JPH0971647A - Silicon-containing polyimide and method for producing the same - Google Patents

Abstract

(57) Abstract: A silicon-containing polyimide, which is a heat-resistant and combustion-resistant material, is provided. SOLUTION: General formula (1) (In the formula, R ¹ is a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, R ² , R ⁵ are alkylene groups, alkenylene groups, alkynylene groups, divalent aromatic groups, and R ³ is an alkylene group. , An alkenylene group, an alkynylene group, a divalent aromatic group and a group obtained by crosslinking these with a silanedyl group, and R ⁴ is a tetravalent aliphatic or aromatic group.
m is a positive integer, n is 0 or a positive integer. ) A silicon-containing polyimide represented by the following, and a method for producing the same.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silicon-containing polyimide having an acetylene bond and a Si--H bond, which is useful as a heat resistant and combustion resistant material, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, many engineering plastics have been developed as heat-resistant materials that are lightweight and have excellent mechanical properties. However, polyimide has the highest heat resistance of practical plastics (heat distortion temperature of about 360 ° C.), and further improvement of heat resistance will significantly reduce the workability of plastics. On the other hand, the heat resistance of silicon-based polymers centering on silicone is still low, and the glass transition temperature of commercialized products is about 100 ° C. Further, in the polyimide containing silicon, there is a silicone polyimide polymer in which silicone is introduced into the diamine component,
The operating temperature is 220 ° C or lower.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventors have made the task of further improving the heat resistance of polyimide, and have made diligent efforts toward this, and have made a diamine compound having a Si—H bond and an acetylene bond and a tetracarboxylic acid. Si-H than dianhydride
The present invention has been reached by producing a polyimide having a bond and an acetylene bond.

[0004]

The present invention provides a compound represented by the general formula (1) having an acetylene bond, a Si--H bond and an imide bond in a repeating unit.

[0005]

Embedded image (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aromatic group such as a phenyl group or a naphthyl group, and R ² and R ⁵ are 1 to 30 carbon atoms.
A divalent aromatic group such as an alkylene group, an alkenylene group, an alkynylene group, a phenylene group or a naphthylene group, an aromatic group directly or by a cross-linking member such as a methylene group, an isopropylidene group, an ether group, a carbonyl group or a sulfide group. A group in which the linked group and the aromatic group are linked to an alkylene group having 1 to 30 carbon atoms, an alkenylene group, and an alkynylene group, and these may contain a substituent such as a halogen atom, a hydroxyl group, and a carboxyl group. R ³ is a divalent aromatic group such as an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, a phenylene group or a naphthylene group, a group in which an aromatic group is linked directly or by a bridging member, and an aromatic group are carbon atoms. Alkylene groups, alkenylene groups, and alkynylene groups of the formulas 1 to 30, which are directly or directly linked to each other by a bridging member such as a methylene group, an isopropylidene group, an ether group, a carbonyl group, a sulfide group, and a silanenedyl group, and these are halogen atoms, It may contain a substituent such as a hydroxyl group or a carboxyl group. R ⁴ is a tetravalent aliphatic or aromatic group having 2 to 30 carbon atoms and a group in which an aromatic group is linked directly or by a crosslinking member, and these are substituents such as a halogen atom, a hydroxyl group, an amino group and a carboxyl group. May be included. l and m are positive integers, n is 0
Or it is a positive integer. ) The silicon-containing polyimide represented by

The present invention also provides a compound represented by the general formula (2)

[0007]

Embedded image (In the formula, R ¹ is a hydrogen atom or an aromatic group such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group or a naphthyl group having 1 to 30 carbon atoms, and R ² is an alkylene group having 1 to 30 carbon atoms or an alkenylene group. , Divalent aromatic groups such as alkynylene group, phenylene group and naphthylene group, and groups and aromatic groups in which aromatic groups are linked directly or by a cross-linking member such as methylene group, isopropylidene group, ether group, carbonyl group, sulfide group The group is a group linked to an alkylene group having 1 to 30 carbon atoms, an alkenylene group, or an alkynylene group, which may contain a substituent such as a halogen atom, a hydroxyl group or a carboxyl group, and R ³ has 1 carbon atom. To 30 alkylene groups, alkenylene groups, alkynylene groups, divalent aromatic groups such as phenylene groups and naphthylene groups, and aromatic groups directly. Is a group linked by a bridging member and an aromatic group is a alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group directly or a methylene group, an isopropylidene group, an ether group, a carbonyl group, a sulfide group, a silanedyl group, etc. A group connected by a member, which may contain a substituent such as a halogen atom, a hydroxyl group, and a carboxyl group, and l is a positive integer.) In a polar organic solvent,
General formula (3)

