JP3226377B2 - Method for producing polyimide having organopolysiloxane side chain - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyimide having a novel organopolysiloxane side chain.

[0002]

2. Description of the Related Art Aromatic polymers such as aromatic polyesters, aromatic polyamides (aramids), and aromatic polyimides are high-performance polymer materials because of their high mechanical strength, heat resistance, and solvent resistance. [Polymer Society, High Performance Aromatic Polymer Materials, Maruzen (199
0) etc.]. However, compared to conventional flexible polymers, these rigid linear polymers have low solubility in solvents and high melting points, and are inferior in processability, so their industrial development and use have recently begun. It's just

[0003] As one of the methods for improving the solubility or 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)). For such purposes, aromatic polyesters having an alkyl or alkyloxy side chain or having an alkyl chain introduced through an ester bond [R. W. Lenz et al., Eu
r. Polym. J. 19, 1043 pages (19
83); Ballauff, Makromol. C
hem. , Rapid Commun. , 7 volumes, 407
Page, (1986); R. Harkness et al.
Macromolecules, Vol. 24, p. 6759 (1991), etc.], aromatic polyesters having polystyrene side chains [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, p. 2865 (1987)]. Further, there has been reported an example in which a polysiloxane side chain is introduced into a quasi-rigid aromatic polyimide for the purpose of a separation membrane material [Nagase et al., Makromol. Ch
em. 193, p. 1509 (1992), etc.].

[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 is still unknown. Not been. Polyimides having such organopolysiloxane side chains can be expected to have novel properties that combine the properties of polyimide and polysiloxane in addition to the above-mentioned improvements in solubility and the like. An object of the present invention is to provide a method for producing a novel polyimide having an organopolysiloxane side chain as described above.

[0005]

According to a first aspect of the present invention, there is provided:
Organopolysiloxane having a diaminobiphenyl group represented by the following formula I

[0006]

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Wherein Z is an organopolysiloxane represented by the following formula II

[0008]

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(Wherein 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. The aromatic diamine and the aromatic tetracarboxylic dianhydride are reacted in a solvent to form a repeating unit represented by the following formula II
I and Formula IV

[0010]

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

[0012]

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Wherein 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 having a molar ratio of the repeating unit represented by the formula III to the repeating unit represented by the formula IV in the range of 100/0 to 1/99. After heat imidization, the repeating units are represented by the following formulas VI and VII

[0014]

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Wherein the molar ratio of the repeating unit of the formula VI to the repeating unit of the formula VII is from 100/0
This 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 that the amino group of the diaminobiphenyl group-containing organopolysiloxane represented by the above formula I and the aromatic diamine is preliminarily silylated with a trialkylhalosilane or a nitrogen-containing silylating agent. Is reacted with an aromatic tetracarboxylic dianhydride in a solvent to form a repeating unit of the formula VIII or IX

[0017]

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

The tetravalent aromatic group represented by A ¹ includes:

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However, the present invention is not limited to these.

A ³ is a divalent aromatic group,

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Examples are given, but the invention is not limited to these.

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 as follows:
The polysiloxane chain Z may be bonded to each benzene ring one by one or one to only one benzene ring.

In the formula II, R¹And a divalent organic group represented by
, Alkylene group, oxyalkylene group, phenylene
Examples include an alkylene group and a phenyleneoxyalkylene group.
Oxyalkyl
Rene groups are preferred. R^Two~ R ⁶Is a monovalent organic group,
These include methyl, ethyl, propyl, octyl
Alkyl group, 2-phenylethyl group, 2-phenyl
Propyl group, 3,3,3-trifluoropropyl group
Aryl groups such as substituted alkyl groups and phenyl groups, or
Examples thereof include a substituted aryl group such as a ril group. Above all R^Two~
R^FiveIs preferably a methyl group and a phenyl group
And a methyl group is preferred from an economic point of view.
New R⁶Is represented by the following formula X

[0025]

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Due to the availability of the raw materials for 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, more preferably 3 to 1,000.

The production of the polyimide having an organopolysiloxane side chain of the present invention can be carried out by the following method. That is, the following formula XI

[0028]

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

H ₂ N—A ³ —NH ₂ XII

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

Further, after the organopolysiloxane having a diaminobiphenyl group represented by the formula I and the aromatic diamine compound represented by the formula XII are silylated, an aromatic tetracarboxylic dianhydride represented by the formula XI and a solvent And the repeating unit consists of the above formulas VIII and IX, and the molar ratio of the repeating unit represented by the formula VIII to the repeating unit represented by the formula IX is in the range of 100/0 to 1/99. It can also be produced by synthesizing a silylated polyamic acid having an organopolysiloxane side chain and imidizing it with heat.

