CA1250583A - Silicon functionalized norbornane carboxyimide and methods for making - Google Patents

Abstract

SILICON FUNCTIONALIZED NORBORNANE
CARBOXYIMIDE AND METHODS FOR MAKING

ABSTRACT OF THE DISCLOSURE

Silicon functionalized carboxyimides are provided which can be made by the hydrosilylation of norbornene terminated polyimides with silicon hydrides having hydrolyz-able radicals attached thereto. The silicon functionalized carboxyimides can be used to make silanol terminated sili-con-polyimide block polymers useful in making room tempera-ture vulcanizable compositions.

Description

~Z~i~583 SILICON FUNCTIONALIZED NORBORNANE
CARBOXYIMIDE AND ~ETHODS FOR MARING
Background of the Invention The present invention relates to norbornanecar-5 boxyimide having silicon functional groups, andmethods for making and modifying such materials. In addition, the present invention relates to use of such silicon containing norbornanecarboxyimide to make silanol terminated polydiorganosiloxanepolyimide 10 block polymers and room temperature vulcanizable compositions (RTV's) resulting therefrom.
Prior to the present inventionl room temperature vulcanizable silanol terminated polydioryanosiloxanes, for example, silanol 15 terminated polydimethylsiloxanes were available in ei ther one-package or two-package systems based on the nature of the moisture sensitive cross-linking agents utilized in the composition. A typical one-package system is based on the use of methyltriacetoxysilane 20 and a silanol terminated polydimethylsiloxane as shown by Ceyzeriat, United States Patent 3,133,891 which issued May 19, 1964. A two-package system as shown by Nitzsche et al, United S-tates Patent Number 3,065,194 which pat:ent issued on November 20, 1962 requires the blending of ~25~S~33 silanol terminated polydimethylsiloxane with a curing catalyst, such as ethyl orthosilicated in combination with dibutyltindilaurate. The two-package system requires mixing of the curing catalyst with the silanol terminated polydimethylsiloxane prior to use.
The above described one-package and two-package room temperature vulcanizable compositions generally require the use of reinforcing filler, for example, a silica filler in amounts of from 5-300 parts, per 100 parts of silicone polymer, if improved tensile strength in the resulting cured silicone is desired. Another procedure available to improve the toughness of cured silicone polymers is the introduction of silarylenesiloxy units into the polymer chain to produce a copolymer consisting essentially of diorganosiloxy units chemically combined with silarylenesiloxy units. Although these procedures substantially enhance the modulus (psi) of the silicone polymer, these procedures are uneconomic or do not achieve the degree of physical properties desired in the end product.
As taught in United States Patent No.
4,472,565, issued September 18, 1984 to Ryang, silicon hydride terminated polyimide having the formula, ~ ~ ~ S ~ RD 14625 R9 si--tOsl~H R--Slt l ~ H

1l ~ ~ .
I IR-N \ \ ~ i~ ~R

\

R~ J

ean be used to prepare silanol terminated polydiorganosilo-xane polyimide eopolymers useful for making high strength RTV compositions, where R is a divalent radical seleeted from the class eonsisting of (a) aromatie hydrocarbon radieals having from 6-20 earbon atoms and halogenated aromatie hydroearbon radicals having from 6-20 earbon atoms, (b) alkylene radicals having from 2-20 earbon atoms and cyeloalkylene radieals having from 2-20 earbon atoms, (e) C(2 8) alkylene terminated polydiorganosiloxane, and (d) radieals included by the general formula ~ Q' ~

~ 583 RD-14625 Q' is a member ~elected from the class consisting of S- , and -CxH2x ~

x i~ a whole number from 1 to 5 inclusive, Q is ~ tetra-valent radical ~elected from ,~
and ~ D

where D is a member selected from lQ ~ g ~ ~ ~

and R8 is a divalent radical selected from Br Br CL C~3 C ~Br ~ CH
C(CH3)~
CH3Br Br CH3 r Br C~3 ~H3 ~2~ RD-14625 and divalent organic radicals of the general formula, ~(X)p~

