FR2581648A1 - POLYIMIDE-SILOXANE COMPOSITIONS - Google Patents

Abstract

Polyanhydridesiloxane chosen from: (CF DRAWING IN BOPI) knowing that in the formulas R represents a monovalent C1-13 hydrocarbon radical or a substituted monovalent C1-13 hydrocarbon radical R ** 1 represents a trivalent C6-13 aromatic organic radical, n represents an integer between 1 and 2000 inclusive and n 'is between approximately 5 and approximately 2000.

Description

Prior to the present invention,

  used various processes to prepare silico polyimides

  xanes consisting essentially of polydioroxide sequences

  ganosiloxane and polyimide chemically combined. The U.S. Patent No. 3,325,450 describes intercondensation

  of a polydiorganosiloxane terminated by diorgano-

  organoaminosiloxy and benzophenonetetrahydride dianhydride

  carboxylic acid resulting in the production of poly-

  imide-siloxane. Another process includes intercondence

  A further example of polyimidesiloxanes is found in the US Pat. No. 5,847,867 to an alkylamino terminated polydiorganosiloxane with an aromatic bis (anhydrous etheroxide) as shown in US Pat.

  USA. No. 4,404,350 using a polyorganosiloxane having

  orbornane dicarboxylic anhydride intercondensed with an organic diamine and possibly with another

aromatic bisanhydride.

  The present invention is based on the discovery that

  a tetraorganic aromatic bis (anhydride) may be used

  NODISILOXANE corresponding to the formula: ## STR2 ## in order to prepare a siloxane polyimide by intercondensation with an organic diamine corresponding to the formula

(2) NH2R2NH2

  knowing that, in formulas, R represents a radical

  monovalent hydrocarbon in C (1.13) or a hydrocarbon radical

  substituted monovalent C (1-C 13) bond, R represents a C (6 13) trivalent aromatic organic radical; R2 represents a divalent C (2-C 13) organic radical; and

  represents an integer between 1 and 2000 inclusive.

  J.R. Pratt et al, described in Journal of Organic Chemistry, Vol. 38, No. 25,

  1973 (4271-4274), the synthesis of bis (dicarboxylic) dianhydride

  3,4-phenyl) -1,3-tetramethyl-1,1,3,3-disiloxane. A synthesis of the bis (aromatic anhydride) disiloxane of formula (1) which will be referred to hereinafter as the "siloxane dianhydride" is also known. The siloxane dianhydride can be prepared by reacting a disilane having a functional group and an aromatic acyl halide in the presence of an effective amount of a catalyst containing

  a transition metal. We can then easily

  lysing the resulting halosilylaromatic anhydride in the

  corresponding disiloxane dianhydride.

  The present invention provides a polyimide-si-

  loxane which comprises chemically combined siloxane imide groups having the formula: - 3

(3) NR N-R2-

  C R nR c or a mixture of these siloxane imide groups and imide groups corresponding to the formula: "N R2

(4) - (N / 9R \ N-R2_

  knowing that in the formulas R, R1, R2 and n are as defined previously, R3 represents a radical

  tetravalent aromatic organic compound C (6_13) defined above

  sub and a represents an integer from 1 to 200 inclusive.

  Among the radicals that can be

  R 1 in the formula (1), preferably aryl radicals and halogenated aryl radicals, for example phenyl, chlorophenyl, tolyl, xylyl, biphenyl,

  naphthyl, etc .; halogenated alkyl radicals and radicals

  C (18) and, for example, methyl radicals.

  thyl, ethyl, propyl, butyl, octyl, trifluoropropyl, etc. We can cite, for example, among the radicals that can represent R1, (R) a A 'knowing that R is as defined previously and that

  represents an integer between 1 and 3 inclusive.

  We can cite, for example, among the radicals that can represent R2 divalent organic radicals in

  C (220) selected from the group consisting of (1)

  aromatic hydrocarbons having from 6 to 20 carbon atoms

  carbon and their halogenated derivatives, (b) alkyl radicals,

  and cycloalkylene radicals having from 2 to 20 carbon atoms, polydiorganosiloxane terminated with C (2-8) organo-S15 radicals, and (c) divalent radicals having the formula Q 'wherein Q' is selected from the group consisting of by: O -O-, -C-, -S-, -S-, and -CxH2x,

  and x represents an integer between 1 and S inclusive.