The aromatic tetracarboxylic dianhydride represented by the formula XI 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'-benzophenonetetracarboxylic 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-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-anthracenetetracarboxylic dianhydride, 3, Examples thereof include 4,9,10-perylenetetracarboxylic dianhydride and 2,3,5,6-pyrazinetetracarboxylic dianhydride, but are not limited thereto. It can also be used.

Examples of the aromatic diamine compound represented by the formula XII include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,6-diaminonaphthalene, , 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 thereof include 1,1,3,3,3-hexafluoro-2,2-bis (4-diaminophenyl) propane and 4,4′-diaminodiphenylsulfone, but are not limited thereto. Also, a mixture of these can be used.

The organopolysiloxane having a diaminobiphenyl group represented by the formula I can be obtained by mixing a terminal hydroorganopolysiloxane represented by the formula X with the following formula XIII

[0036]

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[Wherein, R ⁸ is an organic group having an ethylenically unsaturated bond at a terminal. By a hydrosilylation reaction in the presence of a catalyst with a compound having a terminal olefin represented by the following formula XIV:

[0038]

Embedded image Can be synthesized by synthesizing an organopolysiloxane having a dinitrobiphenyl group represented by the following formula, and further reducing the nitro group.

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

Dinitrobiphenyl compound represented by formula XIII
The product has one nitro group attached to each benzene ring.
And an organic group R having an ethylenically unsaturated bond at a terminal
⁸Is one of each benzene ring
Has one bond to only one benzene ring. Nitro
Group, R⁸And any of the 2- to 6-positions of each benzene ring
It may be attached to a position. R⁸Is -CH = C
H_Two, -CH_TwoCH = CH_Two, -CH_TwoCH_TwoCH = C
H_Two, -CH (CH_Three) CH = CH_Two,-(CH _Two)₆C
H = CH_Two, -OCH = CH_Two, -OCH_TwoCH = CH
_Two, -OCH_TwoCH_TwoCH = CH_Two, -OCH (C
H_Three) CH = CH_Two, -O (CH_Two)₆CH = CH_TwoEtc.
As an example, -OCH = CH
_Two, -OCH_TwoCH = CH_Two, -OCH_TwoCH_TwoCH =
CH_Two, —OCH (CH_Three) CH = CH _Two, -O (CH
_Two)₆CH = CH_TwoAre preferred. These compounds are generally
Is not commercially available, but the method described later as an example, etc.
Can be synthesized by

The terminal hydroorganopolicy represented by the formula X
Hydane of oxane with olefinic compound of formula XIII
The rosilylation reaction is carried out in the presence of a catalyst, preferably in a solvent.
It is done in. Catalysts include chloroplatinic acid, platinum-divinyl
Nyltetramethyldisiloxane complex, platinum such as platinum carbon
It is most common to use a system catalyst, but (Ph _Three
P)_ThreeRhCl, (Ph_TwoPH)_ThreeRhCl, (Ph_Three
P)_Three(CO) RhH, Co (I), Pd (I
Transition metal catalysts such as I) and Ru (II) can also be used.
Wear. The amount of catalyst is usually based on 1 mole of carbon-carbon double bond.
Then 1/10^FourFrom 1/10^TwoIt may be about a mole. Solvent and
Benzene, toluene, xylene, etc.
Hydrogen solvent, dissolving aliphatic hydrocarbons such as hexane and heptane
Medium such as ether, diethyl ether, tetrahydrofuran, etc.
Solvent, methanol, ethanol, propanol, etc.
Alcoholic solvents, acetone, methyl ethyl ketone, etc.
Ketone solvent, ester such as ethyl acetate and butyl acetate
Solvent, chloroform, trichlorethylene, carbon tetrachloride
Halogenated hydrocarbon solvents such as
Muamide, dimethylacetamide, dimethylsulfoxy
And the like. The reaction temperature is preferably from 0 to 200 ° C.
Is carried out at 40-110 ° C. in a dry inert atmosphere
However, a small amount of oxygen is desirable depending on the catalyst.

As a method for reducing the nitro group of the dinitrobiphenyl group-containing organopolysiloxane 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. An example is a catalytic reduction method using the used hydrogen. The reaction is preferably performed in a solvent, and examples of the solvent include the various solvents described above and a mixed solvent thereof.
The reaction temperature preferably ranges from 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. Although the reaction can be carried out without solvent, it is preferably carried out in a solvent, and examples of the solvent include the various solvents described above and mixtures thereof. The reaction temperature is preferably from -50C to 100C, more preferably from 0C to 50C.