X is a member selected from the class consisting of divalent radical~ of the formula, yH2y ~ , and -S- , y is a~ integer from l t~ 5, Rl-R6 are selected fr~m hydr~-gen and C(l 8) alkyl radicals, R is the same or different C(l 13) monovalent l~rocarbon-radical and substituted C(l 13) monovalent hydrocarbon radical, R 7is selected from H or R7, Y is a divalent radical selected from -O- and -C(R )2-' n is an integer equal to 0-200 inclusive, and r and p are whole numbers equal to 0 or 1.
The present invention is based on my discovery that high strength silicon-polyimide copolymer products also can be made by effecting the cure of room temperature or low temperature condensation vulcanizable silanol terminated polydiorganosiloxane-polyimide copolymers resulting from the reaction of silanol terminated polydiorganosiloxane of the formula (l) H (OSi)m OliOH
17 ~7 R R

with silicon functionalized norbornane carboxyimide referred to hereinafter as "silicon-norbornanebisimide"
of the formula R7 ~10 R70 (fl tr-I $~

I \

-- . . . . . . . .. \
O o [R N ~ \ ~/ \

(2) / O ~ \ \

~ ~ N N

where R-R7 are as previously defined, Z is selected from C(l 8) alkoxy, acyloxy, halogen and amine, and R9, R10, and Rll are selected from Z and R7 and n is integer equal to 1-2000 inclusive.
The silanol terminated polydiorganosiloxane-polyimide copolyers which can be made by using the above silicon-norbornane imides of formula (2) comprise by weight from 1 to 99% of polyimide blocks of the formula, ~ ~ ~ ~ RD-146~5 O O

(3) N ~ R-N /Q N ~ R-N
s ~ 1~

chemically combined with from 99% to 1% of polydiorganosi-loxane blocks of the formula, l7 l7 R R
where R-R7, Y, Q, n and m are as previously defined.
Statement of the Invention The silicon-norbornane imides of formula (2~ of the present invention can be made by initially forming a norbornene terminated polyimide by effecting reaction between organic diamine, a norbornene anhydride and organic di~nhydride, in accordance with the following equation:

_ __ _ ~ ~ ~ RD-14625 R5 Rl 0 Ii H N R NH 0/ \Q/ \O

~ ~,4 ~ (~ O O

( 5 ~;~ N- l R-N\ Q Ni nR~~

where Q, R, Rl-R6, n and Y are as previously defined.

The aliphatically unsaturated polyimide of formula (5) or monoimide of the formula lS (6) RR ~ FCfj \/ N-R7 where Rl-R7 and Y are as previously defined, can thereafter be hydrosilated with a silicon hydride having the formula, ~ R7 ~ lRlO
(7) H - sio- si - z ~ R7~ lll where R7, R10, R11 and Z are as previously defined, to produce a silicon-norbornaneimide of formula (2), or silicon-norbornane monoimide of the formula o (~) Z--I --(05~ `C/

where Rl-R7, R9, R10, R11, Y and Z are as previously defined.
The silanol terminated polydiorganosiloxane polyimide copolymers which can be made in accordance with the practice of the present invention have the formula, (9) H~Osi~zl~OI i ~51~) OH
R7 +r+z R7 +1 R7 +1 where zl is a divalent group shown by formula (3), can be prepared by effecting reaction between the silicon-norbornanebisimide of formula (2~ and a silanol terminated polydiorganosiloxane of formula (1), in the presence of an effective amount of condensation catalyst as defined hereinafter, where R7, R9, r and m are as previously defined and s is an integer having a value of from about 1 to 104 inclusive.
g . .
~ . . .

~ ~ RD-14625 Radical~ included within Rl-R~ of formulas 1, 3 and 4 are, for example, hydrogen, methyl, ethyl, propyl, butyl, etc. Radicals included within R7 are, for example, aryl radicals and halogenated aryl radicals, for example, phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc.; alkenyl radicals, for example, vinyl, allyl, cycl~-hexenyl, etc.; C(l_8) alkyl radicals and halogenated alkyl, for example, methyl, ethyl, propyl, butyl, octyl, etc.

There are included within the silicon hydride of formula (7) triethoxysilane, dimethylchlorosilane, ~,N-dimethyl-aminodimethylsilane, etc.

