Stabilized levulinic ester ketals

Abstract

The invention describes methods of preparation and compositions of plasticizers. The plasticizers include at least 2 alkyl ketal ester moieties and have a molecular weight of greater than 300. In one aspect, the alkyl ketal ester moieties are levulinic ester ketals. Certain compositions contain at least one of an antioxidant, a UV stabilizer, a thermal stabilizer or mixtures thereof, present in the composition from about 0.01 to about 5.0 percent by weight of the total composition.

What is claimed is: 
     
         1 . A composition comprising a plasticizer comprising at least 2 alkyl ketal ester moieties and having a molecular weight of greater than 300; and
 at least one of an antioxidant, a UV stabilizer, a thermal stabilizer or mixtures thereof, present in the composition from about 0.01 to about 5.0 percent by weight of the total composition.   
     
     
         2 . The composition of  claim 1 , wherein the plasticizer comprises a formula of: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number; and 
         z is 0 or a positive number provided that z is at least one when R 5  is hydrogen. 
       
     
     
         3 . The composition of  claim 2 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         4 . The composition of  claim 3 , wherein each a=2 and each b=0. 
     
     
         5 . A plasticizer comprising at least 2 alkyl ketal ester moieties, the plasticizer having a molecular weight of greater than 300 comprising a formula of: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number; and 
         z is 0 or a positive number provided that z is at least one when R 5  is hydrogen, wherein the plasticizer has a color index (YI) of less than 50 measured by ASTM method E313 and has a purity of at least 90%. 
       
     
     
         6 . The plasticizer of  claim 5 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         7 . The plasticizer of  claim 6 , wherein each a=2 and each b=0. 
     
     
         8 . A plasticizer comprising at least 2 alkyl ketal ester moieties, the plasticizer having a molecular weight of greater than 300 comprising a formula of: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number; and 
         z is 0 or a positive number provided that z is at least one when R 5  is hydrogen, wherein the mass loss is less than 2% after 10 days at 110° C. and less than 15% RH. 
       
     
     
         9 . The plasticizer of  claim 8 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         10 . The plasticizer of  claim 9 , wherein each a=2 and each b=0. 
     
     
         11 . A process to prepare a plasticizer comprising at least 2 alkyl ketal ester moieties, the plasticizer having a molecular weight of greater than 300, comprising the step:
 contacting under reaction conditions an alkyl ketal ester having an acid number less than 0.3 as determined by ASTM method D664, a multihydric hydrocarbyl moiety, or a monohydric alkyl ketal ester; and   a catalyst, wherein a plasticizer comprising at least 2 alkyl ketal ester moieties is obtained with a molecular weight of greater than 300.   
     
     
         12 . The process of  claim 11 , wherein the plasticizer has a formula comprising: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number. 
       
     
     
         13 . The process of  claim 12 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         14 . The process of  claim 13 , wherein each a=2 and each b=0. 
     
     
         15 . A process to prepare a plasticizer in at least a 90% yield, wherein the plasticizer has a molecular weight of greater than 300 with at least 2 alkyl ketal ester moieties, comprising the step:
 contacting under reaction conditions, an alkyl ketal ester, a multihydric hydrocarbyl moiety, or a monohydric alkyl ketal ester;   a catalyst; and   an antioxidant, a thermal stabilizer or mixtures thereof, wherein a plasticizer comprising at least 2 alkyl ketal ester moieties is obtained with a molecular weight of greater than 300 and is produced in at least a 90% yield.   
     
     
         16 . The process of  claim 15 , wherein the plasticizer has a formula comprising: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number. 
       
     
     
         17 . The process of  claim 16 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         18 . The process of  claim 17 , wherein each a=2 and each b=0. 
     
     
         19 . A process to prepare a plasticizer, wherein the plasticizer has a molecular weight of greater than 300 with at least 2 alkyl ketal ester moieties, comprising the step:
 contacting under reaction conditions an alkyl ketal ester, a multihydric hydrocarbyl moiety, or a monohydric alkyl ketal ester;   a catalyst; and   an adsorbent, carbon, alumina, a buffer solution, a basic solution or mixtures thereof, wherein a plasticizer comprising at least 2 alkyl ketal ester moieties with a molecular weight of greater than 300 is obtained.   
     
