FR2598426A1 - NOVEL POLYANHYDRIDE SILOXANES AND NOVEL POLYIMIDE SILOXANES OBTAINED THEREFROM - Google Patents

Abstract

THE NEW POLYANHYDRIDE-SILOXANES CONTAIN CHEMICALLY COMBINED PATTERNS OF FORMULA: (CF DESIGN IN BOPI) OR A MIXTURE OF THE PREVIOUS PATTERNS WITH PATTERNS OF FORMULA: (CF DESIGN IN BOPI) OR R IS CHOSEN FROM MONDROCARBON OR NON-SUBSTITUTE HYDROCARBON RADICALS C, R IS A TRIVALENT ORGANIC RADICAL IN C, A IS AN INTEGER FROM 0 TO 2 AND B IS AN INTEGER FROM 1 TO 3. APPLICATION TO THE MANUFACTURE OF POLYIMIDE-SILOXANES.

Description

Prior to the present invention, various

  processes for preparing polyimide-siloxanes consisting essentially of chemically combined polydiorganosiloxane and polyimide sequences. The U.S. Patent No. 3,325,450 discloses the intercondensation of a polydiorganosiloxane terminated with diorganoorganoaminosiloxy units and benzophenonetetracarboxylic dianhydride resulting in the production of polyimide siloxane. Another method involves the intercondensation of an alkylamino terminated polydiorganosiloxane with an aromatic bis (anhydrous etheroxide) as shown in U.S. Pat. No. 3,487,867. Another example of polyimidesiloxanes is found in U.S. Pat. No. 4,404,350 using a norbornane dicarboxylic anhydride terminated polyorganosiloxane intercondensed with an organic diamine and optionally with another aromatic bisanhydride. J. R. Prater et al, described in Journal of Organic Chemistry, Vol. 38, No. 25, 1973 (4271-4274), synthesis of bis (3,4-dicarboxy-phenyl) -1,3-tetramethyl-1,1,3,3-disiloxane dianhydride. French patent application No. 85 13102 describes a synthesis of "siloxane anhydride" of Prater and siloxane anhydride corresponding to the formula

2 = -0

  wherein R and n are as defined below, and this application is incorporated herein by reference. The siloxane anhydrides 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 transition metal-containing catalyst and then readily hydrolyzing the resulting halosilyl aromatic.

  The present invention is based on the discovery that siloxane anhydride having the formula (1) can be used, a tetraorganodisiloxane aromatic anhydride having the formula

O O

0 R - Si-O Si-R, (2z) c.R R C

0 0

O O

  or their balanced mixtures to prepare a siloxane polyimide by intercondensation with an organic diamine of the formula

NH2R2NH2 (3)

  knowing that, in the formulas, R represents a monovalent hydrocarbon radical C (1-14) or a hydrocarbon radical

  - 3 monovalent C (1-14) male substituted with the same neutral radicals or different neutral radicals during intercondensation, R1 represents a trivalent aromatic C (6-14) organic radical, R2 represents a divalent organic radical; C (2.14) and n represents an integer between 1 and 2000 inclusive. In formula (2), n is

  preferably between 5 and 2000 inclusive.

  The siloxane anhydrides of formulas (1) and (2) and mixtures thereof can also be equilibrated with a cyclopolydiorganosiloxane of the formula: Si <- (4)

R

  wherein R is as defined above and P is an integer from 3 to 8 inclusive, or the siloxane anhydride of formula (1) can be equilibrated with a mixture of the cyclopolydiorganosiloxane of formula (4) and a chain-limiting triorganosiloxane such as hexamethyldisiloxane. Other chain restrictors such as tetramethyldiphenyldisiloxane, 1,3-divinyl tetramethyldisiloxane or mixtures thereof can also be used.

  The present invention provides a siloxane polyimide having chemically combined siloxane imide repeating groups having the product of the intercondensation reaction of A) a siloxane anhydride having chemically combined groups having the formula: - 4 O

C: ./ (R)

  s - '1! <. (5) Finally, a mixture of. chemical siloxane anhydride groups with siloxane groups having the formula: 4-b 6) e) an organic diamine of formula (3) wherein R and R 1 are as previously defined, a is an integer between 0 and 2 inclusive and

  b is an integer between 0 and 3 inclusive.

  In another aspect of the invention, there is provided a siloxane polyimide which comprises chemically combined siloxane imide repeating groups having the formula: -N / R- (SiO) -R NR (7) CR = R d A: or a repeating mixture of these siloxane-imide groups and 9, 1 of imide groups having the formula:

O O

I #

-t / B 3NR2, (8)

O C

  knowing that in formulas R, RE and R2 and n are as defined previously, R3 represents a tetravalent organic aromatic C (6-14) radical defined below and c represents an integer between 1

and 200 included.