  For example, among the radicals that can represent R3 in the formula (4), and XyD D being chosen from -o-, -s-, -g, C- _o., -_00. R5 CORO !, knowing that R2 is as defined previously, R4 is selected from the group consisting of hydrogen and the radicals that can represent R, R5 is selected from CH3 CH3 CH3Br Br CH3

H3 H H

  ## STR2 ## wherein X is selected from the group consisting of divalent radicals having the formulas, -CyHy -CH In which m is 0 or 1, and y is a

integer between 1 and 5.

  For example, organic dianhydrides which may be used in combination with the siloxane dianhydride of formula (1) in

  in practice of the present invention, the pyrogen dianhydride

  mellitic, benzophenonetetracarboxylic dianhydride, the aromatic bis (anhydrous) anhydride of U.S. No. 3,847,867 and silyl-norbornanedicarboxylic anhydride described

  in U.S. Patent No. 4,381,396.

  Examples of organic diamines that can be

  Formula (2), compounds such as: m-phenylenediamine, pphenylenediamine; 4,4'-diamino-diphenylpropane; diamino-4,4'-diphenylmethane; benzidine; 4,4'-diamino-diphenyl sulfide; 4,4'-diamino-diphenylsulfone; 4,4'-diaminodiphenyl ether; diamino-1,5-naphthalene; 3,3-dimethylbenzidine; 3,3-dimethoxybenzidine; 2,4-diamino toluene; 2,6-diamino toluene; bis (p-amino-t-butyl) -2,4 toluene; diamino-1,3 isopropyl-4-benzene; bis (3-amino-propoxy) -1,2 ethane; m-xylylenediamine; pxylylenediamine; bis (4-aminocyclohexyl) methane; decamethylenediamine; 3-methylheptamethylenediamine; 4,4-dimethylheptamethylenediamine; dodecanediamine-2.11; 2,2-dimethylpropylenediamine; 1'octaméthylènediamine; 3-methoxyhexamethylenediamine; 2,5-dimethyl hexamethylenediamine; 2,5-dimethylheptamethylenediamine; 3-methylheptamethylenediamine, methyl-5-nonamethylenediamine; cyclohexanediamine-1,4; octadecanediamine-1, bis (3-aminopropyl) sulfide; N-methyl bis (3-aminopropyl) amine; hexamethylenediamine; I'heptaméthylènediamine; 2,4-diamino toluene; nonamethylenediamine; 2,6-diamino toluene; bis (3-aminopropyl) tetramethyldisiloxane, etc. It is also possible to use, in combination with the siloxane dianhydride corresponding to formula (1), from 1 to 1000 equivalents of anhydride per equivalent of siloxane anhydride of formula (1) of a siloxane anhydride corresponding to the formula:

(5> -lotitj-

O

\ C C O N O

  wherein R and n are as previously defined

  is lying. The siloxane polyimides of the present invention can be synthesized by reacting with temperatures

  between 1500C and 3500C, molar quantities practically

  of the siloxane dianhydride or a mixture of 8 -

  dianhydride siloxane and organic dianhydride or anhy-

  siloxane of formula (5) with the organic diamine

  presence of an inert organic solvent.

  For example, organic solvents which can be used include orthodichlorobenzene, meta-cresol, and a dipolar aprotic solvent, for example dimethylformamide, dimethylacetamide,

  N-methylpyrrolidone. The dianhydride can be prepared

  loxane of formula (1), wherein n is

  less than 1, representing for example n 'between

  5 and around 2000, by balancing the dianhy-

  dride siloxane having the formula (1) wherein

  is equal to 1 with cyclopolysiloxanes as a hexa-

  ganocyclotrisiloxane or an octaorganocyclotetrasiloxane

  presence of a conventional equilibrium catalyst.

  Poly-sequence polymers can be used

  imide-siloxanes of the present invention as insulators for electrical conductors, adhesives, molding compounds, coatings for the manufacture of laminates and

stubborn elastomers.

  So that the man of the art is better able to

  put the invention into practice, the following examples are given

  for illustrative purposes, but they are not intended to limit the invention. All parts are expressed in

weight.

Example 1

  A mixture of 20.0 grams of bis (3'-dicarboxy) dianhydride was heated to reflux temperature.

  phenyl) -1,3-tetramethyldisiloxane, 5.1 g metaphenylene-

  diamine and 71 ml of ortho-dichlorobenzene. We heated

  mixture at reflux for 2 hours, continuously removing

  the azeotrope formed with the water. A product started to precipitate out of the solution and the heating was stopped. 100 ml of methylene chloride were then added to the mixture after cooling the solution and poured into the mixture.

  homogeneous mixture of products resulting in 500 ml of

  thanol that was agitated quickly. A white product has

  cipité. The process was repeated and product was further obtained, and the resulting product was dried under vacuum. 23.4 grams of product were obtained, a yield of 100%.