[0008]

[Chemical 6] (In the formula, R ⁴ is a tetravalent aliphatic or aromatic group having 2 to 30 carbon atoms and a group in which an aromatic group is linked directly or by a crosslinking member, and these are a halogen atom, a hydroxyl group, an amino group, a carboxyl group. It may also contain a substituent such as). The method for producing a silicon-containing polyimide represented by the general formula (1) is characterized by reacting with a tetracarboxylic dianhydride represented by the formula (1).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The features of the production method of the present invention are summarized in the reaction formula (4).

[0010]

[Chemical 7] As shown in, a polyamic acid is produced by reacting a diamine compound with a tetracarboxylic acid dianhydride in an organic polar solvent, and then the reaction formula (5)

[0011]

Embedded image As represented by the following, the polyamic acid is dehydrated to produce a silicon-containing polyimide having an acetylene bond and a Si—H bond.

An acetylene bond represented by the general formula (1),
The method for producing a silicon-containing polyimide having a Si-H bond and an imide bond will be described in more detail. A method for producing a diamine compound having a acetylene bond and a Si—H bond represented by the general formula (2) as a raw material is easily quantified by dehydrogenating an aminosilane compound and an aminoethynyl compound in the presence of a catalyst. However, the production method is not particularly limited to these. The diamine compound containing the acetylene bond and the Si—H bond represented by the general formula (2) as the raw material is specifically bis (3,3′-).
Aminophenylethynyl) silane (chemical formula (6))

[0013]

Embedded image , Bis (2,2'-aminophenylethynyl) silane,
Bis (4,4′-aminophenylethynyl) silane, bis (3,3′-aminophenylethynyl) methylsilane (chemical formula (7))

[0014]

Embedded image , Bis (2,2'-aminophenylethynyl) methylsilane, bis (4,4'-aminophenylethynyl) methylsilane, bis (3,3'-aminophenylethynyl)
Phenylsilane (chemical formula (8))

[0015]

Embedded image , Bis (2,2'-aminophenylethynyl) phenylsilane, bis (4,4'-aminophenylethynyl) phenylsilane, bis (3,3'-aminophenylethynyl) trifluoromethylsilane, bis (3,3 '-Aminophenylethynyl) vinylsilane, bis (3,3'-
Aminophenylethynyl) ethynylsilane, chemical formula (9)

[0016]

[Chemical 12] , Chemical formula (10)

[0017]

Embedded image , Chemical formula (11)

[0018]

Embedded image , Chemical formula (12)

[0019]

[Chemical 15] , Chemical formula (13)

[0020]

Embedded image , Chemical formula (14)

[0021]

Embedded image , Chemical formula (15)

[0022]

Embedded image , Chemical formula (16)

[0023]

Embedded image , Chemical formula (17)

[0024]

Embedded image , Chemical formula (18)

[0025]

[Chemical 21] , Chemical formula (19)

[0026]

Embedded image , Chemical formula (20)

[0027]

Embedded image , Chemical formula (21)

[0028]

Embedded image , Chemical formula (22)

[0029]

Embedded image , Chemical formula (23)

[0030]

[Chemical formula 26] , Chemical formula (24)

[0031]

Embedded image , Chemical formula (25)

[0032]

Embedded image , Chemical formula (26)

[0033]

[Chemical 29] , Chemical formula (27)

[0034]

Embedded image , Chemical formula (28)

[0035]

[Chemical 31] , Chemical formula (29)

[0036]