  In yet another aspect of the invention there is provided a siloxane polyimide having repeating chemical groups in combination. and answering the formula: R -EiO

\ NX (9)

H 0-- I R

  wherein R and R2 are as previously defined.

  Among the radicals that may be represented by R in formulas (1-7 and 9), for example, halogenated alkyl radicals and C (1-8) alkyl radicals.

  and for example methyl, ethyl, propyl, butyl-

O Sú

  If you are aware of this situation, please contact us at: http://www.youtube.com/wp-content?utm_source=files&lang=en oulueo3 oexolis -ouzoTplod a 'soualllleOI: 1': xne:> pie sop -j sul [lleV] e3! pui sap (oZ-9) 3> uo souaooleq hisblenoze souoqie3 oipliq nBeapui sep "(0Z-9) 3 ua sonbl3uoJe seuoqeioipplq xnumzpe çsap 22d onit3suoa adnolS l [suep sIsIoqI (OZ-Z) 3 Oz ua SlualiUATp sonbluI2Io xnai! puZ so p S za za-uosoaidoi -nad z anb ineaThis is so sold and sold by the slave 'sl; 3 -3nad uo snflju ú -0 [0003] Wherein (e) or (3) is a method for providing a siloxane solution or a mixture thereof. nb sl [3 Sl sozainou s3ualOsIoUOn xnelTpI sop p uosaaidsa ti onb -ueuqes

<1% <01

  q,)? ' olguosasdoxdi -Inad onb xnestpu- sol! wled 'o1daxo iled' 2 or tlnaod uo s33 '', '' '' '' '' '', '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' ! "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "" "

  and x represents an integer from 1 to 5 inclusive.

  For example, among the radicals that R may represent in formula (6),

:: = ::: \ Is_ A / :.

  wherein C and C are selected from the group consisting of: ## STR5 ## wherein R is as defined defined R, R is chosen from the group consisting of hydrogen and the radicals that can represent R, R6 is chosen from

CH ',

CH3 -1y

CH 3. CH 3 - '

_3 HQ ,. cl

CH3 CH3 A.,

CH 3 Br Br CH 3 I I I

CH3

CH3 CH3Br Br CH3 Br B

Q C (CH) 2

  B EBr Br Br and divalent radicals having the general formula - 8 <) (X) m S wherein X is selected from the group consisting of divalent radicals corresponding to the formulas,

O O

  in which m is 0 or 1, and y is a

integer between 1 and 5.

  For example, among the organic dianhydrides which can be used in combination with the siloxane anhydrides of formulas (1) and (2) or mixtures thereof, in the practice of the present invention, dianydride may be mentioned. pyromellitic, benzophenonetetracarboxylic dianhydride, aromatic bis (ethoxide anhydride) of the US Pat. No. 3,847,867 and the silynorbornanedicarboxylic anhydride described in the US Pat.

USA. No. 4,381,396.

  Examples of organic diamines of formula (2) are compounds such as m-phenylenediamine, p-phenylenediarine; 4,4'-diamino-diphenylpropane; 4,4'-diamino-diphenylmethane; benzidine; 4,4'-diamino-4,4'-diphenyl sulphide; 4,4'-diamino-diphenylsulfone; 4,4'-diaminodiphenyl ether; diamino-1,5-naphthalene; 3,3-dimethylbenzidine; 3,3-dimethoxybenzidine; 2,4-diamino toluene; diamino-Z, 6 toluene; 2,4-bis (p-amino-t-butyl) toluene; S diamino-1,3 isopropyl-4 benzene; bis (3-amino-propoxy) -1,2 ethane; m-xylylenediamine; p-xylylenediamine; bis (4-aminocyclohexyl) methane; Decamethylenediamine; 3-methylheptamethylenediamine; 4,4-dimethylheptamethylenediamine; dodecanediamine-2.11; 2,2-dimethylpropylenediamine; 15, octamethylenediamine; 3-methoxyhexamethylenediamine; 2,5-dimethyl hexamethylenediamine; dimethyl-Z, heptamethylenediamine; methyl-3-heptamethylenediamine; methyl-5-nonamethylenediamine; cyclohexanediamine-1,4; octadecanediamine-1, 1S bis (3-aminopropyl) sulfide; N-methyl bis (3-aminopropyl) amine; Hexamethylenediamine; heptamethylenediamine; 2,4-diamino toluene; nonamethylenediamine; diamino-Z, 6 toluene; bis (3-aminopropyl) tetramethyldisiloxane, etc. The siloxane polyimides of the present invention can be synthesized by reacting, at temperatures between 150 ° C. and 350 ° C., substantially equal molar amounts of the siloxane anhydride or a mixture of siloxane anhydride and dianhydride. organic with the

  organic diamine in the presence of an inert organic solvent.

