JPH0551618B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Indication of related applications Related to and related to co-pending U.S. Application No. 647301 ``Process for Silylating Aromatic Imides and Imides Obtained Therefrom'' and U.S. Application No. 647332 ``Process for Silylation'' Both applications were filed on September 4, 1984 and are assigned to the same assignee as the present invention.

BACKGROUND OF THE INVENTION Prior to this application, various methods were used to produce polyimide-siloxanes consisting essentially of chemically bonded blocks of polydiorganosiloxane and polyimide. Holub
U.S. Pat. No. 3,325,450 teaches that polyimide-siloxanes are formed by intercondensation of polydiorganosiloxanes having diorganoorganoaminosiloxy terminal units with benzophenone dianhydride. Another method is to convert polydiorganosiloxanes with alkylamino end groups into aromatic bis(ether anhydrides) as shown in U.S. Pat. No. 3,847,867 to Heath et al.
There is a condensation of Other examples of polyimide-siloxanes are provided by Ryang, US Pat.
No. 4,404,350, which utilizes a norbornane anhydride-terminated organopolysiloxane (optional other aromatic bisanhydride) condensed with an organic diamine.

The present invention is based on the formula Based on the discovery that bis(aromatic anhydride) organosiloxanes having the formula (2) can be used to prepare polyimide-siloxanes by _condensation with organic diamines having the formula ( ₂ ⁾ There is. In the formula, R is C _(1-13) /
valence hydrocarbon group or substituted C _(1-13) / valence hydrocarbon group, R ¹
is a C _(6-13) trivalent aromatic organic group, R ² is a C _(2-13) divalent organic group, and n is an integer of 1 to 2000.

The synthesis of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride was carried out by JR Pratt.
Journal of Organic Chemistry Volume 38, No. 25
No., 1973 (4271-4274). The synthesis of bis(aromatic anhydride) siloxas of formula (1), hereinafter referred to as "siloxane dianhydrides", is also presented in the inventor's US application. Siloxane dianhydrides may be prepared by the reaction between a functionalized disilane and an aromatic acyl halide in the presence of an effective amount of a transition metal catalyst. The resulting halosilyl aromatic anhydride can then be readily hydrolyzed to the corresponding disiloxane dianhydride.

DESCRIPTION OF THE INVENTION According to the present invention, the formula chemically bonded siloxane imide groups,
Or the above siloxane imide group and formula A polyimide-siloxane is provided consisting of a mixture of imide groups, where R, R ¹ , R ² and n are as defined above and R ³ is 4 as defined below.
valence C _(6-13) aromatic organic group, a is an integer from 1 to 200).

The groups contained in R in formula (1) are preferably aryl groups and halogenated aryl groups such as phenyl, chlorophenyl, tolyl, xylyl, biphenyl, and naphthyl, alkenyl groups such as vinyl, allyl, and cyclohexenyl, methyl, ethyl, Propyl, butyl, octyl, trifluoropropyl, etc.
C _(1-8) alkyl group and halogenated alkyl group.

The group contained in R ¹ is, for example, (wherein R is as defined above, and a is an integer having a value of 1 to 3).

Groups included in R ² are, for example, (a) aromatic hydrocarbon groups having 6 to 20 carbon atoms and their halogenated derivatives, (b) alkylene groups and cycloalkylene groups having 2 to 20 carbon atoms, C _{(2- 8)} Organic group-terminated polydiorganosiloxane and formula (c) (In the formula, Q' is -O-, -S- and -C _x H _2x , where x is an integer from 1 to 5) _{. -20)} It is an organic group.

For example, the group contained in R ³ in formula (4) is as well as [In the formula, D is -O-, -S-, −OR ⁵ O− and (In the formula, R ² is as defined above, R ⁴ is selected from hydrogen and R, and R ⁵ is and general formula (X) _n (wherein X is the formula −C _y H _2y −, is a group selected from the group consisting of divalent groups of and -S-,
m0 is a group selected from the divalent organic groups of (or 1, y is an integer from 1 to 5).

Organic dianhydrides that can be used with the siloxane dianhydride of formula (1) in the practice of this invention include, for example, pyromellitic dianhydride, benzophenone dianhydride,
Heath et al. Aromatic Bis(Ether Anhydride) and Ryang U.S. Patent No.
There is a silylnorbornane anhydride shown in No. 4281396.