     
         20 . The process of  claim 19 , wherein the plasticizer has a formula comprising: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number. 
       
     
     
         21 . The process of  claim 20 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         22 . The process of  claim 21 , wherein each a=2 and each b=0. 
     
     
         23 . A process to prepare a plasticizer, wherein the plasticizer comprises at least 2 alkyl ketal ester moieties with a molecular weight of greater than 300, comprising the step:
 contacting an alkyl ketal ester, a multihydric hydrocarbyl moiety, or a monohydric alkyl ketal ester;   a catalyst; and   optionally, an antioxidant under reaction conditions, wherein the reaction is conducted without the substantial presence of air, providing a plasticizer that has a color index (YI) of less than 50 measured by ASTM method E313 having at least 2 alkyl ketal ester moieties with a molecular weight of greater than 300.   
     
     
         24 . The process of  claim 23 , wherein the plasticizer has a formula comprising: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3  and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number. 
       
     
     
         25 . The process of  claim 24 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         26 . The process of  claim 25 , wherein each a=2 and each b=0. 
     
     
         27 . A process to prepare a plasticizer, wherein the plasticizer comprises at least 2 alkyl ketal ester moieties with a molecular weight of greater than 300, comprising the step:
 contacting the plasticizer with a molecular weight of greater than 300 and at least 2 alkyl ketal ester moieties with hydrogen under hydrogenation conditions, providing a purified plasticizer that has a color index (YI) of less than 50 measured by ASTM method E313 having at least 2 alkyl ketal ester moieties with a molecular weight of greater than 300.   
     
     
         28 . The process of  claim 27 , wherein the plasticizer has a formula comprising: 
       
         
           
           
               
               
           
         
         combinations thereof, wherein 
         each a, independently, is from 0 or an integer of 1 to 12; 
         each b, independently, is 0 or 1; 
         c is from 0 to 12; 
         d is 0 or 1; 
         each e, independently, is from 0 to 12; 
         each f, independently, is from 0 to 12; 
         each i is 0 or 1; 
         each j, independently, is 0 to 100; 
         each R 1 , independently, is a hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; 
         each R 2 , R 3 , and R 4  are independently methylene, alkylmethylene, or dialkylmethylene; 
         R 5  is a hydrogen or 
       
       
         
           
           
               
               
           
         
         R 6  is a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 7 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 8 , independently, is a hydrogen, a hydrocarbyl or a substituted hydrocarbyl group; 
         each R 10 , independently, is a hydrocarbyl or a substituted hydrocarbyl group; 
         R 11  is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group terminated with one or more heteroatoms to form a cyclic membered ring and which can include one or more of —O—, —NH—, —NR—, wherein R is a hydrocarbyl or a substituted hydrocarbyl; 
         R 12 , is a covalent bond, a hydrocarbyl group or a substituted hydrocarbyl group; 
         each R 14 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 15 , independently, is a hydrogen, a hydrocarbyl, or a substituted hydrocarbyl group; 
         each R 19 , independently, is a hydrocarbyl, a substituted hydrocarbyl, or a hydrocarbyl group substituted with up to 5 hydroxyl groups; 
         each R 23  is a hydrocarbyl group or substituted hydrocarbyl group having between 1 and 12 carbon atoms 
         each Z, independently, is —O—, —NH— or —NR— where R is a hydrocarbyl or a substituted hydrocarbyl group; 
         n is from 1 to 100; 
         s is at least one; 
         v is from 0 to 100; 
         w is from 1 to 100; 
         x is at least 1; 
         y is 0 or a positive number. 
       
     
     
         29 . The process of  claim 28 , wherein the plasticizer is the compound of formula (IV) wherein R 11  is a C4 alkyl. 
     
     
         30 . The process of  claim 29 , wherein each a=2 and each b=0.