Certain silicone polyethers, methods for making them and uses

Abstract

There are disclosed silicone polyether compositions, methods for making them and their uses. The compositions are based on polyethers initiated by non-isomerizing alkenyl or alkynyl alcohols.

That which is claimed is:  
     
         1 . A silicone based polyether comprising a monovalent group, R, with R having an average formula:  
       
         
           
           
               
               
           
         
       
       wherein, 
 Z is bonded to Si and —Z— is —CH2CH2— or —CH═CH—;  
 R1 and R2 are independently alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever —Z— is —CH2CH2—, or  
 R1 and R2 are independently H, halogen, NO2, NH2, an amine group, alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter mentioned groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever —Z— is —CH═CH—, and regardless of choice of —Z—,  
 R1 and R2 may be independently aldehyde, keto or ester functional;  
 R3 is a divalent hydrocarbon group which may be substituted by one or more of halogen, NO2, NH2 or an amine group, or R3 is a nullity;  
 R4 is —CH(R5)—CH2—, —CH2—CH(R5)— or a combination of these;  
 R5 is H, methyl, ethyl, phenyl or may vary among these within the same molecule in any proportion or order, with the proviso that when —Z— is —CH2CH2—, R1 and R2 are free of halogen and nitrogen, and all R5 groups are solely some combination of H and methyl, then —CH2CH2— groups must make up on average at least 60 percent by weight of the total R4 groups per molecule;  
 m=3 to 100 with the proviso that the range for m is expanded to 1 to 100 whenever —Z— is —CH2CH2— and the equivalent polydispersity of U is less than 1.4 or whenever U contains halogen, NO2, NH2, an amine group, or is aldehyde, keto or ester functional;  
 R6 is H, an alkyl group or  
                     
 and  
 R7 is an alkyl group.  
 
     
     
         2 . The silicone based polyether according to  claim 1 , wherein —Z— is —CH2CH2—.  
     
     
         3 . The silicone based polyether according to  claim 1 , wherein —Z— is —CH═CH—.  
     
     
         4 . The silicone based polyether according to  claim 1 , wherein at least one of R1, R2 and R3 is chlorine or bromine, or chlorine or bromine substituted.  
     
     
         5 . The silicone based polyether according to  claim 1 , wherein at least one of R1, R2 and R3 is NO2, NH2, or an amine group or substituted with NO2, NH2 or an amine group.  
     
     
         6 . The silicone based polyether according to  claim 1 , wherein R5 is all H.  
     
     
         7 . The silicone based polyether according to  claim 1 , wherein R5 is all ethyl or all phenyl or solely a combination of ethyl and phenyl.  
     
     
         8 . The silicone based polyether according to  claim 1 , wherein the weight average molecular weight of the silicone based polyether is less than 10,000 and the weight average equivalent weight of R is less than 700.  
     
     
         9 . The silicone based polyether according to  claim 1  that exists as a liquid at 25 deg C. and 760 mm Hg pressure.  
     
     
         10 . The silicone based polyether according to  claim 1 , wherein the equivalent polydispersity of R is less than 1.4.  
     
     
         11 . The silicone based polyether according to  claim 1 , wherein the equivalent polydispersity of R is 1.25 or less.  
     
     
         12 . A polymer of average formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 R, R1, R2 and R3 are independently alkyl groups having 30 carbons or less or phenyl;  
                     
 x is 0 to 500;  
 y is 1 to 100;  
 m is 3 to 100;  
 R5 is an alkyl group;  
 R6 is H, an alkyl group or C(O)R7;  
 R7 is an alkyl group;  
 R8 is H or an alkyl group;  
 R9 is CH(R10)CH2, CH2CH(R10) or a combination of these;  
 R10 is H, methyl, ethyl or phenyl; and  
 the equivalent polydispersity of R4 is less than 1.4.  
 
     
     
         13 . The polymer composition according to  claim 12 , wherein R10 is H.  
     
     
         14 . A polymer of average formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 R, R1 and R2 are independently alkyl groups having 30 carbons or less or phenyl;  
                     
 x is 0 to 500;  
 m is 3 to 100;  
 R4 is an alkyl group;  
 R5 is H, alkyl or C(O)R6;  
 R6 is an alkyl group;  
 R7 is H or an alkyl group;  
 R9 is CH(R10)CH2, CH2CH(R10) or a combination of these;  
 R10 is H, methyl, ethyl or phenyl; and  
 the equivalent polydispersity of R3 is less than 1.4.  
 
     
     
         15 . The polymer composition of  claim 14 , wherein R10 is H.  
     
     
         16 . A method for making a silicone based polyether, the method comprising: hydrosilating U with a silicone containing an SiH group, where  
       
         
           
           
               
               
           
         
         wherein,  
         Y— is CH2═CH— or CH≡C—;  
         R1 and R2 are independently alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever Y— is CH2═CH—, or  
         R1 and R2 are independently H, halogen, NO2, NH2, an amine group, alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter mentioned groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever Y— is CH≡C—, and regardless of choice of —Y—,  
         R1 and R2 may be independently aldehyde, keto or ester functional;  
         R3 is a divalent hydrocarbon group which may be substituted by one or more of halogen, NO2, NH2 or an amine group, or R3 is a nullity;  
         R4 is —CH(R5)—CH2—, —CH2—CH(R5)— or a combination of these;  
         R5 is H, methyl, ethyl, phenyl or may vary among these within the same molecule in any proportion or order, with the proviso that when Y— is CH2═CH—, R1 and R2 are free of halogen and nitrogen, and all R5 groups are solely some combination of H and methyl, then —CH2CH2— groups must make up on average at least 60 percent by weight of the total R4 groups per molecule;  
         m=3 to 100 with the proviso that the range for m is expanded to 1 to 100 whenever —Y— is —CH2CH2— and the equivalent polydispersity of U is less than 1.4 or whenever U contains halogen, NO2, NH2, an amine group, or is aldehyde, keto or ester functional;  
         R6 is H, an alkyl group or  
         
           
             
             
                 
                 
             
           
         
         and  
         R7 is an alkyl group.  
       
     
     
         17 . The method of  claim 16 , wherein Y— is CH2═CH—.  
     
     
         18 . The method of  claim 16 , wherein Y— is CH≡C—.  
     
     
         19 . The method of  claim 16 , wherein U contains chlorine, bromine, NO2, NH2 or an amine group.  
     
     
         20 . The method of  claim 16 , wherein the polydispersity of U is less than 1.4.  
     
     
         21 . The method of  claim 16 , wherein the polydispersity of U is less than 1.25.  
     
     
         22 . The method of  claim 16 , wherein at least a portion of U employed was produced using a DMC catalyst.  
     
     
         23 . A silicone based polyether produced by the method of  claim 22 .  
     
     
         24 . A method to reduce the surface tension of a system comprising: adding the silicone polyether of  claim 10  to the system or a component or components, to be used to produce the system.  
     
     
         25 . A treatment for hair, skin or underarms comprising the silicone polyether of  claim 10 .  
     
     
         26 . A polyurethane foam comprising the silicone polyether of  claim 10 .  
     
     
         27 . A surfactant or paint, ink or coating formulation comprising the silicone polyether of claim  10 .