Novel partially acetylene end-capped polyimide oligomers

Claim 2

A product selected from the group consisting of: A. An acetylene end-capped polyimide oligomer having the structure: ##STR8## where R has the structure: ##STR9## where X is ##STR10## --O--, --CH 2 --, --S--, ##STR11## --CF 2 --, or a bond, where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR12## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; and where n has an average value of from 1 to about 4; B. A first precursor of a partially acetylene end-capped polyimide oligomer of (A) having the structure: ##STR13## where R, R' and R" and n are as defined above; and C. A second precursor of a partially acetylene end-capped polyimide oligomer of (A) having the structure: ##STR14## where R, R' and R" and n are as defined above and R''' is the alcohol moiety from which the diester of the aromatic tetracarboxylic acid was prepared.

Claim 3

A partially acetylene end-capped polyimide oligomer having the structure: ##STR15## where R has the structure: ##STR16## where X is ##STR17## --O--, --CH 2 --, --S--, ##STR18## --CF 2 --, or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR19## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; and where n has an average value of from 1 to about 4.

Claim 4

A partially acetylene end-capped polyimide oligomer having the structure: ##STR15## where R has the structure: ##STR16## where X is ##STR17## --O--, --CH 2 --, --S--, ##STR18## --CF 2 --, or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR19## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; and where n has an average value of from 1 to about 4.

Claim 5

A precursor of a partially acetylene end-capped polyimide oligomer having the structure: ##STR20## where R has the structure: ##STR21## where X is ##STR22## --O--, --CH 2 --, --S--, ##STR23## --CF 2 --, or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR24## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; and where n has an average value of from 1 to about 4.

Claim 6

A precursor of a partially acetylene end-capped polyimide oligomer having the structure: ##STR20## where R has the structure: ##STR21## where X is ##STR22## --O--, --CH 2 --, --S--, ##STR23## --CF 2 --, or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR24## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; and where n has an average value of from 1 to about 4.

Claim 7

A precursor of a partially acetylene end-capped polyimide oligomer having the structure: ##STR25## where R has the structure: ##STR26## where X is ##STR27## --O--, --CH 2 --, --S--, ##STR28## --CF 2 -- or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR29## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; where n has an average value of from 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 partially acetylene end-capped polyimide oligomer having the structure: ##STR25## where R has the structure: ##STR26## where X is ##STR27## --O--, --CH 2 --, --S--, ##STR28## --CF 2 -- or a bond; where R' is selected from the group consisting of a phenylene group, a naphthylene group, or ##STR29## where X is as defined above; where R" consists of a mixture of about 20-30 mol % of an aryl group and the balance an acetylene substituted aryl group; where n has an average value of from 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 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 0.5-0.8 molar portion of an aromatic diamine thereto and forming a reaction product consisting essentially of a chemical having the structure: ##STR30## 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: ##STR31## said aromatic tetracarboxylic acid dianhydride having the formula: ##STR32## where R has the structure: ##STR33## where X is ##STR34## --O--, --CH 2 --, ##STR35## --CF 2 --, or a bond; said aromatic diamine having the formula: H.sub.2 N--R'--NH.sub.2 ##STR36## and X is as defined above; said aromatic monoamine consisting of a mixture of about 20-30 mol % of an aromatic monoamine and the balance an acetylene substituted aromatic monoamine; and the solvent employed in step (A) is selected from the group consisting of N-methyl-2-pyrrolidone, cyclohexanone, diethyl carbonate, and gammabutyrolactone.

Claim 10

A product of claim 1, 2, 3, or 4 in which R has the structure: ##STR37## and where R" has the structure: ##STR38##

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: ##STR39## where R has the structure: ##STR40## where X is ##STR41## --O--, --CH 2 --, --S--, ##STR42## --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 ##STR43## where X is as defined above; said aromatic monoamine consisting of a mixture of about 20-30 mol % of an aromatic monoamine and the balance an acetylene substituted 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 5 or 7 in which R has the structure: ##STR44## and where R" has the structure: ##STR45##

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 5 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: ##STR46## and where R' has the structure: ##STR47##

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.

Claim 18

A product of claim 1 where R" consists of a mixture of about 15-40 mol % of an aryl group and the balance an acetylene substituted aryl group.