Curing agents also can be utilized in the practice ~f the present inv~ntion in combination with the above-des-cribed condensation vulcanizable compositions. For example, there can be used methyltriacetoxysilane, methyl-tris-(2-ethylhexanoxy)silane, and a curing agent having the formula, 12 (I )b ~lO) (R )4 (a+b)~si(x)a where R7 is as previously defined, R is a C(1 8) aliphatic organic radical selected from the group consisting of alkyl, alkylether, alXylester, alkylketone, and alkylcyano radi-cals, or C(7 13) aralkyl radical, X i6 a hydrolyzable leav-ing group ~elected from the group consisting of acyloxy, amido, amino, carbamato, enoxy, halo, imidato, isocyanato, ketoximato, oximato, thioisocyanato and ureido radicals and b i a whole number equal to 0 or 1, a is a whole number equal to 0 to 4 inclusive and the sum of a + b is equal to 0 to 4 inclusive.

~ ~ ~ 5 ~ RD-14625 In addition to curing agents of formula (10), there also can be utilized in the condensation vulcanizable compositions of the present invention alkoxy functional cross-linking agents of the formula (R7)b (11) (R 0) 4 bSi where R7, Rl and b are as previously defined.

Con~ensation catalysts can be used in the practice of the present invention to facilitate the cure of the condensation vulcanizable compositions and in certain cases facilitate the condensation of the silanol terminated polydiorganosiioxane of formula ~1) with the silicon-norbor-nane imide of formula (2). For example, there can be used from 0.001 to 1 part of condensation catalyst, based on 100 parts of the above described silanol terminated p~lydi-organosiloxane-polyimide copolymer. There are included as condensation catalysts tin compounds, for example, dibutyl-tindilaurate; dibutyltindiacetate; dibutyltindimethoxide;
carbomethoxyphenyl tin tris-uberate; tin octoate; isobutyl tin triceroate; dimethyl tin dibutyrate; dimethyl tin dineodeconate; triethyl tin tartrate; dibutyl tin dibenzo-ate; tin oleate; tin naphthenate; butyltintri-2-ethylhexo-ate; tinbutyrate. The preferred condensation catalysts are tin compounds and dibutyltindiacetate is particularly pre-ferred.

Titanium compounds also can be used and are, forexample, 1,3-propanedioxytitanium bis(ethylacetoacetate);
1,3-propanedioxytitanium bis(acetylacetonate); diisopropoxy-titanium bis(acetylacetonate~; titanium naphthenate; tetra-butyltritanate; tetra-2-ethylhexyltitanate;

. RD-14625 tetraphenyltitanate; tetraoctadecyltitanatei ethyltriethan-olaminetitanate. In addition, beta-dicarbonyltitanium compounds as shown by Weyenberg U.S. patent 3,334,067 can be used as condensation catalysts in the present invention.

Zirconium compounds, for example, zirconium octoate, also can be used.

Further examples of metal condensation catalysts are, for example, lead 2-ethyloctoate; iron 2-ethylhexoate;
cobalt 2-ethylhexoate; manganese 2-ethylhexoate; zinc 2-ethylhexoate; antimony ~ct~ate; bismuth naphthenate; zinc naphthenate; zinc stearate.

Examples of nonmetal condensation catalysts are hexylammonium ac~tate and benzyltrimethylammonium acetate.

ln addition to the above described one-package condensation vulcanizable curing agents, there also can be used in the practice of the present invention, curing agents which can be added to the silanol terminated polydiorgano-5i loxane-polyimide copolymer to provide two-package conden-sation vulcanizable compositions as shown by Nitzsche et al, U.S. Pat2nt 3,127,363 . -~ -Some of the organic dianhydrides which can be used in the practice of the present inv~ntion to produce the norbornene terminated polyimide of formula ~5) along with norbornene anhydride chain-terminating monomers are, for example, benzophenone dianhydride, pyromellitic dianhydride, 2,2-bisl4-(3,4 dicarboxyphenoxy)phenyllpropane dianhydride, 2,2-bisl4-(2,3-dicarboxyphenoxy)phenyllpropane dianhydride,

4-(2,3-dicarboxyphenoxy)~4'-(3,4-dicarboxyphenoxy~diphenyl--~ ~ ~ ~ RD-14625 2,2-propane dianhydride, and bisnorbornanesiloxane dianhy-dride of the formula, .. ~H CH
~3'3~b o o and mixtures thereof.

