Isomaleimides and polymers derived therefrom

• US 5,744,574 A
• Filed: 12/05/1995
• Issued: 04/28/1998
• Est. Priority Date: 12/05/1995
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Hansen, Richard G., Anderson, Gregory J., Ezzell, Stephen A.
• Primary Examiner(s): COONEY, JOHN M
• Application Number:
  US08/557,086
• Time in Patent Office: 875 Days
• Field of Search: 528/315, 528/318, 549/475, 549/480
• US Class Current: 528/315
• CPC Class Codes: C07D 307/52 Radicals substituted by nitrogen atoms not forming part of a nitro radical
• CPC Class Codes: C08G 73/0246 Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
• CPC Class Codes: C08G 73/028 Polyamidoamines

Abstract

Isomaleimides and polyisomaleimides can be prepared by a method comprising the steps in sequence: admixing a maleamic acid or polymaleamic acid with an acid halide, reacting the admixture with a tertiary amine at a temperature sufficiently low to suppress the formation of a maleimide, and isolating the resulting isomaleimide or polyisomaleimide. Polymerization of a polyisomaleimide with a polynucleophilic monomer (polythiol, polyol, polyamine) produces novel polymers.

Claims

1. A method for preparing an isomaleimide or polyisomaleimide comprising the steps in sequence:

(a) admixing at least one of a maleamic acid and a polymaleamic acid with an acid halide,

(b) reacting the admixture with a tertiary amine at a temperature sufficiently low to suppress the formation of a maleimide, and

(c) isolating the resulting isomaleimide or polyisomaleimide.

2. The method according to claim 1 wherein said polyisomaleimide has the formula ##STR16## wherein R represents a polyvalent organic group derived from a polymeric primary polyamine by replacement of both hydrogen atoms from each amino group for each isomaleimide group formed, and

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic;

n represents the degree of isomaleimide functionality, and is an integer of at least 2.

3. The method according to claim 2 wherein n is an integer in the range of 2 to 50,000.

4. The method according to claim 1 further comprising the step of polymerizing said polyisomaleimide with a polynucleophilic monomer selected from the group consisting of polythiols, nonphenolic polyols, and primary or secondary polyamines, and combinations thereof in the absence of solvent.

5. The method according to claim 1 wherein said acid halide has the formula ##STR17## wherein R³ represents a monovalent aliphatic, alicyclic, or aromatic hydrocarbon radical having one or more carbon atoms;

and X represents chlorine, bromine, fluorine or iodine.

6. The method according to claim 5 wherein R³ is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, 2-ethyl-n-hexyl, n-heptyl, n-octyl, n-nonyl, n-dodecyl, and cyclohexyl groups.

7. The method according to claim 5 wherein said acid halide is ethyl chloroformate.

8. The method according to claim 1 wherein said maleamic acid has the formula ##STR18## wherein W is a polyvalent organic group which can include 0 to 100 heteroatoms that interrupt carbon chains and optionally substituent groups, provided that W and its substituent groups do not interfere with formation of isomaleimides, polyisomaleimides, and polymers of the invention,

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic;

and t is an integer having a value greater than 1.

9. The method according to claim 1 wherein said tertiary amine is an aliphatic or aromatic tertiary amine which is free of carboxylic acid, amino, olefinic, and acetylinic groups.

10. The method according to claim 9 wherein said tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-amylamine, tri-n-hexylamine, tri-(2-ethyl-n-hexyl)amine, tri-n-heptylamine, dimethyl butylamine, methyl hexyl propylamine, N-methyl-N-ethylaniline, N,N'"'"'-dimethyl-p-methoxyaniline, N-methylmorpholine, N-ethylmorpholine, N,N'"'"'-dimethylanisidine, 2-chloropyridine, 4-chloropyridine, quinuclidine, quinoline, and N,N'"'"'-dimethylpiperazine, and combinations thereof.

11. The method according to claim 9 wherein said tertiary amine is triethylamine.

12. The method according to claim 4 wherein said polynucleophilic monomer is a polyamine comprising two or more amine groups selected from the group consisting of primary and secondary amines.