The organic diamine of formula (2) includes the following compounds.

m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4' -diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-diaminotoluene, 2,6- Diaminotoluene, 2,4-bis(p-amino-t-butyl)toluene, 1,3-diamino-4-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, m-xylylenediamine, p -xylylenediamine, bis(4-aminocyclohexyl)methane, decamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine, octa Methylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine, 1 , 15-octadecanediamine, bis(3-aminopropyl) sulfide, N-methyl-bis(3-aminopropyl)amine, hexamethylenediamine, heptamethylenediamine, 2,4-diaminotoluene, nonamethylenediamine, 2,6 -diaminotoluene, bis-(3-aminopropyl)tetramethyldisiloxane, etc.

Along with the siloxane dianhydride of formula (1), a formula with an anhydride equivalent of 1 to 1000 relative to the anhydride equivalent. A siloxane anhydride having the formula (wherein R and n are as defined above) can also be used. This siloxane anhydride and its method of preparation are disclosed in my US application Ser. No. 647,332.

The polyimide-siloxane of the present invention has a temperature of 150°C to
At a temperature in the range of 350°C, approximately equimolar amounts of siloxane dianhydride or a mixture of siloxane dianhydride and organic dianhydride or siloxane anhydride of formula (5) are mixed with an organic diamine in the presence of an inert organic solvent. It can be synthesized by reaction.

Organic solvents that can be used are, for example, orthodichlorobenzene, meta-cresol and dipolar aprotic solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone.
The siloxane dianhydride of formula (1) in which n is greater than 1, e.g. It can be prepared by equilibrating the anhydride with a cyclopolysiloxane such as hexaorganocyclotrisiloxane or octaorganocyclotetrasiloxane.

The polyimide-siloxane block polymers of this invention can be used as insulation for electrical conductors, adhesives, molding compounds, coatings for laminates, and tough elastomers.

The following examples are presented by way of illustration, but not limitation, to enable those skilled in the art to easily practice the invention. All parts are by weight.

Example 1 A mixture consisting of 20.0 g of 1,3-bis(4'-phthalic anhydride)tetramethyldisiloxane, 5.1 g of meta-phenylenediamine and 71 ml of ortho-dichlorobenzene is heated to reflux temperature. 2 of the mixture
Reflux for an hour, constantly removing the water azeotrope. Stop heating when material begins to precipitate from solution. next,
After cooling the solution, add 100ml of methylene chloride to the mixture.
The resulting homogeneous product mixture is poured into 500 ml of rapidly stirred methanol. A white product precipitates out.
Further product is obtained by repeating the operation and the product obtained is dried in vacuo. 23.4g or yield 100
% of material was obtained. Depending on the manufacturing method, the product has the formula A polyimide-siloxane consisting essentially of chemically bonded units. Analysis by GPC showed the product to have a molecular weight of approximately 75,000. Polyimide-siloxane also has a Tg of 169 and an IV of 0.76 in chloroform.
It is. Dipping the wire in a 10% solution of the polymer in chloroform and air drying forms a useful insulating coating on the copper wire.

Example 2 A mixture of 5 g of 1,3-bis(4'-phthalic anhydride)tetramethyldisiloxane and 20.84 g of octamethylcyclotetrasiloxane in 50 ml of orthodichlorobenzene containing 0.5 ml of fuming sulfuric acid and 1.0 ml of concentrated sulfuric acid. Heat to 110°C for 18 hours. The mixture is cooled to room temperature, 100 ml of methylene chloride is added and excess sodium bicarbonate is added to neutralize the acid.
The solution is filtered through decolorizing carbon and the solvent is removed under reduced pressure. The product is then heated to 80° C. under a high vacuum of 0.01 Torr to remove volatile products. A clear viscous oil was obtained which was a polydimethylsiloxane with terminal dimethylsilicon anhydride siloxy units and an average of about 16 chemically bonded dimethylsiloxy units. Production method and proton
Based on NMR and IR analysis, the product has the following formula:

Example 3 A mixture of 50 ml of toluene, 7 g of bis(phthalic anhydride)tetramethyldisiloxane, 29 g of octamethylcyclotetrasiloxane, 75 μ of fluoromethanesulfonic anhydride and 26 μ of water is heated to 67°. After 48 hours, the resulting homogeneous solution is cooled to room temperature and the acid is neutralized with 300 mg of anhydrous magnesium oxide.
About 100 ml of methylene chloride is added to the mixture and the solution is filtered using decolorizing carbon. The mixture is stripped of the solvent under reduced pressure and the resulting viscous oil is heated to 80° C. under a vacuum of 0.01 torr to remove volatile cyclosiloxanes. No sublimation of phthalic anhydride was observed, indicating that equilibration occurred without cleavage of the end groups. 21.4 g of clear viscous oil was obtained, a yield of 59%. According to the method of preparation and proton NMR and infrared analysis, the product is a polydimethylsiloxane with an average of about 27 chemically bonded dimethylsiloxy units and terminal dimethylsiloxyphthalic anhydride siloxy units.