Organic diamines which can be used to make the polyimide blocks of the silanol terminated polydiorganosi-loxane-polyimide copolymers are, for example, o-phenylenediamine;
m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane (commonly named 5 4,4'-methylenedianiline);
4,4'-diaminodiphenyl sulfide (commonly named 4,4'-thiodianiline);
4,4'-diaminodiphenyl ether ~commonly named 4,4'-oxydianiline);
1,5-diaminonaphthalene;
3,3'-dimethylbenzidine;
3,3'-dimethoxybenzidine;
2,4-bis(~-amino-t-butyl)toluene;
1,3-diamino-4-isopropylbenzene;
1,2-bis(3-aminopropoxy)ethane;
benzidine;
m-xylylenediamine;
p-xylylenediamine;

~Z~S83 RD- 14625 2,4 diaminotoluene;
2,6-diaminotoluene;
bis(4-aminocyclohexyl)methane;
3-methylheptamethylenediamine;
5_ 4,4-dimethylheptamet~ylenediamine;
2,11-d~decanediamine;
2,2-dimethylpropylenediamine;
~ctamethylenediamine;
3-methoxyhexamethylenediamine;
1~ 2,5-dimethylhexamethylenediamine;
2,5-dimethylheptamethylenediamine;
3-methylheptamethylenediamine;

5-methylnonamethylenediamine;
1,4-cyclohexanediamine;
1,12-octadecanediamine;
bis(3-aminopropyl)sulfide;
N-methyl-bis(3-aminopropyl)amine;
hexamethylenediamine;
heptamethylenediamine;
nonamethylenediamine;
decamethylenediamine, bis(3-aminopropyl)tetramethyldisiloxane;
bis(4-aminobutyl)tetramethyldisiloxane, and mixtures of ~uch diamines.

Some of the silicon hydrides of formula (7) which can be employ~d in the practice of the present invention to introduce silicon hydride functional groups into the poly-imide having aliphatically unsaturated norbornene groups are, for example ! triethoxysilane, dimethylchlorosilane, M,N-dimethylaminodimethvlsilane, etc.

~ RD-14625 Silanol terminated polydiorganosiloxane~ of formula (1) which can be used in combination with the silicon-norbornaneimides of formula 2 or 8 or mixture3 thereof, to produce the silanol terminat~d polydiorgano-5- 5i loxane-polyimide copolymer such as formula (9~ preferably have a vi~cosity in the range of from about 10 to 400,000 centipoise and preferably from about 1000 to about 250,000 centipoise when measured at about 25C. These silanol terminated fluids can be made by treating a higher molecular weight organopolysiloxane, for example, a dimethylpolysilox-ane with water in the presence of a mineral acid or base catalyst. Hydrolysis of diorganohalosilane, for example, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyl-dichlorosilane, methylfluoropropyldichlorosilane, methyl-cyanoethyldichlorosilane, or mixtures thereof can produce low molecular weight pvlymer. E~uilibration thereafter can provide for higher molecular weight organopolysiloxane.
Organopolysiloxane also can be treated with steam under pressure or other procedures described in U.S. patent 2,607,792 and U.K. patent 835,790.

Some of the condensation catalysts which can be used to make the ~ilanol terminated polydiorganosiloxane polyimide copolymer of formula (9~ are platinum catalysts, for example, platinum complexes of unsaturated siloxanes, as shown by Karstedt U.S. patent 3,775,442, Ashby U.S~ patents 3,159,601, and 3,159,662 and Lamoreaux U.S. patent 3,220,972, a~signed to the same assignee as the present invention. An effective amount of a platinum, catalyst is about 10 4% to 0.1% by weight of platinum, based on the weight of curable hydrosilylation mixture.