Embedded image , Chemical formula (30)

[0037]

[Chemical 33] , Chemical formula (31)

[0038]

Embedded image , (3-aminophenyl) (3-aminophenylethynyl) silane (chemical formula (32))

[0039]

Embedded image , (2-aminophenyl) (2-aminophenylethynyl) silane, (4-aminophenyl) (4-aminophenylethynyl) silane, (3-aminophenyl) (3-
Aminophenylethynyl) methylsilane (chemical formula (3
3))

[0040]

Embedded image , (2-aminophenyl) (2-aminophenylethynyl) methylsilane, (4-aminophenyl) (4-aminophenylethynyl) methylsilane, (3-aminophenyl) (3-aminophenylethynyl) phenylsilane (chemical formula (34 ))

[0041]

Embedded image , (2-aminophenyl) (2-aminophenylethynyl) phenylsilane, (4-aminophenyl) (4-aminophenylethynyl) phenylsilane or bis (4
-Amino-1-butynyl) (phenyl) silane and the like.

The diamine compounds having an acetylene bond and a Si--H bond can be used alone or in admixture of two or more. Furthermore, it can be used as a mixture with another diamine compound containing no Si—H bond. Si that can be mixed
As a diamine compound containing no —H bond, ethylenediamine, bis (4,4′-aminophenyl) ether,
Bis (3,3′-aminophenyl) ether, bis (4,4′-aminophenyl) methane, bis (3,3 ′)
-Aminophenyl) methane, 2,2'-bis (4,4 '
-Aminophenyl) propane and the like.

Another formula (3) which is another raw material
The tetracarboxylic dianhydride represented by, specifically,
Ethylene tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic carboxylic acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2 ′, 3, 3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2 '-Bis (3,4
-Dicarboxyphenyl) propane dianhydride, 2,2 '
-Bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2'-bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride and the like can be mentioned. These tetracarboxylic dianhydrides are used alone or in combination of two or more. As the organic polar solvent, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N
-Methylcaprolactane, 1,3-dimethylimidazolidinone, dimethyl sulfone, m-cresol, pyridine, and the like.

The reactor comprises a part for supplying raw materials, a stirrer inside the reaction container, a part for controlling the temperature of the reaction container and the like. A diamine compound having an acetylene bond and a Si—H bond represented by the general formula (2) and a solvent are charged in a container. An organic polar solvent is used as the solvent. The inside of the container may be an air atmosphere, but it is preferably replaced with an inert gas such as high-purity nitrogen. Further, a tetracarboxylic acid dianhydride that is equimolar to the diamine compound is added and completely dissolved. The order of charging the diamine compound and the tetracarboxylic dianhydride is not particularly limited. The reaction is performed for a certain period of time while maintaining the reaction container at a predetermined temperature. The reaction temperature is usually 75 ° C or lower, preferably 50 ° C or lower. The reaction time varies depending on the solvent used, the tetracarboxylic dianhydride and the reaction temperature, and usually the reaction is performed for a time sufficient to complete the production of polyamic acid. 2-12 hours is usually sufficient. The reaction pressure is not particularly limited, and it can be carried out at normal pressure.

The polyamic acid obtained is 100 to 100 in use.
It can be dehydrated at 300 ° C. or dehydrated in advance to be used as a polyimide. For the method of dehydration in advance, a solvent that is azeotropic with a predetermined amount of water is added to the polyamic acid reaction solution,
A thermal method of dehydrating by azeotroping for a predetermined time and a chemical method of dehydrating by adding a dehydrating reagent and a catalyst to the reaction solution and reacting for a predetermined time can be used, but are not particularly limited to these methods. . As the solvent which is azeotropic with water by the thermal method, benzene, toluene, m-xylene, ethylbenzene, anisole, dioxane, p-chlorotoluene, heptane, cyclohexane and the like can be used.
The azeotropic temperature is 70 to 150 ° C., and the azeotropic time is 5 to 40 hours, depending on the type of solvent and the azeotropic temperature. As a dehydrating reagent in the chemical method, anhydrous carboxylic acid, specifically acetic anhydride, propionic anhydride, butyric anhydride, trifluoroacetic anhydride, phthalic anhydride, as a catalyst pyridine, pyrazine, pyrimidine, pyridazine, trimethylamine,
Bases such as triethylamine, tributylamine, N, N dimethylaniline can be used.

