Thermally stable biuret and isocyanurate based surface modifying macromolecules and uses thereof

Abstract

The invention relates to surface modifying macromolecules (SMMs) having high degradation temperatures and their use in the manufacture of articles made from base polymers which require high temperature processing. The surface modifier is admixed with the base polymer to impart alcohol and water repellency properties.

1 . A surface modifier of formula (I): 
       
         
           
           
               
               
           
         
         wherein 
         (i) A is a soft segment; 
         (ii) B is a hard segment comprising a urethane trimer or biuret trimer; and 
         (iii) each G is a surface active group;
 wherein n is an integer between 0 to 10. 
 
       
     
     
         2 . The surface modifier of  claim 1 , wherein
 said surface modifier has a thermal degradation temperature of between 200° C. and 450° C.; or   said soft segment has a number average molecular weight (Mn), of 500 to 3,500 Daltons; or   soft segment comprises hydrogenated polybutadiene (HLBH), poly (2,2 dimethyl-1-3-propylcarbonate) (PCN), polybutadiene (LBHP), polytetramethylene oxide (PTMO), diethyleneglycol-orthophthalicanhydride polyester (PDP), poly (hexamethyhlenecarbonate)diol, hydroxyl terminated polydimethylsiloxanes (PrO-PDMS-PrO) block copolymer, poly(tetramethyleneoxide)diol, hydrogenated-hydroxyl terminated polyisoprene, poly(ethyleneglycol)-block-poly(propyleneglycol))-block-poly(ethylene glycol), 1,12-dodecanediol, hydrogenated polyisoprene (HHTPI), poly(hexamethylene carbonate), poly(2-butyl-2-ethyl-1,3-propyl carbonate), or hydroxylterminated polydimethylsiloxanes block copolymer (C22); or   said hard segment is formed by reacting a triisocyanate with a diol comprising said soft segment, wherein said triisocyanate is selected from hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer; or   each surface active group has a molecular weight of between 100-1,500 Da; or   said surface active group comprises polydimethylsiloxanes hydrocarbons, polyfluoroalkyl, fluorinated polyethers, and combinations thereof; or   n is 0 or 1; or   said surface modifier has a theoretical molecular weight of less than 10,000 Daltons; or   said surface modifier comprises from 5 to 30% (w/w) of said hard segment, from 40 to 90% (w/w) of said soft segment, and from 25 to 55% (w/w) of said surface active group.   
     
     
         3 .- 9 . (canceled) 
     
     
         10 . The surface modifier of  claim 1 , wherein said surface active group is selected from the group consisting of radicals of the general formula CH m F (3-m) (CF 2 ) r CH 2 CH 2 — and CH m F (3-m) (CF 2 ) s (CH 2 CH 2 O) χ —, wherein
 m is 0, 1, 2, or 3; 
 χ is an integer between 1-10; 
 r is an integer between 2-20; and 
 s is an integer between 1-20. 
 
     
     
         11 . The surface modifier of  claim 10 , wherein
 m is 0 or 1; or   each surface active group is selected, independently, from (CF 3 )(CF 2 ) 5 CH 2 CH 2 O—, (CF 3 )(CF 2 ) 7 CH 2 CH 2 O—, (CF 3 )(CF 2 ) 5 CH 2 CH 2 O—, CHF 2 (CF 2 ) 3 CH 2 O—, and (CF 3 )(CF 2 ) 2 CH 2 O—.   
     
     
         12 .- 17 . (canceled) 
     
     
         18 . The surface modifier of any of  claim 1 , wherein said surface modifier is formed by a process that comprises the steps of
 a) combining a solution comprising a biuret or urethane trimer with a solution comprising the surface active group; and   b) combining the product of (a) with a solution comprising the soft segment; and wherein
 step (a) or step (b) is performed in the presence of a bismuth catalyst; or 
 both step (a) and step (b) are performed in the presence of a bismuth catalyst. 
   
     
     
         19 .- 20 . (canceled) 
     
     
         21 . An admixture comprising the surface modifier of  claim 1  admixed with a base polymer. 
     
     
         22 .- 24 . (canceled) 
     
     
         25 . An article formed from the admixture of  claim 21 . 
     
     
         26 .- 31 . (canceled) 
     
     
         32 . A method for making an article, said method comprising the steps of:
 (i) combining a base polymer with the surface modifier of  claim 1  to form a mixture; and   (ii) heating said mixture to at least 200° C.   
     