Yarious fillers and pigments can be incorporated into the room temperature vulcanizable compositions of the preYent invention. For example, there can be ~sed, titanium dioxide, zirconium silicate, ~ilica aerogel, iron oxide, S diatomaceous earth, fumed silica, carbon black, precipitated ~ilica, glas~ fibers, polyvinyl chloride, ground quartz, calcium carbonate, etc. The amounts of filler used can obviously be varied within wide limits in accordance with the intended use. For example, in some sealant applica-tions, the curable compositions of the present invention canbe used free of filler. In other applications, such as the employment of the curable compositions for making binding material on a weight basis, as much as 700 parts or more of filler, per 100 parts of polydiorganosiloxane-polyimide copolymers can be employed. In such applications, the filler can consist of a major amount of extending materials, such as qround quartz, polyvinyl chloride, or mixtures thereof, preferably having an average particle size in the range of from about 1 to 10 microns.

The condensation vulcanizable compositions of the present invention also can be employed as construction seal-ants and caulking compounds. The exact amount of filler, therefore, will depend upon such factors as the application for which th2 organopolysiloxane composition is intended, the type of filler utilized ~that is, the density of the filler and its particle size). Preferably, a proportion of from 5 to 300 parts of filler, which can include up to about 35 parts of reinforcing filler, such as fumed silica filler, per 100 parts of silanol terminated organopolysiloxane is utilized.

~g3S~3 The silicon-norbornaneimides of formulas (2) and ~B) can be used a~ an adhesion promoter in room temperature vulcanizable organopolysiloxane compositions.

~ here are included within the silicon-norbornane S monoimide of formula (8), compound~ such as 0 CH3 H5 H~H / C

H2~C~\c3 ~ ~ / 3 ~H3 H2 0 CH30-Si~ o Additional compounds which are the above compounds with chlorine or amine radicals attached to silicon.

In the practice of one form of the present inven-tion, the 6ilicon-norbornanebisimide can be r~acted with sila~ol terminated polydiorganosiloxane to produce the ~ilanol terminated polydiorganosiloxane-polyimide copolymer of formula (9) referred to hereinafter as the "silanol polyimide copoly~er". The silanol polyimide copolymer can thereafter be used to make condensation vulcanizable polydi organosiloxane-polyimide copolymer compositionS by mixing the curing agent, condensation catalyst and optionally cross-linking agent with the silanol polyimide copolymer.

~Z~S83 RD-14625 There can be utilized in the condensation vulcan-izable composition~ of the present invention, an effective amount o~ the curing agent as previously defined which may vary depending upon whether a one-package or two-package is S desired, or whether the curing agent utilized will generate an acidic or ~ubstantially neutral by-product. For example, in instances where an acyloxy curing agent i~ used, such as methyltriacetoxysilane, effective results can be achieved if from 0.002 to 10 parts of methyltriacetoxysilane per 100 part~ of the silanol-polyimide copolymer is used. A curing agent, s~ch as shown by formula (10), can be utilized at from 0.002 to 10 parts of curing agent per 100 parts of the silanol-polyimide copolymer. A cross-linking agent, as shown by formula [11) also can be used in ~ombination with the curing agent of formula (10) in proportions of from 0 to 10 parts of cross-linking agent per 100 parts of the silan-ol-polyimide copolymer. Condensation catalyst also can be used in the proportions as previously defined.

As taught previously, the above-described conden sation vulcaniza~le compositions also can be combined with various fillers, pigments and extenders which can be option-ally incorporated into the silicone~polyimide copolymer prior to, alon~ with, or af~er the incorporation of the curing agent, condensation catalyst, etc.

2S The synthesis of the norbornene terminated poly-imide of formula (5) or the corresponding monoimide can be accomplished by conventional procedures, utilizing substan-tially equal molar amounts of the organic diamine dianhy dride along with an effective amount of the chain-stopping norbornene a~hydride or the latter with organic amine such a~ methyl amine or other C(l 8) alkyl amine aniline, etc., ~lB-which can be utilized in an amount sufficient to produce the polyimide at a desired mclecular weight. During the poly-merization of the norbornene termina~ed polyimide, there can be utilized organic 601vents, for ~xample, orthodichloroben-zene, and temperature in the range of from 140~C to 200C
can be employed. Reaction can be conducted in an inert atmo~phere, for example, under nitrogen to minimize undesir-able side reactionq. Reaction times can vary from 30 minute~ or less to 3 hours, depending upon the nature of the reactants, the molecular weight of the polyimide desired, etc.

