Polymer compositions and methods

Abstract

The present invention encompasses polyurethane compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses polyurethane foams, thermoplastics and elastomers derived from aliphatic polycarbonate polyols and polyisocyanates wherein the polyol chains contain a primary repeating unit having a structure:In another aspect, the invention provides articles comprising the inventive foam and elastomer compositions as well as methods of making such compositions.

1 - 105 . (canceled) 
     
     
         106 . A reaction mixture comprising:
 aliphatic polycarbonate polyols derived from copolymerization of carbon dioxide and one or more epoxides, wherein the aliphatic polycarbonate polyols comprise end groups selected from the group consisting of hydroxyl groups and isocyanate groups; and   one or more additional polyols selected from the group consisting of polyether polyols, polyester polyols, and mixtures of thereof.   
     
     
         107 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols comprise end groups selected from isocyanate groups. 
     
     
         108 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols comprise a primary repeating unit having a structure: 
       
         
           
           
               
               
           
         
         where R 1 , R 2 , R 3 , and R 4  are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40  aliphatic group, an optionally substituted C 1-20  heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4  may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms. 
       
     
     
         109 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols comprise poly(ethylene carbonate) derived from copolymerization of ethylene oxide and carbon dioxide. 
     
     
         110 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols comprise poly(propylene carbonate) derived from copolymerization of propylene oxide and carbon dioxide. 
     
     
         111 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols have a number average molecular weight (M n ) between about 500 g/mol and about 10,000 g/mol. 
     
     
         112 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols are characterized in having a polydispersity index (PDI) of less than 2.0. 
     
     
         113 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols have a head-to-tail ratio greater than about 80%. 
     
     
         114 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols are characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater. 
     
     
         115 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols are characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater. 
     
     
         116 . The reaction mixture according to  claim 106 , wherein the reaction mixture is suitable for preparing a polyurethane elastomer composition. 
     
     
         117 . The reaction mixture according to  claim 116 , wherein the aliphatic polycarbonate polyols are characterized in having a Tg of less than about 20° C. 
     
     
         118 . The reaction mixture according to  claim 116 , wherein the aliphatic polycarbonate polyols are characterized in having a viscosity of below 6,000 cps at 20° C. 
     
     
         119 . The reaction mixture according to  claim 116 , wherein the aliphatic polycarbonate polyols have a functionality between 1.9 and 3.0. 
     
     
         120 . The reaction mixture according to  claim 106 , wherein the reaction mixture is suitable for preparing a polyurethane thermoplastic composition. 
     
     
         121 . The reaction mixture according to  claim 120 , wherein the aliphatic polycarbonate polyols are characterized in having a Tg greater than about −30° C. 
     
     
         122 . The reaction mixture according to  claim 120 , wherein the thermoplastic composition is a thermoplastic elastomer composition, wherein the aliphatic polycarbonate polyols are characterized in having a viscosity of below 6,000 cps at 20° C. 
     
     
         123 . The reaction mixture according to  claim 120 , wherein the aliphatic polycarbonate polyols have a functionality between 1.9 and 2.1. 
     
     
         124 . The reaction mixture according to  claim 106 , wherein the one or more additional polyols comprise a polyol selected from the group consisting of materials available commercially under the trade names: Voranol® (Dow), SpecFlex® (Dow), Tercarol® (Dow), Caradol® (Shell), Hyperliter®, Acclaim® (Bayer Material Science), Ultracel® (Bayer Material Science), Desmophen® (Bayer Material Science), and Arcol® (Bayer Material Science). 
     
     
         125 . A polyurethane composition derived from the reaction mixture according to  claim 106 . 
     
     
         126 . A polyurethane elastomer composition derived from the reaction mixture according to  claim 116 . 
     
     
         127 . A polyurethane thermoplastic composition derived from the reaction mixture according to  claim 120 . 
     
     
         128 . A process for preparing a polyurethane composition comprising the steps of:
 providing the reaction mixture according to  claim 106 ; and   allowing the reaction mixture to cure.   
     
     
         129 . The reaction mixture according to  claim 106 , wherein the aliphatic polycarbonate polyols have a structure P1: 
       
         
           
           
               
               
           
         
         wherein, R 1 , R 2 , R 3 , and R 4  are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-30  aliphatic group, and an optionally substituted C 1-20  heteroaliphatic group, and an optionally substituted C 6-10  aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4  may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; 
         Y is, at each occurrence, independently —H or the site of attachment to any of the chain-extending moieties; 
         n is at each occurrence, independently an integer from about 3 to about 1,000; 
            is a multivalent moiety; and 
         x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6. 
       
     
     
         130 . The reaction mixture according to  claim 129 , wherein   is derived from a dihydric alcohol. 
     
     
         131 . The reaction mixture according to  claim 130 ,
 wherein the dihydric alcohol is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propane diol, 1,5-hexanediol, 1,6-hexanediol, 1, 8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these;   wherein the dihydric alcohol is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol) having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) having number average molecular weights of from 234 to about 2000 g/mol; or   wherein the dihydric alcohol is a polymeric diol selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyethercopolyesters, polyether polycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylated analogs of any of these.   
     
     
         132 . The reaction mixture according to  claim 129 , where   is derived from a polymeric diol or triol, and the polymeric diol or triol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polyoxymethylene polymers, polycarbonate-copolyesters, and alkoxylated analogs of any of these. 
     
     
         133 . The reaction mixture according to  claim 106 , wherein the one or more additional polyols comprise a polyether polyol. 
     
     
         134 . The reaction mixture according to  claim 106 , wherein the one or more additional polyols comprise a polyester polyol.