Novel vinyl end-capped polyimide oligomers

Claim 2

A product selected from the group consisting of: A. A vinyl end-capped polyimide oligomer having the structure: ##STR10## where R has the structure: ##STR11## where X is ##STR12## --O--, --CH 2 --, --S--, ##STR13## --CF 2 --, or a bond, where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR14## where X is as defined above; and where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; and where n has an average value of from 1 to about 4; B. A first precursor of a vinyl end-capped polyimide oligomer of (A) having the structure: ##STR15## where R, R' and R" and n are as defined above; and C. A second precursor of a vinyl end-capped polyimide oligomer of (A) having the structure: ##STR16## where R, R' and R" are as defined above and R'" is the alcohol moiety from which the diester of the aromatic tetracarboxylic acid was prepared.

Claim 3

A vinyl end-capped polyimide oligomer having the structure: ##STR17## where R has the structure: ##STR18## where X is ##STR19## --O--, --CH 2 --, --S--, ##STR20## --CF 2 --, or a bond, where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR21## where X is as defined above; where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; and where n has an average value of from 1 to about 4.

Claim 4

A vinyl end-capped polyimide oligomer having the structure: ##STR17## where R has the structure: ##STR18## where X is ##STR19## --O--, --CH 2 --, --S--, ##STR20## --CF 2 --, or a bond, where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR21## where X is as defined above; where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; and where n has an average value of from 1 to about 4.

Claim 5

A precursor of a vinyl end-capped polyimide oligomer having the structure: ##STR22## where R has the structure: ##STR23## where X is ##STR24## --O--, --CH 2 --, --S--, ##STR25## ##STR26## --CF 2 -- or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR27## where X is as defined above; where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; and where n has an average value of from 1 to about 4.

Claim 6

A precursor of a vinyl end-capped polyimide oligomer having the structure: ##STR22## where R has the structure: ##STR23## where X is ##STR24## --O--, --CH 2 --, --S--, ##STR25## ##STR26## --CF 2 -- or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR27## where X is as defined above; where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; and where n has an average value of from 1 to about 4.

Claim 7

A precursor of a vinyl end-capped polyimide oligomer having the structure: ##STR28## where R has the structure: ##STR29## where X is ##STR30## --O--, --CH 2 --, --S--, ##STR31## --CF 2 -- or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR32## where X is as defined above; where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; where n has an average value of about 1 to about 4; and where R'" is the alcohol moiety from which the diester of the aromatic tetracarboxylic acid was prepared.

Claim 8

A precursor of a vinyl end-capped polyimide oligomer having the structure: ##STR28## where R has the structure: ##STR29## where X is ##STR30## --O--, --CH 2 --, --S--, ##STR31## --CF 2 -- or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR32## where X is as defined above; where R" consists of about 50-100 mol % of a vinyl substituted aryl group and the balance (if any) an unsubstituted aryl group; where n has an average value of about 1 to about 4; and where R'" is the alcohol moiety from which the diester of the aromatic tetracarboxylic acid was prepared.

Claim 9

A product of claim 1, 2, 3, or 4 in which R has the structure: ##STR33## and where R' has the structure: ##STR34##

Claim 10

A process for preparing a product of claim 3 which consists essentially of: a. Dissolving at least 17 weight % of an aromatic tetracarboxylic acid dianhydride in a solvent at a temperature of at least 60° C., b. Maintaining a solution of step (a) containing substantially 1 molar portion of said aromatic tetracarboxylic acid dianhydride at a temperature in a range of about 30°-100° C. and adding substantially 0.50 molar portion of an aromatic diamine thereto and forming a reaction product consisting essentially of a chemical having the structure: ##STR35## c. Adding substantially 1.0 molar portion of an aromatic monoamine to the product of step (b) and forming a reaction product consisting essentially of a chemical having the structure: ##STR36## said aromatic tetracarboxylic acid dianhydride having the formula: ##STR37## where R has the structure: ##STR38## where X is ##STR39## --O--, --CH 2 --, ##STR40## --S--, ##STR41## --CF 2 --, or a bond; said aromatic diamine having the formula: H.sub.2 N--R'--NH.sub.2 where R 1 is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR42## where X is as defined above; said aromatic monoamine consisting of about 50-100 mol % of a vinyl substituted aromatic monoamine and the balance (if any) of an unsubstituted aromatic monoamine; and the solvent employed in step (a) is selected from the group consisting of N-methyl-2-pyrrolidone, cyclohexanone, diethyl carbonate, and gamma-butyrolactone.

Claim 11

A process for preparing a product of claim 4 which consists essentially of: A. Adding, with stirring, a solution containing substantially 0.5-0.8 molar portion of an aromatic diamine to a solution containing substantially 1.0 molar portion of a dialkyl ester of an aromatic tetracarboxylic acid, and B. Adding substantially 1.0 molar portion of an aromatic monoamine to the solution of (A); the dialkyl ester of the aromatic tetracarboxylic acid employed in step (A) having the formula: ##STR43## where R has the structure: ##STR44## where X is ##STR45## --O--, --CH 2 --, ##STR46## --S--, ##STR47## --CF 2 --, or a bond, and where R" is the moiety of an alkanol containing up to about 5 carbon atoms; said aromatic diamine having the formula: H.sub.2 N--R'--NH.sub.2 where R' is a phenylene group, a naphthylene group, or ##STR48## where X is as defined above; said aromatic monoamine consisting of about 50-100 mol % of a vinyl substituted aromatic monoamine and the balance (if any) an unsubstituted aromatic monoamine; and the solvent employed in step (A) having an atmospheric boiling point of less than about 150° C. and is selected from the group consisting of lower alkanols containing up to about 5 carbon atoms, lower ethers containing up to about 6 carbon atoms, and mixtures thereof.

Claim 12

A process of claim 6 or 7 in which R has the structure: ##STR49## and where R' has the structure: ##STR50##

Claim 13

A process for preparing a product of claim 2 which consists essentially of preparing a product of claim 3 by the method of claim 6 and effecting ring closure of the amic acid groups by a dehydration reaction.

Claim 14

A process for preparing a product of claim 2 which consists essentially of preparing a product of claim 4 by the process of claim 7 and heating said product to effect a ring closure to form imide groups.

Claim 15

A process of claim 9 or 10 in which R has the structure: ##STR51## and where R' has the structure: ##STR52##

Claim 16

A coating and laminating varnish consisting essentially of a product of claim 3 dissolved in a solvent selected from the group consisting of N-methyl-2-pyrrolidone, cyclohexanone, diethyl carbonate, and gamma-butyrolactone.

Claim 17

A coating and laminating varnish consisting essentially of a product of claim 4 dissolved in a solvent having an atmospheric boiling point of less than about 150° C. and selected from the group consisting of lower alkanols containing up to about 5 carbon atoms, lower ethers containing up to about 6 carbon atoms, and mixtures thereof.