The silicon-norbornanebisimide of or~ula (2) or monoimide of formula (8) can be synthesized by effecting reaction between the appropriate norbornene imide and an appropriate silicon hydride of formula (7), in the presence of an effective amount of a platinum catalyst. An effective amount of platinum catalyst is from about 10 6 parts to 10 3 parts of platinum, per part of the hydrosilylation mixture consisting of the norbornene terminated polyimide, silicon hydride and an inert organic solvent which can be utilized in an amount sufficient to produce a mixture having from lO~o to 50% by weight of solids. Suitable inert organic solvents which can be used are, for example, chlorobenzene and orthodichlorobenzene. Hydrosilylation is preferably con-ducted under substantially anhydrous conditions at a temp-erature in the range of from 15C to 90C.

The preparation of the silanol-polyimide can be achi~ved by effecting reaction between the silicon-norbor-naneimide of formula ~2) and the silanol~terminat~d polydi-organosiloxane of formula (1) at a temperature in the rangeof from 15C to 150C in the presence of an effective amount ~Z~i~5~33 of copolymeri~ation catalyst. Suitable copolymerization catalysts include for example, amine, alkali metal fluoride, colloidal nic~el, zinc chloride, platinum, or rhodium com-plexes, dibutyltindiacetate, with or without an aprotic solvent to facilitate reaction, such as dichloromethane, chlorobenzene, orthodichlorobenzene, etc, depending upon the mutual solubility of the reactants.

The condensation vulcanizable silicon-polyimide compositions also can be blended with silanol-terminated polydiorganosiloxane of formula (2~ as described above. The blending can be accomplished under substantially anhydrous conditions at a temperature in the range of from about 15C
to about 290C or higher. The resulting cured silicon-poly-imide copolymers can be utilized in a variety of applica-tions requiring high strength, high performance, temperatureresistant elastomers.

In order that those skilled in ~he art will be better able to practice the invention, the following exam-ples are given by way of illustration and not by way of limitation. All parts are by weight.

Exampl~ 1.

A solution of 6.56 grams of norbornene dicarboxyl-dianhydride, 20.8 grams of 2,2-bisl4-(3,4-dicarboxyphenoxy)-phenyllpropane dianhydride and 6.48 grams of meta-phenylene-diamine was refluxed in 100 ml of dry chlorobenzene forthree hours. During the reflux period, water was continu-ously removed azeotropically. After some of the solvent was removed under reduced pressure, the residue was poured into 600 ml of methanol and stirred vigorously. A precipitate . RD-14625 ~L~S~3 was collected which was washed with methanol and dried.
There was obtained 31 grams of product. A 98% yield of an oligomer was recovered having the formula q ~.
~ C

~ d /

o o lo ~o~7_~0~0~ N ~

There was added 5 drops of a 5% platinum catalyst prepared in accordance with Karstedt, U.S. Patent 3,775,442 to a solution of 2 grams of the above norbornen@ terminated oligoi-mide, 0.3 grams of dimethylchlorosilane in 30 ml of dry chlorobenzene. The addition was performed under substan-tially dry conditions. The ~olution was heated to 80C over a period of about 12 hours under sealed conditions. Based on method of preparation there was obtained a dimethyl-chlorosilylnorbornane end-stopped oligomide corresponding to the norbornene terminated oligomide shown above which was confirmed by NMR. After excess dimethylchlorosilane was removed from the mixture, there was added 0.4 gr ms of sodium acetate and the mixture was stirred at a~bient 5~33 conditions for an additional 12 hours. Carbon black was then added to the mixture which was filtered resulting in a colorless solution. Based on method of preparation and NMR spectra, there was obtained a dimethylacetoxysilyl-norbornane imide end-capped oligomide having the formula, O O