  According to the preparation process, the product was a poly-

  imide-siloxane composed essentially of chemical

  combined with the formula

0 0

  N of C fSiRCo \ o J J GPC analysis (permeation chromatography)

  gel) showed that the product had a moderate mass

  The polyimide siloxane also had a Tg (glass transition temperature) of 169 and an IV (viscosity limit) in chloroform of 0.76. An interesting insulating coating is formed on a wire

  of copper when the wire is dipped in a solution of

  10% in chloroform and allowed to air dry.

Example 2

  A mixture of 5 grams of bis (dicarboxy-3 ', 4'-phenyl) -1,3 dianhydride was heated at 110 ° C. for 18 hours.

  tetramethyldisiloxane and 20.84 grams of octamethylcyclo

  tetrasiloxane in 50 ml of orthodichlorobenzene containing

  0.5 ml of fuming sulfuric acid and 1.0 ml of sulfuric acid

  than concentrated. The mixture was allowed to cool to room temperature

  and 100 ml of methylene chloride were added and excess sodium bicarbonate was added to neutralize the acid. The solution was filtered with carbon

  bleaching and the solvent was removed in vacuo. We have

- 10 -

  After heating the product to 80 C under a high vacuum of 1.33

  Pa to remove all volatile substances. We have

  held a transparent viscous oil which was a polydi-

  methylsiloxane containing an average of about 16 motifs

  Chemically combined dimethylsiloxy compounds with

  anhydride dimethylsiloxy. According to the process of preparation

  infrared NMR analysis, the product meets the

to the following formula:

1Q F O

  m C i3ZI3 X H 3JZ tQC - i (O-O-Si - w CH3 3 CH

Example 3

  A mixture of 50 ml of toluene was heated to 67.degree.

  7 grams of bis (3,4-dicarboxyphenyl) tetrahydride dianhydride

  methyldisiloxane, 29 grams of octamethylcyclotetrasiloxane and 75 1 of fluoromethanesulfonic anhydride and 26 1 of water. After 48 hours, the resulting homogeneous solution was cooled to room temperature and

  neutralized the acid with 300 milligrams of magnesium oxide

  anhydrous sium. About 100 ml of methylene chloride was added to the mixture and the solution was filtered using bleaching carbon. The solvent was removed from

  vacuum and the resulting viscous oil was heated.

  at 80 ° C. under a vacuum of 1.33 Pa to remove any volatile cyclosiloxanes that might have been present. Sublimation of phthalic anhydride was not observed, which showed that equilibrium was reached without cleavage of the end groups. 21.4 grams of a clear viscous oil was obtained, representing a yield of 59% by weight.

  isolated product. According to the process of preparation and the

  lysis by H1 NMR and infrared, the product was a polydimide

  methylsiloxane containing an average of about 27 motifs

- 11 -

  Chemically Combined Dimethylsiloxy and Terminal Designs

  phthalic anhydride dimethylsiloxy.

  A mixture of S grams of

  siloxane dianhydride obtained by equilibration

  4 grams of dianhydride bis (dicarboxy-3 ', 4'-phenol

  nyl) -1,3-tetramethyldisiloxane and 1.24 gram of metaphenyl-

  Linediamine in 30 ml of orthodichlorobenzene in the presence

  a catalytic amount of N, N-dimethylamino-4-pyridine.

  Water was formed during the reaction and it was continued

  naked during the two hours of heating. After cooling, 75 ml of methylene chloride were added to the mixture to redissolve the precipitated product. The mixture was then poured into methanol and the product was precipitated twice, separated and dried. 2 grams of a product was obtained which was dissolved in 10 ml of chloroform. We got a

  transparent thermoplastic elastomeric film of 10 micro-

  meters when the product was poured. According to the method of preparation, the product was a polyimidesiloxane composed essentially of chemically combined units having the formula:

O O

2C.7C

N I 1 3

_ Si) our M \ N, y

/ O O

(CH3H)

? '', 1 3%.

c siosi c I I

0 CH3CH3 0

  where x and y represent positive integers

  within the limit of the possible values for n, as defined previously. GPC analysis (chromatography

- 12 -

  by gel permeation) showed that the polyimidesiloxane

  had a molar mass of about 17,300 and an IV (

  viscosity limit) of 1.2 in chloroform. It has been found that the polyimide siloxane can be easily extruded on a copper wire and that it has

  interesting insulating and dielectric properties.