  For example, organic solvents which may be used include orthodichlorobenzene, meta-cresol, and a dipolar aprotic solvent, for example dimethylformamide, dimethylacetamide, N-methylpyrrolidone. The siloxane dianhydride of formula (2), wherein n is greater than 1, for example n is from about 5 to about 2000, can be prepared by equilibrating the siloxane dianhydride of formula (2). wherein n is 1 with cyclopolysiloxanes such as hexaorganocyclotrisiloxane or octaorganocyclotetrasiloxane

  presence of a conventional equilibrium catalyst.

  The polyimide-siloxane block polymers of the present invention can be used as insulators for electrical conductors, adhesives, molding compounds, coatings for the manufacture of laminates and

stubborn elastomers.

  In order for those skilled in the art to be in a better position to practice the invention, the following examples are given for illustrative purposes, but are not meant to limit the invention. All parts are by weight.

Example 1

  A mixture of 20.0 grams of bis (dicarboxy-3 ', 4'-phenyl) -1,3-tetramethyldisiloxane dianhydride, 5.1 g of metaphenylenediamine and 71 ml of orthodichlorobenzene was heated to reflux temperature. The mixture was refluxed for 2 hours continuously removing the azeotrope formed with 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 the solution was cooled and poured into the mixture.

  homogeneous mixture of products resulting in rapidly stirring. A white product precipitated. The process was repeated and the 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 method of preparation, the product was a polyimide-siloxane composed essentially of chemically combined units of the formula o O

"#

  However, GPC (gel permeation chromatography) analysis showed that the product had a molecular weight of about 75,000. The siloxane polyimide also had a Tg (glass transition temperature). ) of 169 and an IV (viscosity limit index) in chloroform of 0.76. An interesting insulating coating is formed on a copper wire when the wire is soaked in a solution of the 10% polymer in chloroform and allowed to air dry.

Example 2

  A mixture was heated at 110 ° C. for 18 hours.

  of S grams of bis (dicarboxy-3 ', 4'-phenyl) -1,3-tetramethyldisiloxane dianhydride and 20.84 grams of octamethylcyclotetrasiloxane in 50 ml of orthodichlorobenzene containing 0.5 ml of fuming sulfuric acid and 1.0 ml of concentrated sulfuric acid. The mixture was allowed to cool to room temperature and 100 ml of methylene chloride was added and excess sodium bicarbonate was added to neutralize the acid. The solution was filtered with decolorizing carbon and the solvent removed in vacuo. We have

  The product was then warmed to 80 ° C under inverted pressure of 1.33 Pa to remove all volatiles. A clear viscous oil was obtained which was a polydimethylsiloxane containing an average of about 16 chemically combined dimethylsiloxy units with anhydridedimethylsiloxy end units. According to the method of preparation and the infrared NMR Hlet analysis, the product had the following formula: ## EQU1 ##

XC - O Y6-1> -

CH R3 CH3O

Example 3

  A mixture of 50 ml of toluene, 7 grams of bis (3,4-dicarboxyphenyl) tetramethyldisiloxane dianhydride, 29 grams of octamethylcyclotetrasiloxane and 7S 1 of fluoromethanesulfonic anhydride and 26 liters of water was heated to 50 ml. After 48 hours, the resulting homogeneous solution was cooled to room temperature and the acid was neutralized with 300 milligrams of anhydrous magnesium oxide. About 100 ml of methylene chloride was added to the mixture and the solution was filtered using bleaching carbon. The solvent was removed from the mixture in vacuo and the resulting viscous oil heated to 800 ° 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 representing a yield of S9% isolated product were obtained. According to the method of preparation and analysis by H1 and infrared NMR, the product was a methylsiloxane polydi3S containing an average of about 27 chemically combined 13-dimethylsiloxy units and the terminal ioti

  phthalic anhydride dimethylsiloxy.

  A mixture of S grams of

  siloxane dianhydride obtained by equilibrium equilibration, 4 grams of bis (dicarboxy-3 ', 4'-phenyl) -1,3-tetramethyldisiloxane dianhydride and 1.24 gram of metaphenylenediamine in 30 ml of orthodichlorobenzene in the presence of a catalytic amount of N, N-dimethylamino-4-pyridine.

