Adhesive compositions and methods

Abstract

The present invention encompasses polyurethane adhesive compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses polyurethane adhesives 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 polyurethane compositions as well as methods of making such compositions.

1 - 97 . (canceled) 
     
     
         98 . An isocyanate-terminated prepolymer comprising segments derived from one or more aliphatic polycarbonate polyols derived from the copolymerization of carbon dioxide and one or more epoxides and having a primary repeating unit with 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. 
       
     
     
         99 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol is characterized in that at least 99%, at least 99.5%, at least 99.7%, or at least 99.8% of the end groups are —OH groups. 
     
     
         100 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and ethylene oxide. 
     
     
         101 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and propylene oxide. 
     
     
         102 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol comprises a terpolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins. 
     
     
         103 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol comprises a terpolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins. 
     
     
         104 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) in the range of about 500 g/mol to about 10,000 g/mol, or between about 500 g/mol and about 5,000 g/mol, or between about 500 g/mol and about 4,000 g/mol, or between about 500 g/mol and about 3,000 g/mol, or between about 500 g/mol and about 2,500 g/mol, or between about 500 g/mol and about 1,500 g/mol. 
     
     
         105 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the polyol, the percentage of carbonate linkages is 95% or greater or is 99% or greater. 
     
     
         106 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the polyol, the percentage of carbonate linkages is 99% or greater. 
     
     
         107 . The isocyanate-terminated prepolymer of  claim 98 , having the following structure: 
       
         
           
           
               
               
           
         
         wherein black rectangles   represent the carbon skeleton of the diisocyanate reacted with the aliphatic polycarbonate polyol to produce the isocyanate-terminated prepolymer; 
         Q is 0 or an integer between 1 and about 50; 
         n is at each occurrence, independently an integer from about 3 to about 1,000; and 
       
       
         
           
           
               
               
           
         
       
       is a multivalent moiety. 
     
     
         108 . The isocyanate-terminated prepolymer of  claim 107 , wherein 
       
         
           
           
               
               
           
         
       
       is derived from a polyfunctional chain transfer agent having a formula: 
       
         
           
           
               
               
           
         
       
     
     
         109 . The isocyanate-terminated prepolymer of  claim 108 , wherein 
       
         
           
           
               
               
           
         
       
       is derived from a dihydric alcohol. 
     
     
         110 . The isocyanate-terminated prepolymer of  claim 108 , wherein y is 0 and x is greater than 2. 
     
     
         111 . The isocyanate-terminated prepolymer of  claim 98 , further comprising one or more additional polyols selected from the group consisting of polyether polyols, polyester polyols, and mixtures of these. 
     
     
         112 . The isocyanate-terminated prepolymer of  claim 98 , wherein the aliphatic polycarbonate polyol is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         wherein, t is an integer from 1 to 12 inclusive, and R t  is independently at each occurrence —H, or —CH 3 . 
       
     
     
         113 . The isocyanate-terminated prepolymer of  claim 98 , comprising urethane linkages derived from aliphatic polyisocyanates. 
     
     
         114 . The isocyanate-terminated prepolymer of  claim 113  wherein the aliphatic isocyanate is selected from the group consisting of: 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), and 4,4′-diisocyanato dicyclohexylmethane, (H 12 MDI or hydrogenated MDI). 
     
     
         115 . The isocyanate-terminated prepolymer of  claim 98 , comprising urethane linkages derived from aromatic polyisocyanates. 
     
     
         116 . The isocyanate-terminated prepolymer of  claim 115  wherein the aromatic diisocyanate is selected from the group consisting of: toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI). 
     
     
         117 . An isocyanate-terminated prepolymer having the formula: 
       
         
           
           
               
               
           
         
         where 
       
       
         
           
           
               
               
           
         
       
       is derived from a dihydric alcohol; and
 n is an integer from 2 to about 50. 
 
     
     
         118 . The isocyanate-terminated prepolymer of  claim 117  wherein the dihydric alcohol from which 
       
         
           
           
               
               
           
         
       
       is derived 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. 
     
     
         119 . The isocyanate-terminated prepolymer of  claim 117  wherein the dihydric alcohol from which 
       
         
           
           
               
               
           
         
       
       is derived is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycol) such as those having number average molecular weights of from 234 to about 2000 g/mol. 
     
     
         120 . An isocyanate-terminated prepolymer having the formula: 
       
         
           
           
               
               
           
         
         where 
       
       
         
           
           
               
               
           
         
       
       is derived from a dihydric alcohol; and
 n is an integer from 2 to about 50. 
 
     
     
         121 . (canceled) 
     
     
         122 . (canceled)