Polymer with upper critical solution temperature

Abstract

Aspects generally relate to a temperature responsive polymer, more specifically to a polymer exhibiting an upper critical solution temperature (UCST) in an aqueous solution. In one aspect, a monomer compound includes one or more amide or thioamide groups; one or more ureido or thioureido groups; and one or more ethylenically unsaturated groups. In one aspect, a polymer, such as a homopolymer or a copolymer, is produced by polymerization of the monomer compound. The copolymer is produced by polymerization of the monomer compound and a comonomer, such as a hydrophobic comonomer, a hydrophilic comonomer, a pH responsive comonomer, a light responsive comonomer, and combinations thereof. The polymer exhibits a UCST from about 1° C. to about 100° C. in an aqueous solution at 1 atm.

What is claimed is: 
     
         1 . A compound, comprising:
 one or more amide or thioamide groups;   one or more ureido or thioureido groups; and   one or more ethylenically unsaturated groups.   
     
     
         2 . The compound of  claim 1 , represented by formula (I): 
       
         
           
           
               
               
           
         
         wherein:
 Q 1 , Q 2 , Q 3 , and Q 4  are each independently oxygen or sulfur; 
 R 1  and R 2  are independently an alkylene or haloalkylene; and 
 R 3 , R 4 , R 5 , and R 6  are independently hydrogen, an alkyl, or a haloalkyl. 
 
       
     
     
         3 . The compound of  claim 2 , wherein Q 1 , Q 2 , Q 3 , and Q 4  are each oxygen and wherein R 3 , R 4 , R 5 , and R 6  are each hydrogen. 
     
     
         4 . The compound of  claim 3 , wherein:
 R 1  is —C 2 H 4 —; and   R 2  is —CH 2 —.   
     
     
         5 . A method of making the compound of  claim 1 , comprising purifying the compound without chromatography. 
     
     
         6 . A polymer, comprising:
 a plurality of repeating units (n) of monomer units, each monomer unit independently comprising one or more amide or thioamide groups and one or more ureido or thioureido groups, wherein n is an integer from 10 to 200;   an optional plurality of repeating units (m) of comonomer units, wherein m is an integer from 0 to 100 and wherein n>m; and   at least part of a reversible addition fragmentation chain transfer (RAFT) agent;   wherein the polymer is configured to exhibit an upper critical solution temperature from about 1° C. to about 100° C. when present in an aqueous solution at 1 atm.   
     
     
         7 . The polymer of  claim 6 , wherein the monomer units are represented by formula (II): 
       
         
           
           
               
               
           
         
         wherein:
 Q 1 , Q 2 , Q 3 , and Q 4  are each independently oxygen or sulfur 
 R 1  is alkyl or haloalkyl; 
 R 2  and R 3  are independently an alkylene or haloalkylene; and 
 R 4 , R 5 , R 6 , and R 7  are each independently hydrogen, an alkyl, or a haloalkyl. 
 
       
     
     
         8 . The polymer of  claim 7 , wherein Q 1 , Q 2 , Q 3 , and Q 4  are each oxygen and wherein R 4 , R 5 , R 6 , and R 7  are each hydrogen. 
     
     
         9 . The polymer of  claim 6 , wherein the upper critical solution temperature is in the aqueous solution having a sodium ion concentration from above zero to about 160 mM. 
     
     
         10 . The polymer of  claim 6 , wherein the polymer has a number average molecular weight (Mn) as determined by triple detection from about 7,000 Da to about 40,000 Da. 
     
     
         11 . The polymer of  claim 6 , wherein the polymer has a polydispersity as determined by triple detection from about 1.0 to about 1.3. 
     
     
         12 . The polymer of  claim 6 , wherein the polymer is configured to exhibit the upper critical solution temperature from about 5° C. to about 60° C. when present in the aqueous solution. 
     
     
         13 . A copolymer, comprising:
 a plurality of repeating units (n) of monomer units, each monomer unit independently comprising one or more amide or thioamide groups and one or more ureido or thioureido groups, wherein n is an integer from 10 to 200;   a plurality of repeating units (m) of comonomer units, each comonomer unit selected from a group consisting of a hydrophobic comonomer, hydrophilic comonomer, pH responsive comonomer, light responsive comonomer, and combinations thereof, wherein m is an integer from 1 to 100 and wherein n>m; and   at least part of a reversible addition fragmentation chain transfer (RAFT) agent;   wherein the copolymer is configured to exhibit an upper critical solution temperature from about 1° C. to about 100° C. in an aqueous solution at 1 atm.   
     
     
         14 . The copolymer of  claim 13 , wherein the monomer units are represented by formula (II): 
       
         
           
           
               
               
           
         
         wherein:
 Q 1 , Q 2 , Q 3 , and Q 4  are each independently oxygen or sulfur 
 R 1  is alkyl or haloalkyl; 
 R 2  and R 3  are independently an alkylene or haloalkylene; and 
 R 4 , R 5 , R 6 , and R 7  are each independently hydrogen, an alkyl, or a haloalkyl. 
 
       
     
     
         15 . The copolymer of  claim 13 , wherein the comonomer units are hydrophobic comonomer units. 
     
     
         16 . The copolymer of  claim 15 , wherein the hydrophobic comonomer units reduce the upper critical solution temperature. 
     
     
         17 . The copolymer of  claim 15 , wherein the comonomer units are represented by formula (III): 
       
         
           
           
               
               
           
         
         wherein:
 Q 1  and Q 2  are each independently oxygen or sulfur; and 
 R 1  and R 2  are each independently an alkyl or haloalkyl. 
 
       
     
     
         18 . The copolymer of  claim 17 , wherein Q 1  and Q 2  are each oxygen. 
     
     
         19 . The copolymer of  claim 13 , wherein the upper critical solution temperature is in the aqueous solution having a sodium ion concentration from above zero mM to about 160 mM. 
     
     
         20 . The copolymer of  claim 13 , wherein the copolymer is configured to exhibit the upper critical solution temperature from about 5° C. to about 60° C. when present in the aqueous solution.