  Water formed during the reaction and was continuously removed 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. Z grams of a product which was dissolved in 10 ml of chloroform was obtained. A 10 micron transparent thermoplastic elastomeric film was obtained when the product was cast. According to the process of preparation, the product was a polyimidesiloxane composed essentially of chemically combined units having the formula:

N 1 I 1

  2s s 5i) our \ C S io i 0 o CH3CH3 i sio / 0

0 37I3 '0

  wherein T and s represent positive integers, within the limit of the possible values for n, as previously defined. GPC analysis (salt permeation chromatography) showed that the polylinesiloxane had a molecular weight of about 17,300 and an IV (viscosity limit) of 1, 2 in chloroform. It has been found that the polyimide can be easily extruded

  S siloxane on a copper wire and had interesting insulating and dielectric properties.

Example 4

  A mixture containing 5 grams of the equilibrium siloxane dianhydride as described in Example 3, 1.7 grams of benzophenonetetracarboxylic dianhydride and 1.24 grams of methylenylenediamine in 30 ml of o-chlorobenzene was refluxed. a catalytic amount of dimethylamino-4-pyridine. The water was continuously removed during the two hours that lasted. heating. A product was isolated in a manner similar to that described in Example 3. According to the method of preparation, the product was a siloxane polyimide composed essentially of chemically combined units having the formula: ## STR5 ## wherein: ## STR1 ##

7 \ N

oo

  t and u are defined in the same way as r and s in Example 3. -

- 15

Example 5

  To a solution of 25 ml of methylene chloride containing 0.5 grams of dichloromethylsilyl-4-phthalic anhydride was added, an excess of water representing 5 times the molar amount. After drying and removal of the solvent in vacuo, a quantitative yield was obtained.

  methylsiloxane bearing silyl phthalic anhydride substituents according to formula (1), as demonstrated by NMR and IR analyzes. The 5 gram methylsiloxane of a polydimethylsiloxane fluid containing dimethylsiloxy phthalic anhydride terminal units and an average of 27 chemically combined dimethylsiloxy units were added.

  The mixture was dissolved in 50 ml of toluene and then 2 drops of concentrated sulfuric acid were added. The resulting solution was heated for 4 hours at 80 ° C. After cooling, 50 ml of methylene chloride was added and the solution was neutralized with sodium bicarbonate, then dried and removed. solvent under vacuum. To the resulting silicone fluid was added 0.5 gram of methylenylenediamine and the mixture was heated to remove water. The resulting crosslinked polymer was a tough polymer with interesting insulating and dielectric properties.

Example 6

  75.degree. C., in 50 ml of toluene, was heated

  solution of 3.0 g of phthalic anhydride, methylsiloxane of Example 5, 3.0 g of octamethylcyclotetrasiloxane and 6 mg of hexamethyldisiloxane as chain limiter. A catalytic amount of Nafion acid resin was introduced and the mixture was heated at 75 ° C. for 15 hours. Filtration of the catalyst and vacuum removal of the solvent, toluene, gave a trimethylsiloxy terminated copolymer containing methylsiloxy, dimethylsiloxy and 4-phthalic anhydride units. NMR and infrared analysis were in agreement with the structure of the copolymer. It was easy

  The polymer with a polyamine such as gamma aminopropyltetramethyldisiloxane to produce an elastomer of

  thermoplastic silicone, crosslinked, tenacious.

Example 7

  It was reacted at 145 C under an atmosphere

  of nitrogen in the presence of 1 mol of palladium (11) on silica gel a mixture of 30 g (0.11 mol) of hexachlorodisilane and 23 g (0.11 mol) of anhydride acid chloride trimellitic. Carbon monoxide was released and tetrachlorosilane was continuously removed as it was formed. Vacuum distillation of the resulting mixture yielded 4-trichlorosilyl phthalic anhydride.

  The hydrolysis of 4-trichlorosilyl phthalic anhydride provides a crosslinked resin of the formula: ## STR2 ## A mixture of 4-trichlorosilyl phthalic anhydride and dimethyldichlorosilane is cohydrolysed in water to produce a silicone fluid. . The silicone fluid is

  consists essentially of chemically combined siloxyphthalic anhydride units chemically combined with demethylsiloxy units. A siloxane polyimide was thus formed by intercondensing the silicone fluid with an aminopropyl tetramethyldisiloxane.