Example 4

  A mixture containing 5 grams of the siloxane dianhydride obtained by equilibrium was refluxed.

  described in Example 3, 1.7 grams of benzo-dianhydride

  phenonetetracarboxylic acid and 1.24 gram of m-phenylenedi

  amine in 30 ml of o-chlorobenzene in the presence of a

  catalytic content of dimethylamino-4-pyridine. The water was continuously removed during the two hours of heating. A product was isolated in a manner similar to that described in Example 3. According to the method

  the product was a polyimide siloxane com-

  predominantly chemically combined units

  having the formula: ## STR1 ##

/ 0 0 \

I N

7 1

O O

  where x, y and z are positive integers

  within the limit of the defined values popur n.

- 13 -

Example 5

  To a solution of 25 ml of

  methylene containing 0.5 gram of dichloromethyl

  phthalic silyl-4, an excess of water representing 5 times the molar amount. After drying and removal of the solvent

  under vacuum, a quantitative yield was obtained

  thylsiloxane bearing silyl phthalic anhydride substituents according to formula (5), as demonstrated by NMR and IR analyzes. The methylsiloxane was added to 5 grams of a polydimethylsiloxane fluid containing dimethylsiloxy phthalic anhydride end units and a

  average of 27 chemically combined dimethylsiloxy units.

  The mixture was dissolved in 50 ml of toluene and

  added 2 drops of concentrated sulfuric acid. The resulting solution was heated for 4 hours at 80 ° C.

  added, after cooling, 50 ml of methylene chloride

  and the solution was neutralized with sodium bicarbonate, then dried and the solvent removed in vacuo. To the resulting silicone fluid was added 0.5 gram

  m-phenylenediamine and the mixture was heated to eliminate

  to undermine the water. The resulting crosslinked polymer was a poly-

  tenacious mother with insulating and dielectric properties

interesting topics.

  Although the above examples relate to only a few of the very many variants that can be used in the manufacture of polyimides-siloxanes of the

  present invention, it should be understood that the present invention

  vention concerns a much greater diversity of poly-

  imides-siloxanes that can be prepared by reacting a

  dianhydridesiloxane having the formula (1) and a di-

  organic amine corresponding to formula (2), optionally in the presence of an organic dianhydride as shown in FIG.

  description preceding these examples.

- 14 -

Claims (8)

REVENOICATIONS   1. Polyanhydridesiloxane selected from o $ R I- R -f S O | - in -1 I n c R 'R O = C C = O 0 = 1C = O   knowing that in the formulas R represents a hydrogen radical   carbon monovalent C (1 to 13) or a hydrocarbon radical   monovalent C (113) substituted, Ri represents a radical   trivalent aromatic organic callus C {613), n represents   an integer between 1 and 2000 inclusive and not   is between about 5 and about 2000.   2. Polyanhydride-siloxane according to claim   1, characterized in that R represents CH3 and R1 represents   ZS feels 3. Polyanhydride-siloxane corresponding to the formula O O M l 6 C H3 CH3 CH3 0 1 3% (: SiO_ '_1eO_0 - 15 -   4. Polyanhydride-siloxane having the formula CH 3 SiO 2.   in which n is between 1 and 2000 inclusive.   5. Polyimide-siloxane characterized in that it comprises chemically combined siloxane-imide groups, corresponding to the formula o o It t C R C   ## STR2 ## or a mixture of these siloxaneimide groups and of imide groups corresponding to the formula -E /% 'R3 / L R2   in which R represents a monovalent hydrocarbon radical   slow at C (1.13) or a substituted C (1.13) monovalent hydrocarbon radical, R1 represents an organic radical   trivalent aromatic C (6_13). R represents a radical   C (2-13) divalent organic callus R3 represents a C (6-13) tetravalent aromatic organic radical and - 165 -   represents an integer between 1 and 200 inclusive.   6. Polyimide siloxane according to claim 5, characterized in that R represents the methyl group, R1 represents: and Rz represents 7. Siloxane polyimides of the formula o o C C l CH3 CiI3 Ch 1 N 3 Oo O> \\ si 0 0 H30 0 Y   o CH3CH3 where x and y represent positive integers within the limit of the values defined for n 8. Polyimidesiloxanes corresponding to the formula ## STR1 ## '' He h 1O w C.'NHCH. c3 o 8 CH3 CH3 J y / 0 \ o / \ IOOOO WE 'c - 17 -   in which x, y and z represent whole numbers   positive within the limit of the values defined for n.