Phenylated polyimides prepared from 3,6-diarylpyromellitic dianhydride and aromatic diamines

A process for preparing a phenylated polyimide polymer having repeating units of the formula (VI) ##STR35## where R is an acid or acid derivative, or nitro group and n is an integer between 1 and 4 inclusive and where Q is a divalent organic radical selected from the group consisting of:

• ##STR36## where the terminal covalent bonds are either in the meta or para position with respect to each other;
• ##STR37## where G is O, S, keto, sulfoxy, sulfonyl or a linking bond, Z is hydrogen or a halogen atom or alkyl, alkoxy, or halogenated alkyl containing between 1 to 4 carbons, both terminal covalent bonds are located in the meta or para position with respect to G and Z is located in the ortho or meta position with respect to the covalent bond;
• ##STR38## where G' is O, S or an isopropylidine group, Z' is hydrogen or phenyl, and both terminal covalent bonds are either in the ortho or meta or para position with respect to G';
• ##STR39## where G" is O, or S, and R' is phenyl, biphenyl, or naphthyl;
• ##STR40## where G.sup.3 is O or S, and both terminal covalent bonds are in the ortho or meta position with respect to G.sup.3 and X is H, F, Cl or Br;
• and ##STR41## where both terminal covalent bonds are in para or meta position with respect to the fluorene ring covalent bonds, which comprises the steps of:
• (1) reacting a dianhydride of the formula (VII) ##STR42## (2) with a diamine of the formula (VIII)
• H.sub.2 N--Q--NH.sub.2 (VIII)
• or a mixture thereof, for a time and at a temperature sufficient to synthesize the phenylated polyimide polymer which is characterized by solubility in NMP and m-cresol and the ability of the phenylated polyimide polymer to be solution cast into films and membranes.

A phenylated polyimide polymer characterized by the presence of repeating units of the formula (VI) ##STR44## where R is an acid or acid derivative, or nitro group and n is 0 and where Q is a divalent organic radical selected from the group consisting of:

• ##STR45## where the terminal covalent bonds are either in the meta or para positions with respect to each other;
• ##STR46## where G is O, S, keto, sulfoxy, sulfonyl or a linking bond, Z is hydrogen or a halogen atom or alkyl, alkoxy, or halogenated alkyl containing between 1 to 4 carbon atoms, both terminal covalent bonds are located in the meta or para position with respect to G, and Z is located in the ortho or meta position with respect to the covalent bond;
• ##STR47## where G' is O, S or an isopropylidine group, Z' is hydrogen or phenyl, and both terminal covalent bonds are either in the ortho or meta or para position with respect to G';
• ##STR48## where G" is O or S and R' is phenyl, biphenyl, or naphthyl;
• ##STR49## where G.sup.3 is O or S, and both terminal covalent bonds are in the ortho or meta position with respect to G.sup.3 and X is H, F, Cl or Br;
• and ##STR50## where both terminal covalent bonds are in the para or meta position with respect to the fluorene ring covalent bonds.

A process for preparing a phenylated polyimide polymer having repeating units of the formula (VI) ##STR51## where R is an acid or acid derivative, or nitro group and n is 0 and where Q is a divalent organic radical selected from the group consisting of:

• ##STR52## where the terminal covalent bonds are either in the meta or para position with respect to each other;
• ##STR53## where G is O, S, keto, sulfoxy, sulfonyl or a linking bond, Z is hydrogen or a halogen atom or alkyl, alkoxy, or halogenated alkyl containing between 1 to 4 carbons, both terminal covalent bonds are located in the meta or para position with respect to G and Z is located in the ortho or meta position with respect to the covalent bond;
• ##STR54## where G' is O, S or an isopropylidine group, Z' is hydrogen or phenyl, and both terminal covalent bonds are either in the ortho or meta or para position with respect to G';
• ##STR55## where G:
• is O or S and R' is phenyl, biphenyl, or naphthyl;
• ##STR56## where G.sup.3 is O or S, and both terminal covalent bonds are in the ortho or meta position with respect to G.sup.3 and X is H, F, Cl or Br;
• and ##STR57## where both terminal covalent bonds are in para or meta position with respect to the fluorene ring covalent bonds, which comprises the steps of
• (a) reacting a dianhydride of the formula (VII) ##STR58## (b) with a diamine of the formula (VIII)
• H.sub.2 N--Q--NH.sub.2 (VIII)
• or a mixture thereof, for a time and at a temperature sufficient to synthesize the phenylated polyimide polymer which is characterized by solubility in NMP and m-cresol and the ability of the phenylated polyimide polymer to be solution cast into films and membranes.