C~H3<~ ' ~ \ ~ ~Hi~3 CH3 ~ / C~ 3 ,'11 11 ~
O O ~

~O~ ~;t~

There was added to the above solution 14.5 grams of a silanol terminated dimethylpolysiloxane having 3.15 weight percent chemically combined hydroxy radicals. The resulting solution was stirred at ambient conditions for 12 hours. Upon evaporation of the volatiles of the resulting mixture, there was obtained an opaque, high viscous residue. Based on method of preparation, the product was a silanol terminated siloxane-imide block copolymer.
A blend of 2 grams of the block copolymer and 20 miligrams of methyltriacetoxysilane along with 0.1 part of dibutyltindiacetate is exposed for 1 week under 58%
relative humidity. A tack-free elastomer is obtained.

~ZS~3 RD-14625 Example 2.

Th~r~ was refluxed for a three hour period, a solution of 9.Bl grams of norbornene dicarboxylic acid _ monoet~ylester, 9.66 ~rams of benzophenone tetracarboxylic acid dimethylester, 9.91 qrams of 4,4'omethylenedianiline and lO0 ml of dry methanol. After the solvent was removed, the re~idue was heated to 150~C for 3 hours under nitrogen.
The resulting product was dissolved in dry chlorobenzene and then poured into methanol. There was obtained a precipitate which was collected, washed with methanol and dried in accordance with the procedure of Example l. A yield of 98%
of a product was obtained having the following formula O
~ C \ N ~ ~ \21 .

O O '"
..

CH2 ~ N\ ~ ~ N ~ C ~ CH
0 0 n where n i 6 1 .

A mixture of 3.14 grams of the above norbornene imide end-capped oligomide, 2 grams of triethoxysilane, lO0 ~L;25~ 3 ml of dry chlorobenzene and 5 drops o a 5% platinum cata-lyst of Exampl~ 1, was heated under ~ubstantially anhydrous conditions to 80"C over a 12 hour period. After removal of 50 ml of ~olvent and excess trietho~y~ilane, the residue was S poured into 100 ml of dry ethylether. There was obtained 3.96 grams, or 96% yield of a triethoxysilyl end-capped oligom~de. After the product was collected, washed with diethylether and dried. The identity of the product was . confirmed by lH NMR. The formula of the product was as follows O O
2 5 ~ ~ ~ N ~ H2 rSitOC2H5)3 /0 0\ ~
/ \
, \

O ~~ O '~
~CH2{>--N' ~/ \~, C ~}CH

O O ~

A blend of 0.3 grams of the above oligomide, 3 grams of a silanol terminated polydimethylsiloxane having a vi~co ity of 126,000, 200 centipoise, 0.15 grams of fumed lS ~ilica and one drop of dibutyltindiacetate in 20 ml of dry methylene chloride was poured into a glass dish. After removal of th~ 601vent, the residue was heated to 150C for 4 hours resulting in the formation of a cured tough elasto-mer exhibiting ~ood adhesion to the gla s.

Example 3.

There was ~ixed 4.2 grams of the norborneneimide e~d-capped oligomide of Example 2 with 3 grams of dimethyl-chlorosilane, 100 ml of chlorobenzene and 5 drops of the 5%
platinum catalyst of Example 1 under nitrogen. The result-ing mixture was heated to 80-100C for 24 hours. After removal of unreacted dimethylchlorosilane, the residue was 0 510wly added to a solution of dimethylamine to a solution of 2 grams of dimethylamine in 20 ml of chlorobenzene at about 0C. The resulting mixture was stirred at room temperature for a period of 12 hours. Carbon black was then added to the solution and the mixture was further stirred for 2 more hourR. Filtration of the mixture resulted in a clear filtrate of a dimethylaminosilane terminated oligomide having the formu-l~a~
/

_ _ _ _ _ _ _ _ _ _ , .. .. .. . ..... ... . .. . .