[0046]

EXAMPLES The present invention will be described below with reference to examples. Reference Example First, a raw material is manufactured. A quartz firing tube was charged with 7.2 g of magnesium hydroxide having a particle size of 30 to 60 mesh, and the amount of 0.2 g.
Pyrolysis was performed at 350 ° C. for 3 hours under a reduced pressure of 3 mmHg to obtain 5.0 g of magnesium oxide. A magnetic stir bar was installed inside a 100 ml glass container, and the inside of the container was replaced with high-purity nitrogen gas. Subsequently, 4.7 g of 3-ethynylaniline, 8.9 g of 3-aminophenylethynyl (phenyl) silane and 40 ml of toluene as a solvent were charged in a container, and 5.0 g of magnesium oxide produced above was stirred under a nitrogen blanket while stirring. added. After stirring at 30 ° C. for 24 hours, the reaction solution was filtered with a glass filter to remove the catalyst. After further concentrating the reaction solution, bis (3,3′-aminophenylethynyl) phenylsilane was separated by GPC (gel permeation chromatography). Yield 3.8g
Met.

Example 1 A method for producing a silicon-containing polyimide having a Si—H bond and an acetylene bond when n is 0 in the general formula (1): A magnetic stirrer is installed inside a 50 ml glass container. The inside of the container was replaced with high-purity nitrogen gas. Subsequently, 1.70 g (5.03 mmol) of bis (3,3′-aminophenylethynyl) phenylsilane and 10 ml of N, N-dimethylacetamide as a solvent were charged into the container. 1.10 g of pyromellitic dianhydride with stirring
(5.05 mmol) was added and completely dissolved. After stirring at room temperature for 4 hours, 4 ml of toluene was added, and the stirring was continued at 90 ° C. for 10 hours. After adding 4 ml of toluene and filtering the reaction solution, the filtered product was washed with toluene and vacuum dried at 60 ° C. overnight. 2.2 g of polymer powder was obtained. The yield was 70%.

The polystyrene-reduced weight average molecular weight by GPC (gel permeation chromatography) was 5,300 in the state of the polyamic acid before dehydration. Since the polyimide is almost insoluble in the solvent, the NMR spectrum was measured in the polyamic acid state. ¹ H-NMR (ppm, d-DMSO) 3.3 (N H ), 5.2 (Si H ), 7.2 to 8.3
(Ph), 10.6 (COO H ). ^{13 C-NMR (ppm, d} -DMSO) 86.5 (Si- C ≡C), 108.1 (C≡ C -P
h), 128.2~141.1 (Ph), 163.3~166.6 (N- C O-, C OOH). ²⁹ Si-NMR (ppm, d-DMSO) 63.9 (Ph- Si H <) The elemental analysis measurements (polyimide) are carbon 73.0% (theoretical value 73.8%), hydrogen 3.6% (theoretical value 3.1%). , The measured value is in good agreement with the theoretical value within the range of measurement error. IR measurement (polyimide, KBr tablet) confirmed the formation of imide groups from the absorption at 1380 cm ^-1 and 1720 cm ^-1 . IR (cm ^-1 ) 720 (m), 790 (m), 840 (m), 1120 (s), 1380
(s), 1720 (s), 1780 (w), 2160 (s). Next, the thermophysical properties of this polyimide were measured by TGA-DTA. Almost no weight loss was observed in the argon atmosphere, the weight residue at 1000 ° C. was 67%, and Td ₅ (5% weight loss temperature) was 619 ° C. This value is 1000 ℃ in Argon atmosphere of polyimide (Capton)
The remaining weight is 55%, which is superior to Td ₅ 586 ℃,
It is shown that the silicon-containing polyimide having an acetylene bond and a Si—H bond in the present invention is extremely excellent in heat resistance.