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

The 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 by a silylating agent. As a silylating agent, trimethylchlorosilane,
Triethylchlorosilane, triphenylchlorosilane,
Examples include trialkylhalosilanes such as methyldiethylbromosilane, and nitrogen-containing silylating agents such as hexamethyldisilazane, N, N-diethylaminotrimethylsilane, N, O-bis (trimethylsilyl) carbamate, and N-trimethylsilylimidazole. . When using a trialkylhalosilane, it is preferable to neutralize the by-produced hydrogen halide in the presence of a base. When a nitrogen-containing silylating agent is used, a catalyst such as trimethylchlorosilane or ammonium sulfate may be added. The silylation reaction can be carried out in the above-mentioned various solvents other than the alcohol solvent, but the solvent may be omitted. Reaction temperature is 0-20
0 ° C, preferably 20 to 140 ° C.

The silylated polyamic acid is synthesized by using these silylated diamines in the same manner as in the synthesis of the above-mentioned polyamic acid. Further, a polyimide is obtained by heating the silylated polyamic acid in the same manner as described above. Of course, the ordinary polyamic acid can be obtained by hydrolyzing the silyl ester, and this can be heated or imidized in a solution as described above.

[0047]

EXAMPLES Next, the present invention will be described in more detail by 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) To 13.0 g of 4,4'-dinitro-2-aminobiphenyl was added 15.0 ml of water 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 thereto in an ice bath, stirred for 10 minutes, and left for several minutes. 33.4 concentrated sulfuric acid in 25 ml of water
After adding the ml, the mixture was boiled, and the above reaction mixture was slowly added dropwise to the mixture. After boiling for 5 minutes, the mixture was poured into a beaker in an ice bath. This was filtered by suction, and the filter cake was purified by column chromatography.
4'-dinitro-2-hydroxybiphenyl 10.9 g
(83.9% yield) as a tan powder.

Next, the obtained 4,4'-dinitro-2-
Acetone 9 obtained by drying 10.4 g of hydroxybiphenyl
Dissolved in 5 ml, potassium carbonate 5.52 g, 4-bromo-
7.56 g of 1-butene was added and refluxed for 71 hours. Purified by a conventional method, 2- (3-butenyloxy) -4,4 '
-Dinitrobiphenyl (5.20 g, yield 41.4%) 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 a 3% solution of chloroplatinic acid in isopropyl alcohol,

[0051]

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The terminal hydropolysiloxane (n)
(Average value of 14.4) in 20 ml of dry toluene was added dropwise 7.88 g, and stirring was continued at 100 ° C. for 4 hours. Purified by column chromatography, 8.68
g of a polysiloxane having a 4,4'-dinitrobiphenyl group 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.

[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 the suspension. 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 with stirring for 3 hours, the catalyst was filtered off and the solvent was distilled off under reduced pressure to obtain a polysiloxane having a 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 degrees of polymerization as shown in Table 2 were synthesized.

[0057]

[Table 2]

Example 1 Synthesis of Polyamic Acid Having Polysiloxane Side Chain 1
Polysiloxane having a 4,4'-diaminobiphenyl group synthesized in Reference Example 5 (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 resulting polyamic acid solution was applied on a glass plate, and the solvent was removed at 30 ° C. under reduced pressure to obtain a polyamic acid film.

The polyamic acid having a polysiloxane side chain obtained has an intrinsic viscosity of 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 near 00 and aromatic C—H near 3050 were weak in intensity and could not be identified. s refers to strong absorption, vs refers to very strong absorption, m refers to moderate absorption, and sh refers to what appears as a shoulder of another absorption. )

Examples 2 and 3 (Synthesis of Polyamic Acid Having Polysiloxane Side Chain)
3) Polyamic acids having different degrees of polymerization of polysiloxane as shown in Table 3 were synthesized in the same manner as in Example 1. An IR spectrum similar to that of Example 1 was obtained, but in Examples 2 and 3, N—H and 3050 cm ⁻¹ were around 3290 cm ^−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 placed in an argon atmosphere at 60 ° C. for 20 minutes, at 100 ° C. for 20 minutes, and at 200 ° C. for 20 minutes. Heating was performed for 2 hours to obtain a polyimide film having a polysiloxane side chain.

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
And the polyamic acid obtained in 3 was imidized.

