Claims
- 1. A composition capable of being converted into a polyimide or poly(amide-imide) which, when present in the form of a shaped article, is relatively free of voids, pinholes, cracks and bubbles, said composition comprising a polyamic acid containing about 0.75 to about 5 mole percent of a polysiloxane incorporated in its backbone, dissolved in a solvent selected from the group consisting of tetrahydrofuran, m-dioxane, p-dioxane, monoglyme, diglyme, triglyme, tetraglyme and mixtures thereof.
- 2. The composition of claim 1 in which the polyamic acid is present in the solvent in an amount of about 5 to about 50 weight percent.
- 3. The composition of claim 2 in which the polyamic acid is present in the solvent in an amount of 20 to 40 weight percent.
- 4. The composition of claim 1 in which the polysiloxane is present in an amount of 1.5 to 2.5 mole percent.
- 5. The composition of claim 1 in which the polysiloxane has a monomeric unit formula of ##STR51## or of formula ##STR52## where Q is a substituted or unsubstituted aromatic group,
- Z is --O--, --S--, ##STR53## R and D is each unsubstituted or substituted hydrocarbylene; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each, independently, is unsubstituted or substituted hydrocarbyl;
- x, y and z each independently has a value from 0 to 100, and w has a value from 1 to 100.
- 6. The composition of claim 5 in which the polysiloxane has a monomeric unit formula of ##STR54## in which Q is substituted or unsubstituted carbocyclic aromatic of 6 to 18 ring carbon atoms or substituted or unsubstituted heterocyclic aromatic of 5 to 18 ring atoms where the hetero atoms are selected from the group consisting of N, O and S and where any substituents present are selected from the group consisting of alkyl of 1 to 12 carbon atoms, alkynyl of 2 to 12 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkylthio of 1 to 12 carbon atoms, phenyl, alkylphenylene having 1 to 12 carbon atoms in the alkyl group, phenoxy, phenylthio, alkylcarbonyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms, bromo, chloro, fluoro, iodo, nitro, cyano, cyanothio, carbonyl, hydroxy, mercapto, formyl, thioformyl and mercaptocarbonyl;
- D is substituted or unsubstituted hydrocarbylene of 1 to 3 to 18 carbon atoms;
- R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6, each independently, is an unsubstituted or substituted alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkynyl of 2 to 12 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, phenyl, alkylphenylene where the alkyl group contains 1 to 12 carbon atoms, phenylalkylene where the alkylene group contains 1 to 12 carbon atoms in the alkenyl group and when substituted, these hydrocarbyl groups are substituted by Br, Cl, I, R, --NC, --NO.sub.2, --OCN, alkoxy of 1 to 8 carbon atoms, --S--(C.sub.1 -C.sub.8)alkyl, ##STR55## --S--S--(C.sub.1 -C.sub.8)alkyl, --COOH, --COSH, --CSOH, --CONH.sub.2, --CN, --CHO, --CHS, --OH, --SH, --NCO and --NR.sub.7 R.sub.8 where R.sub.7 and R.sub.8 independently are hydrogen or lower alkyl.
- 7. The composition of claim 6 in which
- Q is unsubstituted or substituted carbocyclic aromatic of 6 to 18 carbon atoms;
- D is branched or linear alkylene of 1 or 3 to 12 carbon atoms; and
- x, y and z is each 0,
- 8. The composition of claim 7 in which the polysiloxane has a monomeric unit formula of ##STR56## where v is 0 or 4;
- R.sub.9 is lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl of 4 to 8 carbon atoms, lower alkoxy, lower alkylthio, phenyl, loweralkylphenylene, phenylloweralkylene, loweralkenylphenylene, phenoxy, phenylthio, loweralkylcarbonyl, loweralkylcarbonyloxy, loweralkoxycarbonyl, bromo, chloro, fluoro, iodo, nitro, cyano, cyanthio, carboxyl, carbonyl, hydroxyl, mercapto, or mercaptocarbonyl;
- Z is --O--, --S--, ##STR57## D.sub.1 is methylene or alkylene of 3 to 8 carbon atoms; R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl, phenyl, loweralkylphenylene, phenylloweralkylene, or lower alkenylphenylene.
- 9. The composition of claim 5 in which the polysiloxane has a unit formula of ##STR58## wherein R" is alkylene or arylene and each R"' is independently C.sub.1 -C.sub.4 alkyl or phenyl.
- 10. The composition of claim 9 in which the polysiloxane has a monomeric unit formula of ##STR59## wherein n is an integer of 1 to 6, a has a value of 1 to 30 and each R"' is independently C.sub.1 -C.sub.4 alkyl or phenyl.
- 11. The composition of claim 10 in which the polysiloxane has the monomeric unit formula of ##STR60##
- 12. The composition of claim 11 in which the polysiloxane has the monomeric unit formula of ##STR61##
- 13. The composition of claim 1 in which the polyamic acid is prepared by reacting benzophenone tetracarboxylic acid dianhydride with 3,3' diaminodiphenyl sulfoxide in the presence of 1.5 to 2.5 mole percent of a bis(amino)polysiloxane having the formula ##STR62##
- 14. The composition of claim 1 in which the solvent is diglyme.
REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 664,129, filed Oct. 24, 1984, now abandoned.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
PCT/US85/02061 |
10/24/1985 |
|
|
10/24/1985 |
10/24/1985 |
Publishing Document |
Publishing Date |
Country |
Kind |
WO86/02593 |
5/9/1986 |
|
|
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
3926911 |
Greber et al. |
Dec 1975 |
|
4395527 |
Berger |
Jul 1983 |
|
4520075 |
Igarashi et al. |
May 1985 |
|
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
664129 |
Oct 1984 |
|