Fire-resistant phosphorus containing polyimides and copolyimides

A method of producing a polymer having the formula:

• ##STR15## wherein:
• Ar is, independently in each case, a tetravalent aromatic group containing from 6 to 20 carbon atoms selected from among phenyls, naphthalenes, phenanthrenes, benzophenones and benzosulfones;
• R is an alkyl, haloalkyl or aryl group;
• n is a positive integer;
• and the linkage of the group:
• ##STR16## is in a 4-position or 6-position relative to the (phosphonyl)methyl group, which method comprises:
• (a) reacting at 20.degree. C. to 50.degree. C. a (phosphonyl)methyl diaminobenzene of the formula ##STR17## wherein R is as described herein with a substantially equimolar amount of a compound of the formula:
• ##STR18## wherein Ar is as defined herein, in a polar aprotic solvent to form an intermediate of the formula:
• ##STR19## wherein Ar, R and n defined hereinabove;
• and (b) dehydrating said intermediate of step (a) by thermal or chemical means or a combination thereof.

A method of producing a polymer having the formula:

• ##STR20## wherein:
• Ar is a tetravalent aromatic group containing from 6 to 20 carbon atoms selected from among phenyls, naphthalenes, phenanthrenes, benzophenones and benzosulfones;
• R is an alkyl, haloalkyl or aryl group;
• R' is an aliphatic or aromatic group containing from 2 to 20 carbon atoms;
• x and y are independently positive integers;
• and the linkage of the group:
• ##STR21## is in a 4-position or a 6-position relative to the (phosphonyl)methyl group which process comprises:
• (a) reacting at 20.degree. C. to 50.degree. C. a mixture which itself contains:
• (i) a (phosphonyl)methyl diaminobenzene of the formula ##STR22## wherein R is as defined herein;
• (ii) an aryl tetracarboxylic dianhydride of the formula:
• ##STR23## wherein Ar is as defined herein;
• and (iii) a diamine of the formula:
• H.sub.2 N--R'--NH.sub.2
• wherein R' is as defined herein with the number of equivalents of anhydride in the dianhydride (ii) being substantially equal to the number of equivalents of amine in amines (i) plus (iii);
• in a polar aprotic dipolar solvent to produce an intermediate of the formula:
• ##STR24## wherein Ar, R, R', x and y are as defined herein;
• and (b) dehydrating the said intermediate of step (a) by thermal or chemical means or a combination thereof.

A method of producing a polymer having the formula:

• ##STR25## wherein:
• Ar is, independently in each case, a tetravalent aromatic group containing from 6 to 20 carbon atoms selected from among phenyls, naphthalenes, phenanthrenes, benzophenones and benzosulfones;
• R is an alkyl, haloalkyl or aryl group;
• n is a positive integer;
• and the linkage of the group:
• ##STR26## is in a 4-position or 6-position relative to the (phosphonyl)methyl group, which method comprises:
• (a) reacting at 20.degree. C. to 50.degree. C. a (phosphonyl)methyl diaminobenzene of the formula ##STR27## wherein R is as described herein with a sustantially equimolar amount of a compound of the formula:
• ##STR28## wherein Ar is as defined herein, in a polar aprotic solvent;
• and thereafter
• (b) recovering said polymer.

A method of producing a polymer having the formula:

• ##STR29## wherein:
• Ar is a tetravalent aromatic group containing from 6 to 20 carbon atoms selected from among phenyls, naphthalenes, phenanthrenes, benzophenones and benzosulfones;
• R is an alkyl, haloalkyl or aryl group;
• R' is an aliphatic or aromatic group containing from 2 to 20 carbon atoms;
• x and y are independently positive integers;
• and the linkage of the group:
• ##STR30## is in a 4-position or a 6-position relative to the (phosphonyl)methyl group which process comprises:
• (a) reacting at 20.degree. C. to 50.degree. C. a mixture which itself contains:
• (i) a (phosphonyl)methyl diaminobenzene of the formula ##STR31## wherein R is as defined herein;
• (ii) an aryl tetracarboxylic dianhydride of the formula:
• ##STR32## wherein Ar is as defined herein;
• and (iii) a diamine of the formula:
• H.sub.2 N--R'--NH.sub.2
• wherein R' is as defined herein with the number of equivalents of anhydride in the dianhydride (ii) being substantially equal to the number of equivalents of amine in amines (i) plus (iii);
• in a polar aprotic dipolar solvent;
• and thereafter
• (b) recovering said polymer.