- 17

Claims (18)

  1. Polyanhydride-siloxane having chemically combined units of formula O0   (R) ac / a / -SiO 13-; a 'I. or chemically combined units comprising a mixture of silylanhydride units of formula 3.5 (C a) Go and organosiloxane units of formula (R> bSiO (4; b Wherein R is selected from C (1-14) monovalent hydrocarbon radicals and monovalent C (1-14) hydrocarbon radical substituted radicals, R4 is a trivalent C (6-14) organic radical, a is a number of integer 0 to 2 inclusive and b is an integer 1 to 3 inclusive. 2. Polyanhydride-siloxane according to claim 35, RtCHetRes -1 $ - 2598426   3. Polyanhydride-siloxane according to claim 2 having the formula, O O 0 - - Si (o-s-o-O-S '- O CH3 HCH3   O j 0 4. A polyanhydride siloxane according to claim 2 having the formula   o n has a value from 1 to 2000 inclusive.   5. Polyanhydride-siloxane according to claim 1, corresponding to the formula, 0 = 0 O = C-O   R is a C (1-14) monovalent hydrocarbon radical or a C (11) substituted monovalent hydrocarbon radical;   and n is an integer equal to 1 to 2000 inclusive.   6. A polyanhydride-siloxane according to claim 1-19 selected from the class consisting of (A) polyanhydride-siloxanes having from about 5 to about 2000 diorganosiloxy units chemically combined with terminal units of the formula, R C   There are (B) polyorganosiloxy anhydrides having combined chiller units of the formula, O R1 / I \ _______________ Si'O \ o: co O = C 0 0 /   (C) polyanhydride-siloxanes consisting essentially of chemically combined diorganosiloxy units and a mixture of terminal units of (A) and organosiloxy-anhydride units of (B), where the organo radicals of the diorganosiloxy units of A) and (C) and R are members selected from the class consisting of C (1-14) monovalent hydrocarbon radicals and substituted C (1-14) monovalent hydrocarbon radicals; R1 is a trivalent C (6-14) aromatic organic radical; ) and n is an integer equal to 1 to 2000 inclusive.   7. Polyanhydride-siloxane selected from the class consisting of (A) polyanhydride-methylsiloxanes having from about 5 to about 2000 diorganosiloxy units and terminal units of formula, wherein 0   (B) polyanhydride-methylsiloxyphthalic acid having chemically combined units of formula I H3-SiO = ne and (C) polyanhydridemethylsiloxanes consisting essentially of dimethylsiloxy units and a mixture of terminal units of (A) and methylsiloxyphthalic anhydride units of (B) and n is   an integer equal to 1 to 2000 inclusive.   8. A polyanhydride-siloxane according to claim 1 comprising chemically combined anhydride-siloxane units of the formula: ## STR2 ## 9. A polyanhydride siloxane according to claim 1, comprising anhydride-siloxane units of the formula ## STR2 ## or chemically combined with organosiloxane units of the formula, -2   o a is an integer equal to 0 or 1 and b is an integer equal to 1 or 3 included.   10. The polysilylanhydride-siloxane according to claim 1, comprising chemically combined units of formula: ## STR2 ## 11. The polysilylanhydride-siloxane according to claim 1, comprising chemically combined units of the formula: ## STR5 ## C R   tc 12. Polyanhydride-siloxane according to claim Where R is the methyl radical.   13. A polyimide siloxane having recurring chemically combined imidesiloxane groups comprising the product of the intercondensation reaction of   (A) a polysiloxane-anhydride according to any one of claims 1 to 12   (B) an organic diamine of formula: H2NR2NH   R is a divalent C (2-14) organic radical and optionally (C) a dianyride of formula O 0 he He C, \ / CII O C   R3 is a tetravalent aromatic organic radical C (6-14)   The polyimide-siloxane according to claim 13 comprising basic units selected from the class consisting of, -L3 i 2 o 11 -N R '-S: C) R-TR N-R 0R C = C C   N / N R -SC and mixtures thereof, and mixtures of these groups with imide groups of formula, O O He II 2C 3 C XC C he has O   R is a divalent organic radical at C (214) and u is (2-14) an integer equal to 1 to 2000 inclusive.   15. Polyimide-siloxane according to claim 13 comprising recurring groups of formula, -Ai -N R - x ': O) r -SRR1 RN-R Nc --I C R CR   or a mixture of these siloxaneimide groups and imide groups of the formula: O 0 There is no need   c is an integer from 1 to 200 inclusive, and n is an integer equal to 1 to 2000 inclusive.   16. Polyimide-siloxane according to claim 13, characterized in that R is methyl, R1 is O   and R is 17. Polyimide-siloxanes according to claim 13 corresponding to the formula: -ES - o0 IN -   1 SiSi) ## STR5 ## wherein CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH C CH r   o r and s are positive integers.   18. Polyimide-siloxanes according to claim 13, having the formula: ## STR2 ## wherein: ## STR1 ##   o t and u are positive integers.