Poly((polythioalkyl)esters), their applications and derivatives

Abstract

Compounds and polymers of such compounds are prepared based on the reaction product of a polysulfide containing diol and a dibasic acid, conveniently using an acid catalyst for the reaction. By appropriate choice of mole ratios, the resulting compound may have a hydroxyl and carboxyl, two hydroxyls or two carboxyls as terminal groups. The compounds can be modified by adding augmenting groups to change the terminal groups or properties of the monomer. The polymers find advantageous use as adhesives, sealants, coatings, paints, elastomers, plastic formulations, fibers, films and molded objects.

1 . A condensation copolymer characterized by having a unit formed from a polysulfide diol and an organic dibasic carboxylic acid or its anhydride, wherein the hydroxyl groups are separated from said polysulfide by at least 2 carbon atoms, having a total of at least about 5 carbon atoms, said polysulfide having from 2 to 8 sulfur atoms.  
     
     
         2 . An addition polymer characterized by having a unit formed from a polysulfide diol and an organic dibasic carboxylic acid or its anhydride, wherein the hydroxyl groups are separated from said polysulfide by at least 2 carbon atoms, having a total of at least about 5 carbon atoms, said polysulfide having from 2 to 8 sulfur atoms  
     
     
         3 . A polymer comprising as a monomer a composition of the formulae:  
         MF m ORS n R 1 OM 1 ; or   (a)  MZAORS n R 1 F 1   m OAZ 1 M 1 ;   (b)  
       wherein 
 O and S have their normal meaning of oxygen and sulfur;  
 n is at least 2 and not more than about 8;  
 F is of the formula —ORS n R 1 OA-;  
 F 1  is of the formula —OAORS n R 1 —;  
 m is at least 1;  
 Z and Z 1  are the same or different and are oxy or amino;  
 M and M 1  are the same or different and are hydrogen or an organic substituent;  
 R and R 1  are the same or different and are organic divalent radicals, each having from 2 to 20 carbon atoms;  
 A is the residue of a dicarboxylic acid of from 2 to 40 carbon atoms;  
 said organic substituent for M is defined as WR 2 — and for M 1  as —R 3 W 1 ;  
 R 2  and R 3  are the same or different and are an organic divalent radical having from 2 to 12 carbon atoms; and  
 W and W 1  are the same or different, and are amino and substituted amino of from about 1 to 6 carbon atoms, hydroxyl, carboxyl, isothiocyanate, isocyanate, oxo-carbonyl, non-oxo-carbonyl, siloxane, silane, cyclocarbonate, active olefin, or active halogen.  
 
     
     
         4 . A compound according to  claim 3 , wherein said polymer is a polyurethane.  
     
     
         5 . A compound according to  claim 3 , wherein said polymer is a polyether.  
     
     
         6 . A compound according to  claim 3 , wherein said polymer is a polyester.  
     
     
         7 . A compound according to  claim 3 , wherein A is a dicarboxylic acid residue of from 2 to 8 carbon atoms and n is 2 to 4.  
     
     
         8 . A copolymer comprising as a monomer a composition of the formulae:  
         MF m ORS n R 1 OM 1 ; or   (a)  MZAORS n R 1 F 1   m OAZ 1 M 1 ;   (b)  
       wherein 
 O and S have their normal meaning of oxygen and sulfur;  
 n is at least 2 and not more than about 8;  
 F is of the formula —ORS n R 1 OA-;  
 F 1  is of the formula —OAORS n R 1 —;  
 m is at least 1;  
 Z and Z 1  are the same or different and are oxy or amino;  
 M and M 1  are the same or different and are hydrogen or an organic substituent;  
 R and R 1  are the same or different and are organic divalent radicals, each having from 2 to 20 carbon atoms;  
 A is the residue of a dicarboxylic acid of from 2 to 40 carbon atoms;  
 said organic substituent for M is defined as WR 2 — and for M 1  as —R 3 W 1 ;  
 R 2  and R 3  are the same or different and are an organic divalent radical having from 2 to 12 carbon atoms; and  
 W and W 1  are the same or different, and are amino and substituted amino of from about 1 to 6 carbon atoms, hydroxyl, carboxyl, isothiocyanate, isocyanate, oxo-carbonyl, non-oxo-carbonyl, siloxane, silane, cyclocarbonate, active olefin, or active halogen.  
 
     
     
         9 . A compound according to  claim 8 , wherein said copolymer is a polyurethane.  
     
     
         10 . A compound according to  claim 8 , wherein said copolymer is a polyether.  
     
     
         11 . A compound according to  claim 8 , wherein said copolymer is a polyester.  
     
     
         12 . A compound according to  claim 8 , wherein said copolymer is an addition polymer.  
     
     
         13 . A compound according to  claim 12 , wherein at least one of W and W 1  is hydroxyl.  
     
     
         14 . A compound according to  claim 12 , wherein at least one of W and W 1  is carboxyl.  
     
     
         15 . A compound according to  claim 12 , wherein at least one of W and W 1  is an amine.  
     
     
         16 . A copolymer according to  claim 8 , wherein A is a dicarboxylic acid residue of from 2 to 8 carbon atoms and n is 2 to 4.