5 g of the above equilibrated siloxane dianhydride, 1,3-
A mixture of 4 g of bis(4'-phthalic anhydride)tetramethyldisiloxane and 1.24 g of metaphenylenediamine is heated to form 30 ml of orthodichlorobenzene in the presence of a catalytic amount of 4-N,N-dimethylaminopyridine. Reflux inside. Water is formed during the reaction and is continuously removed during the 2 hours of heating. After cooling, a further 75 ml of methylene chloride are added to the mixture in order to redissolve the precipitated product. The mixture is then poured into methanol and the product is precipitated twice, decomposed and dried. 2 g of product are obtained and dissolved in 10 ml of chloroform. 10 when casting the product
A transparent thermoplastic elastic film of micron size is obtained. Depending on how the product is manufactured, the product has the formula (where x and y are positive integers within the definition of n as defined above) consisting essentially of chemically linked units. GPC analysis determined that the polyimide-siloxane had a molecular weight of approximately 173,000 and an intrinsic viscosity of 1.2 in chloroform. It has been found that polyimide-siloxanes are easily extruded onto copper wire and exhibit useful insulating properties.

Example 4 5 g of equilibrated siloxane dianhydride as described in Example 3, 1.7 g of benzophenone dianhydride and m-
A mixture containing 1.24 g of phenylenediamine is heated to reflux in 30 ml of o-chlorobenzene in the presence of a catalytic amount of 4-dimethylaminopyridine.
Water is continuously removed during the 2 hour heating period. The product is isolated in a manner similar to that described in Example 3. Depending on the manufacturing method, the product has the formula A polyimide-siloxane consisting essentially of chemically bonded units of the formula (where x, y, and z are as described in Example 3).

Example 5 4-dichloromethylsilyl phthalic anhydride 0.5
A 5-fold molar excess of water is added to 25 ml of a methylene chloride solution containing g. After drying and removal of the solvent in vacuo, methylsiloxane with silyl phthalic anhydride side chains within the range of formula 5 was obtained in good yield as shown by NMR and IR analysis. This methylsiloxane is added to 5 g of a polydimethylsiloxane liquid having terminal dimethylsiloxyphthalic anhydride units and an average of 27 chemically bonded dimethylsiloxy units. Dissolve the mixture in 50 ml of toluene and then add 2 drops of concentrated sulfuric acid. The resulting solution is 80
Heat at ℃ for 4 hours. After cooling, add 50 ml of methylene chloride.
is added and the solution is neutralized with sodium bicarbonate, followed by drying and removal of the solvent under vacuum. Add m-phenylenediamine to the resulting silicone liquid.
Add 0.5g and heat the mixture to remove water.
The resulting crosslinked polymer is a tough rubber with useful insulating properties.

Although the above examples relate to only a few of the numerous variations used in the preparation of the polyimide-siloxanes of the present invention, the present invention, as shown in the preceding description of these examples, Of course, this relates to a wide variety of polyimide-siloxanes which can be prepared by reacting the siloxane dianhydride of formula (2) and the organic diamine of formula (2) in the presence of any organic dianhydride.

Claims (1)

[Claims] 1 formula an anhydride-terminated siloxane having from about 5 to about 2000 diorganosiloxy units chemically bonded thereto, where the organic group of said diorganosiloxy units and R are C _(1-13) a monovalent hydrocarbon group or a substituted C _(1-13) monovalent hydrocarbon group and R ¹ is a C _(6-13) trivalent aromatic organic group). 2 R is CH ₃ and R ¹ is The siloxane according to claim 1. 3 formulas The siloxane according to claim 2, which has the following. 4 formula The siloxane of claim 1 having from about 5 to about 2000 dimethylsiloxy units chemically bonded to the terminal units.