Macrocyclic oligomers containing spiro(bis)indane moieties

Abstract

Macrocyclic oligomers, including polycarbonates, polyesters, polyamides, polyimides, polyetherketones and polyethersulfones, are conveniently prepared from various spiro(bis)indane compounds, especially the 6,6'-difunctional 3,3',3'-tetramethylspiro(bis)indanes. The macrocyclic oligomers may be conveniently converted to linear polymers.

What is claimed is: 
     
       1. A composition comprising random macrocyclic monomer and oligomer compounds corresponding to the formula ##STR20## wherein the Z 1  radicals are identical linking groups; A 1  is a spiro (bis)indane moiety of the formula ##STR21## about 60% of the R 1  groups are divalent aromatic organic radicals and the balance thereof are divalent aliphatic, alicyclic or aromatic organic radicals; each R 2  is independently C 1-4  primary or secondary alkyl or halo; a is from 1 to about 12, b is from 0 to 90% of total --A 1  --Z 1  --and --R 1  --Z 1  --moieties and n is 0-3. 
     
     
       2. A composition according to claim 1 wherein n is 0. 
     
     
       3. A composition according to claim 1 wherein the compounds contain at least one --R 1  --Z 1  --group. 
     
     
       4. A composition according to claim 3 wherein R 1  is ##STR22## 
     
     
       5. A composition according to claim 1 which comprises macrocyclic polyamides. 
     
     
       6. A compositon according to claim 5 which comprises structural units of the formula ##STR23## wherein: R 4  is a substituted or unsubstituted C 2-4  alkylene, m-phenylene or p-phenylene radical; R 5  is a substituted or unsubstituted alkylene radical or arylene radical other than o-arylene; and   p is 0 or 1.   
     
     
       7. A composition according to claim 6 wherein R 5  is m-phenylene and p is 0. 
     
     
       8. A composition according to claim 6 wherein R 4  is m- or p-phenylene; R 5  is A 1 , m-phenylene, ##STR24## and p is 1. .Iadd. 
     
     
       9.  A composition according to claim 5 which comprises structural units of the formula ##STR25##.Iaddend. wherein A 4  is a monocyclic or bicyclic m- or p-linked arylene radical or ##STR26## R 3  is a divalent aliphatic or m- or p-linked monocyclic aromatic or alicyclic radical, and R 6  is C 1-4  primary or secondary alkyl, phenyl or substituted phenyl.  .Iadd. 
     
     
       10.  A composition according to claim 9 wherein A 4  is m-phenylene, ##STR27##.Iaddend. has formula VIII wherein R 3  is trimethylene and R 6  is methyl.  .Iadd. 
     
     
       11.  A composition according to claim 5 wherein n is 0. .Iaddend. .Iadd.12. A composition according to claim 1 which comprises macrocyclic polyimides. .Iaddend. .Iadd.13. A composition according to claim 12 which comprises structural units of the formula ##STR28##.Iaddend. wherein: Z 2  is a single bond, a divalent aliphatic or alicyclic radical containing about 1-12 carbon atoms, --O--, --CO--, --S--, --SO 2  --, --O--Q--O--, --SO 2  --Q--SO 2  --, ##STR29## Q is a divalent aliphatic or aromatic radical;   R 4  is a substituted or unsubstituted C 2-4  alkylene, m-phenylene or p-phenylene radical;   R 6  is C 1-4  primary or secondary alkyl, phenyl or substituted phenyl; and   
     
     
       p is 0 or 1.  .Iadd.14.  A composition according to claim 13 wherein Z 2  is --S-- and p is 0. .Iaddend. .Iadd.15. A composition according to claim 13 wherein Z 2  is S, ##STR30## 
     
     
       .Iaddend. R 4  is p-phenylene and p is 1.  .Iadd.16.  A composition according to claim 12 which comprises structural units of the formula ##STR31##.Iaddend. wherein: Z 3  is R 3 , --R 4  --Z 4  --R 4  -- or ##STR32## Z 4  is ##STR33##   R 3  is a divalent aliphatic or m- or p-linked monocyclic aromatic or alicyclic radical;   R 4  is a substituted or unsubstituted C 2-4  alkylene, m-phenylene or p-phenylene radical; and   R 6  is C 1-4  primary or secondary alkyl, phenyl or substituted   
     
     
        phenyl.  .Iadd.17.  A composition according to claim 16 wherein Z 3  is m-or p-phenylene, ##STR34## 
     
     
       .Iaddend.  .Iadd.18.  A composition according to claim 16 wherein n is 0. .Iaddend. .Iadd.19. A composition according to claim 1 which comprises macrocyclic polyetherketones or polyethersulfones comprising structural units of the formula   (XI) --O--A.sup.1 --O--A.sup.5 --,     wherein A 5  is an aromatic radical containing at least one --CO-- or --SO 2  group. .Iaddend. .Iadd.20. A composition according to claim 19 wherein A 5  is ##STR35##   
     
     
       .Iaddend. .Iadd.21.  A composition according to claim 19 wherein n is 0. .Iaddend.