     
         33 . (canceled) 
     
     
         34 . A method for increasing the thermal degradation temperature of a surface modifier of formula (I): 
       
         
           
           
               
               
           
         
         wherein
 (i) A is a soft segment comprising two hydroxyl end groups that are each covalently bound to B; 
 (ii) B is a hard segment comprising a triisocyanate; and 
 (iii) each G is a surface active group; and 
 (iv) n is an integer between 0 to 10; 
 
         said method comprising the steps of: 
         (a) reacting a triisocyanate with a monohydroxylic surface active group; and 
         (b) reacting the product of (a) with a soft segment diol; 
         wherein step (a) or (b) is performed in the presence of a bismuth catalyst. 
       
     
     
         35 . The method of  claim 34 , wherein
 said diol soft segment comprises hydrogenated hydroxyl terminated polybutadiene (HLBH), poly(2,2 dimethyl-1-3-propylcarbonate)diol (PCN), hydroxyl terminated polybutadiene polyol (LBHP), polytetramethylene oxide (PTMO), diethyleneglycol-orthophthalicanhydride polyester polyol (PDP), hydrogenated hydroxyl terminated polyisoprene (HHTPI), poly(hexamethylene carbonate)diol, poly(2-butyl-2-ethyl-1,3-propyl carbonate) diol, or hydroxylterminated polydimethylsiloxanes block copolymer (C22); or   step (a) comprises reacting a monohydroxylic surface active group with HLBH or PCN; or   said triisocyanate comprises hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer; or   said monohydroxylic surface active group is selected from compounds of the general formula CH m F (3-m) (CF 2 ) r CH 2 CH 2 —OH and CH m F (3-m) (CF 2 ) s (CH 2 CH 2 O) χ —CH 2 CH 2 OH, wherein m is 0, 1, 2, or 3; χ is an integer between 0-10; r is an integer between 2-20; and s is an integer between 1-20.   
     
     
         36 .- 38 . (canceled) 
     
     
         39 . A surface modifier of formula (II): 
       
         
           
           
               
               
           
         
         wherein 
         (i) A is a soft segment; 
         (ii) B is a hard segment comprising a urethane trimer or biuret trimer; 
         (iii) B′ is a hard segment comprising a urethane; and 
         (iv) each G is a surface active group; 
         wherein n is an integer between 0 to 10 and said surface modifier has a thermal degradation temperature of between 220° C. and 450° C. 
       
     
     
         40 . The surface modifier of  claim 39 , wherein said surface modifier is formed by a process that comprises the steps of
 a) combining a solution comprising a biuret or urethane trimer with a solution comprising the surface active group; and   b) combining the product of (a) with a solution comprising the soft segment; wherein step (a) or step (b) is performed in the presence of a bismuth catalyst, or both step (a) and step (b) are performed in the presence of a bismuth catalyst.   
     
     
         41 .- 42 . (canceled) 
     
     
         43 . An admixture comprising a surface modifier of any of  claim 39  admixed with a base polymer. 
     
     
         44 .- 46 . (canceled) 
     
     
         47 . An article formed from the admixture of  claim 43 . 
     
     
         48 .- 53 . (canceled) 
     
     
         54 . A method for making an article, said method comprising the steps of:
 (i) combining a base polymer with the surface modifier of  claim 39  to form a mixture; and   (ii) heating said mixture to at least 200° C.   
     
     
         55 . The method of  claim 54  wherein step (ii) comprises heating said mixture to a temperature of between 220° C. and 345° C. 
     
     
         56 . A method of increasing repellency by annealing a surface modifier with a base polymer wherein the annealing temperature is between 50° C. and 75° C. and the annealing time is between 1-24 hours, wherein said surface modifier has a structure selected from 
       
         
           
           
               
               
           
         
       
       wherein
 (i) A is a soft segment; 
 (ii) B is a hard segment comprising a urethane trimer or biuret trimer; and 
 (iii) each G is a surface active group;
 wherein n is an integer between 0 to 10 and said surface modifier has a thermal degradation temperature of between 250° C. and 450° C.; or 
 
 
       
         
           
           
               
               
           
         
       
       wherein
 (i) A is a soft segment; 
 (ii) B is a hard segment comprising a urethane trimer or biuret trimer; 
 (iii) B′ is a hard segment comprising a urethane; and 
 (iv) each G is a surface active group; and
 wherein n is an integer between 0 to 10 and said surface modifier has a thermal degradation temperature of between 200° C. and 450° C. 
 
 
     
     
         57 .- 60 . (canceled)