A ³ have the same meanings as described in formulas I and II, and R ⁷ represents an alkyl group),

[0029]

[Chemical 12]

The molar ratio of the repeating unit represented by the formula XI to the repeating unit represented by the formula XII is 100/0 to 1/9.
It can also be produced by synthesizing a silylated polyamic acid having an organopolysiloxane side chain in the range of 9 and subjecting this to thermal imidization.

The aromatic tetracarboxylic dianhydride represented by the formula VI includes 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 VIII, 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 VII includes a terminal hydroorganopolysiloxane represented by the formula V and the following formula XIII.

[0034]

[Chemical 13]

[In the formula, R ⁸ is an organic group having 2 or more carbon atoms having an ethylenically unsaturated bond at the terminal, and m is 0 or 1. And a compound having a terminal olefin represented by the following formula XIV

[0036]

[Chemical 14]

It can be synthesized by synthesizing an organopolysiloxane having a dinitrobiphenyl group represented by the formula (wherein Z and m have the same meanings as described in formula III) and further reducing the nitro group.

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

The dinitrobiphenyl compound represented by the formula XIII has one nitro group bonded to each benzene ring and an organic group R having an ethylenically unsaturated bond at the terminal.
⁸ is bonded to each benzene ring one by one or only to one of the benzene rings. Both the nitro group and R ⁸ may be bonded to any of the 2 to 6 positions of each benzene ring. R ⁸ is -CH =
_{CH 2, -CH 2 CH = CH} 2, -CH 2 CH 2 CH =
_{CH 2, -CH (CH 3)} CH = CH 2, - (CH 2)
_{6 CH = CH 2, -OCH =} CH 2, -OCH 2 CH =
_{CH 2, -OCH 2 CH 2 CH} = CH 2, -OCH (C
_{H 3) CH = CH 2,} -O (CH 2) 6 CH = is CH ₂ and the like, -OCH = C from the material availability viewpoint
_{H 2, -OCH 2 CH = CH} 2, -OCH 2 CH 2 CH
_{= CH 2, -OCH (CH 3} ) CH = CH 2, -O (C
H ₂ ) ₆ CH═CH _{2 and the} like are preferable. These compounds are not commercially available in general, but can be synthesized by the method shown in Examples later.

A terminal hydroorganopolysiloxane of the formula V
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 thermal imidization of polyamic acid is carried out by heating at 100 ° C. to 400 ° C., preferably 150 ° C. to 350 ° C. after removing the solvent. At this time, the atmosphere may be air, an inert gas, or a reduced pressure. The imidization in the solution is carried out in the various solvents described above, for example, using acetic anhydride and a base such as amine as the imidizing agent at a reaction temperature of about 50 ° C. to 150 ° C., or without using the imidizing agent. The method is, for example, performed at a temperature of about 150 ° C. to 200 ° C., but the method of imidization in a solution is not limited to these. In the imidization in solution, the imidization rate is 100% depending on the reaction conditions.
Although it can be made smaller, the imidization can be completed by post-heating under the above-mentioned heating imidization conditions.

Silylation of the organopolysiloxane having a diaminobiphenyl group represented by the formula VII and the aromatic diamine compound represented by the formula VIII is performed with a silylating agent. Examples of the silylating agent include trialkylhalosilanes such as trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, and methyldiethylbromosilane, or 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. The reaction temperature is 0 to 200 ° C, preferably 20 to 140 ° C.

The silylated polyamic acid is synthesized by using these silylated diamines in the same manner as the synthesis of the 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.

[0046]

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.

Then, 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,

[0050]

[Chemical 15]

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 degrees of polymerization as shown in Table 1 were synthesized.

[0053]

[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. However, 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 In the same manner as in Reference Example 5, polysiloxanes having 4,4′-diaminobiphenyl groups having different polymerization degrees as shown in Table 2 were synthesized.

[0056]

[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 obtained 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.

[0061]

[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.

[0065]

[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 which had been purged with argon. 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 this 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).

[0085]

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

Claims (3)

[Claims] 1. Repeating units are represented by the following formulas I and II: [In the formula, A ¹ is a tetravalent aromatic group, and A ² is the following formula II:
I [Chemical 2] Is a divalent organic group represented by the following formula, and in the formula III, Z is represented by the following formula IV: An organopolysiloxane group represented by the formula (wherein R ¹ is 2
Valent organic groups, R ^{2 to} R ⁶ are the same or different monovalent organic groups, n is an integer of 1 or more), m is 0 or 1, and A
³ is a divalent aromatic group. However, A ¹ , A ³ , R ¹
To R ^6, m, may be different for each n mother repeating units. ] And a repeating unit of formula II
The molar ratio of repeating units represented by is from 100/0 to 1 /
Polyimides having organopolysiloxane side chains in the range of 99. 2. In formula III, m is 0.
A polyimide having an organopolysiloxane side chain. 3. The polyimide having an organopolysiloxane side chain according to claim 1, wherein R ^{2 to} R ⁵ in the formula IV are methyl groups.