13. The method according to claim 12 wherein said polyamine is selected from the group consisting of amine-terminated polyethers, amine-terminated butadiene-acrylonitrile copolymers, amine-terminated poly(dimethylsiloxanes), and oligomeric alkyleneamines.

14. The method according to claim 4 wherein said polynucleophilic monomer is selected from the group consisting of polythiols and nonphenolic polyols.

15. The method according to claim 1 wherein said isomaleimide has a weight average molecular weight of greater than about 400.

16. The method according to claim 1 wherein said polyisomaleimide has a weight average molecular weight in the range of 300 to 50,000.

17. An isomaleimide comprising the formula ##STR19## wherein R'"'"' represents an organic group derived from a polymeric primary amine by replacement of both hydrogen atoms from the amino group for the isomaleimide group formed, and R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic.

18. A polyisomaleimide comprising the formula ##STR20## wherein R represents a polyvalent organic group derived from a polymeric primary polyamine by replacement of both hydrogen atoms from each amino group for each isomaleimide group formed,

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic, and

n represents the degree of isomaleimide functionality, and is an integer of at least 2.

19. A polymaleamide comprising structural units of the formula ##STR21## wherein A is any polyvalent polymeric organic group and can include 0 to 100 heteroatoms that interrupt carbon chains, which group optionally can contain substituent groups, provided that A and its substituent groups do not interfere with formation of isomaleimides, polyisomaleimides, or polymers of the invention,

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic.

and n is an integer of at least 2 representing the degree of functionality of A.

20. The polymaleamide according to claim 19 wherein said structural units comprise the formula:

##STR22## wherein --HN--A--NH-- is a polyvalent polymeric group derived from a primary polyamine by removal of at least one hydrogen atom from each primary amine group,

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic, and

A is any polyvalent polymeric organic group and can include 0 to 100 heteroatoms that interrupt carbon chains, which group optionally can contain substituent groups, provided that A and its substituent groups do not interfere with formation of isomaleimides, polyisomaleimides, or polymers of the invention.

21. A polymer comprising the formula ##STR23## wherein Y is independently --HN--, --O--, or --S--, W is any polyvalent organic group that can include 0 to 100 heteroatoms that interrupt carbon chains, and optionally substituent groups, so long as W and its substituent groups do not interfere with formation of polyisomaleimides, polymaleamides, and polymers of the invention,

T is any polyvalent polymeric organic group and can include 0 to 100 heteroatoms that interrupt carbon chains, which group optionally can contain substituent groups, provided that T and its substituent groups do not interfere with formation of polymers of the invention,

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic, and

s and m independently are integers representing the degree of functionality of W and T, respectively.

22. The polymer according to claim 21 comprising repeating units of the formula:

##STR24## wherein W, Y, T, R¹, and R² are as previously defined, and each Y is independently selected.

23. A prepolymer comprising any of the formulae V, VI, and VIII:

##STR25## where E'"'"' is H and E'"'"' is --Y--T--(Y--H)_m-1 ;

or E'"'"' is ##STR26## E" is ##STR27## and wherein

p is an integer of 2 or more and represents the degree of polymerization of the repeating unit,

T is any polyvalent polymeric organic group and can include 0 to 100 heteroatoms that interrupt carbon chains, which group optionally can contain substituent groups, provided that T and its substituent groups do not interfere with formation of polymers of the invention,

Y is independently --HN--, --O--, or --S--,

A is any polyvalent polymeric organic group and can include 0 to 100 heteroatoms that interrupt carbon chains, which group optionally can contain substituent groups, provided that A and its substituent groups do not interfere with formation of isomaleimides, polyisomaleimides, or polymers of the invention,

R¹ and R² are the same or different and are independently selected from the group consisting of hydrogen, C₁ to C₂₀ linear, branched or cyclic aliphatic groups, C₆ to C₂₀ aromatic groups, fluorine, chlorine, bromine, and iodine, or R¹ and R² can be joined together to form a cyclic ring that is aromatic or alicyclic, m is an integer representing the degree of functionality of T,

and n represents the degree of isomaleimide functionality, and is an integer of at least 2,

and each A and Y is independently selected.