Example 2 In the general formula (1), Si when n is a positive integer
Method for producing silicon-containing polyimide having —H bond and acetylene bond: Bis (3,
3'-aminophenylethynyl) phenylsilane 0.8
A reaction was carried out under the same conditions as in Example 1 except that a mixture of 5 g and bis (4,4′-aminophenyl) ether 0.50 g was used. 2.0 g of silicon-containing polyimide was obtained. The yield was 72%.

[0050]

EFFECTS OF THE INVENTION A novel silicon-containing polyimide having a Si—H bond and an acetylene bond, which is excellent in heat resistance and combustion resistance, is synthesized from a diamine compound having a Si—H bond and an acetylene bond and tetracarboxylic dianhydride. I was able to.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masayoshi Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (2)

[Claims] 1. A acetylene bond, Si in a repeating unit.
General formula (1) having —H bond and imide bond: (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aromatic group such as a phenyl group or a naphthyl group, and R ² and R ⁵ are 1 to 30 carbon atoms.
A divalent aromatic group such as an alkylene group, an alkenylene group, an alkynylene group, a phenylene group or a naphthylene group, an aromatic group directly or by a cross-linking member such as a methylene group, an isopropylidene group, an ether group, a carbonyl group or a sulfide group. A group in which the linked group and the aromatic group are linked to an alkylene group having 1 to 30 carbon atoms, an alkenylene group, and an alkynylene group, and these may contain a substituent such as a halogen atom, a hydroxyl group, and a carboxyl group. R ³ is a divalent aromatic group such as an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, a phenylene group or a naphthylene group, a group in which an aromatic group is linked directly or by a bridging member, and an aromatic group are carbon atoms. Alkylene groups, alkenylene groups, and alkynylene groups of the formulas 1 to 30, which are directly or directly linked to each other by a bridging member such as a methylene group, an isopropylidene group, an ether group, a carbonyl group, a sulfide group, and a silanenedyl group, and these are halogen atoms, It may contain a substituent such as a hydroxyl group or a carboxyl group. R ⁴ is a tetravalent aliphatic or aromatic group having 2 to 30 carbon atoms and a group in which an aromatic group is linked directly or by a crosslinking member, and these are substituents such as a halogen atom, a hydroxyl group, an amino group and a carboxyl group. May be included. l and m are positive integers, n is 0
Or it is a positive integer. ) A silicon-containing polyimide represented by: 2. A compound of the general formula (2) (In the formula, R ¹ is a hydrogen atom or an aromatic group such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group or a naphthyl group having 1 to 30 carbon atoms, and R ² is an alkylene group having 1 to 30 carbon atoms or an alkenylene group. , Divalent aromatic groups such as alkynylene group, phenylene group and naphthylene group, and groups and aromatic groups in which aromatic groups are linked directly or by a cross-linking member such as methylene group, isopropylidene group, ether group, carbonyl group, sulfide group The group is a group linked to an alkylene group having 1 to 30 carbon atoms, an alkenylene group, or an alkynylene group, which may contain a substituent such as a halogen atom, a hydroxyl group or a carboxyl group, and R ³ has 1 carbon atom. To 30 alkylene groups, alkenylene groups, alkynylene groups, divalent aromatic groups such as phenylene groups and naphthylene groups, and aromatic groups directly. Is a cross-linking group such as an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group or a methylene group, an isopropylidene group, an ether group, a carbonyl group, a sulfide group, and a silanenedyl group, which are linked by a bridging member and an aromatic group. A group connected by a member, which may contain a substituent such as a halogen atom, a hydroxyl group, and a carboxyl group, and l is a positive integer.) In a polar organic solvent,
General formula (3) (In the formula, R ⁴ is a tetravalent aliphatic or aromatic group having 2 to 30 carbon atoms and a group in which an aromatic group is linked directly or by a crosslinking member, and these are a halogen atom, a hydroxyl group, an amino group, a carboxyl group. May be substituted with a tetracarboxylic acid dianhydride. 4. The method for producing a silicon-containing polyimide according to claim 1, wherein the tetracarboxylic acid dianhydride is reacted.