[0066]

[Table 4]

Example 7 Synthesis of Polyimide Having Polysiloxane Side Chain 4) Polysiloxane having 4,4'-diaminobiphenyl group (average value of n is 14.4) as in Example 1. 735
g of pyromellitic dianhydride and 0.112 g of pyromellitic dianhydride in 4 ml of tetrahydrofuran, and 0.434 g of triethylamine and 0.44 g of acetic anhydride were added to the resulting 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) 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 at 60 ° C. for 2 hours in an oil bath, and at 80 ° C. for 38 hours. After the salt was separated by filtration, the solvent and the like were removed under reduced pressure.
A polysiloxane having a 4'-bis (trimethylsilylamino) biphenyl group was obtained (yield 1.04 g, 83.
1%).

Example 8 (Synthesis of Silylated Polyamic Acid Having Polysiloxane Side Chain) All reactions were carried out in a glove bag purged with argon. In a 10 ° C. water bath, 1.00 g of the polysiloxane having a 4,4′-bis (trimethylsilylamino) biphenyl group synthesized in Reference Example 8 was dissolved in 4 ml of tetrahydrofuran, and pyromellitic dianhydride previously prepared was dissolved. A solution of the product in tetrahydrofuran 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 resulting 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 inherent viscosity of the polyamic acid obtained by desilylation of 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 imidized by heating 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 polysiloxane side chain)
Polysiloxane having a 4,4'-diaminobiphenyl group synthesized in Reference Example 5 (average value of n: 14.4) 0.20
1 g of polysiloxane having a 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 generated 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 types of side chains having different lengths (ratio of two units: 1: 1).

The intrinsic viscosity of the obtained polyamic acid having a polysiloxane side chain is determined in tetrahydrofuran at 25 ° C.
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 broad absorption)

Example 11 Synthesis of Polyimide Having Polysiloxane Side Chain 6) The polyamide acid film obtained in Example 10 was used in Example 4
Imidized by heating in the same manner as described above, and an imide copolymer having two kinds of side chains having different lengths (ratio of two kinds of units 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 of polyamic acid having polysiloxane side chain 5)
Polysiloxane having a 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, and pyromellitic dianhydride 0.1 was dissolved.
59 g was added and the mixture was stirred at room temperature. The resulting polyamic acid solution was applied on a glass plate, and the solvent was removed at 30 ° C. under reduced pressure to remove the polysiloxane unit containing a biphenyl group having a side chain and the unit containing a p-phenylene group having no side chain. An amic acid copolymer film having a ratio of 1: 1 was obtained.

The intrinsic viscosity of the obtained polyamic acid having a polysiloxane side chain is determined by using tetrahydrofuran and N, N-
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 polyamide acid film obtained in Example 12 was replaced with Example 4
By heat imidization in the same manner as described above, an imide copolymer was obtained in which the 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 was 1: 1.

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]

The polyimide having a polysiloxane side chain of the present invention can be freely designed in terms of the length, number, etc. of the side chain. It can have new properties that combine the properties of polysiloxanes. It can also be used as a blend with polyimide or polysiloxane, or as a compatibility-imparting agent.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-294327 (JP, A) JP-A-5-220210 (JP, A) Polym. Sci. Part A: Polym. Chem. (1994), 32 (8), 1581-92 (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An organopolysiloxane having a diaminobiphenyl group represented by the following formula I: Wherein Z is an organopolysiloxane represented by the following formula II: (Where 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, and the same applies hereinafter), and m is 0 or 1. . same as below. ], An aromatic diamine and an aromatic tetracarboxylic 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. A polyamic acid having an organopolysiloxane side chain having a molar ratio of the repeating unit represented by the formula III to the repeating unit represented by the formula IV in the range of 100/0 to 1/99,
This is heated to be imidized, and the repeating units are represented by the following formulas VI and VII. Wherein the molar ratio of the repeating unit represented by the formula VI to the repeating unit represented by the formula VII is in the range of 100/0 to 1/99. 2. An organopolysiloxane having a diaminobiphenyl group represented by the formula I and an amino group of an aromatic diamine which have been previously silylated with a trialkylhalosilane or a nitrogen-containing silylating agent, and then an aromatic tetracarboxylic acid By reacting with an anhydride in a solvent, the repeating units are represented by the formulas VIII and IX. Wherein R ⁷ is an alkyl group. A silylated polyamic acid having an organopolysiloxane side chain having a molar ratio of the repeating unit represented by the formula VIII to the repeating unit represented by the formula IX in the range of 100/0 to 1/99. The method for producing a polyimide having an organopolysiloxane side chain according to claim 1, wherein 3. The polyamic acid having an organopolysiloxane side chain according to claim 1, wherein the polyamic acid is imidized in a solution or, if necessary, the imidization is completed by further post-heating. For producing a polyimide having an organopolysiloxane side chain.