CH3 ~ CH3 (CH3)2N-S ~ N~CH3)2 O O ~

f O O

~2 ~ \C ~ ~ t o o n The identity of the above product was confirmed by NMR. The above filtrate was slowly added to a solution of 44 grams of a silanol terminated polydimethylsiloxane having about 3.15 weight percent of silanol at 80C over an addition period of about 40 manutes. The resulting opaque mixture was further ~tirred at 80C until evolution of dimethylamine had ceased.
The resulting solution was then washed with water several times and volatiles were removed from the mixture under reduced pressure. There was obtained an opaque residue which was a silanol terminated siloxane imide block copoly-mer having an intrinsic viscosity in chloroform of about 28,500 centipoises. The block copolymer was mixed with ~S83 RD-14625 1-1/2 grams of methyltriacetoxysilane in 0.3 gram of dibut-yltindiacetate under substantially anhydrous conditions.

The resulting mixture was exposed at room temper-- ature for about 1 week under a 58% relative humidity. There S was obtained an opaque elastomer having a tensile strength (psi) of 139 and an eiongation (percent) of 500.

Although the above examples are directed to only a few of the very many variables within the scope of the pr~ent invention it should be understood that the present invention is directed to a much broader variety of sili-con-norbornane imides as shown by formula ~2) which can be used to maXe silanol terminated 6ilicone imide block copoly-mers useful in making room temperature vulcanizable composi-tion~ convertible to high strength elastomers.

Claims (5)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. Silicon functionalized norbornane carboxy-imides of the formula, where R is a divalent radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6-20 carbon atoms, and halogenated aromatic hydrocarbon radicals having from 6-20 carbon atoms, (b) alkylene radi-cals having from 2-20 carbbon atoms and cycloalkylene radicals having from 2-20 carbon atoms, (c) C(2-8) alkylene terminated polydiorganosiloxane, and (d) radicals included by the general formula Q' is a member selected from the class consisting of and -CXH2x , x is a whole number from 1 to 5 inclusive, Q is a tetra-valent radical selected from and where D is a member selected from and -OR8O-and R8 is a divalent radical selected from
1. Claim 1 continued:
   
   and divalent organic radicals of the general formula, X is a member selected from the class consisting of divalent radicals of the formula, y is an integer from 1 to 5, R1-R6 are selected from hydrogen and C(1-8) alkyl radicals, R7 is the same or different C(1-13) monovalent hydrocarbon radical and substituted C(1-13) monovalent hydrocarbon radical, Y is a divalent radical selected from -0- and -C(R1)2-, Z
   is selected from C(1-8) alkoxy, acyloxy, halogen and amine, n is an integer equal to 1-2000 inclusive, and p is equal to 0 or 1, and R10-R11 are selected from Z or R7.
2. 2. A silicon functionalized carboxyimide of claim 1 having the formula
3. 3. A silicon functionalized carboxyimide of claim 1 having the formula where n is 1.
4. 4. A silicon functionalized carboxyimide of claim 1 having the formula where n is 1.
   5. A method for making a silicon functionalized norbornane carboxyimide which comprises (1) effecting reation in the presence of an inert organic solvent at a temperature in the range of from 15°C to 90°C and under substantially anhydrous conditions between an aliphatically unsaturated polyimide of the formula, and a silicon hydride of the formula in the presence of an effective amount of a platinum catalyst, where R is a divalent radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated aromatic hydrocarbon radicals having from 6-20 carbon atoms, (b) alkylene radi-cals having from 2-20 carbon atoms and cycloalkylene radi-cals having from 2-20 carbon atoms, (c) C(2-8) alkylene terminated polydiorganosiloxane, and (d) radicals included by the general formula, Q' is a member selected from the class consisting of x is a whole number from 1 to 5 inclusive, Q is a tetra-valent radical selected from and where D is a member selected from and R8 is a divalent radical selected from and divalent organic radicals of the general formula, X is a member selected from the class consisting of divalent radicals of the formula, and -S- , y is an integer from 1 to 5, R1-R6 are selected from hydro-gen and C(1-8) alkyl radicals, R7 is the same or different C(1-13) monovalent hydrocarbon radical and substituted C(1-13) monovalent hydrocarbon radical, Y is a divalent radical selected from -O- and -C(R1)2-, Z is selected from
5. Claim 5 continued:
   C(1-8) alkoxy, acyloxy, halogen and amine, n is an integer equal to 0-200 inclusive, and p is equal to 0 or 1, and R10-11 are selected from Z or R7.