Polymerization processes for ionic monomers

Abstract

A controlled polymerization process is described in which the polymerization free radically (co)polymerizable ionic monomers is initiated in the presence of a system initially comprising a transition metal complex, and an initiator comprising a radically transferable azide group. The process may include an excess of one or more uncomplexed ligand and at least a portion of the nonionic monomers may be polar monomers. The ionic monomer may be anionic or cationic. A controlled polymerization process for the preparation of water soluble block copolymers including polymerizing radically (co)polymerizable monomers in the presence of a system initially comprising a water soluble macroinitiator, and a transition metal complex comprising one or more ligands is also disclosed.

We claim:  
     
         1 . A controlled polymerization process for (co)polymerization of radically polymerizable ionic monomers, comprising: 
 initiating the polymerization of free radically (co)polymerizable ionic monomers in the presence of a system initially comprising:    a transition metal complex, and    an initiator comprising a radically transferable azide group.    
     
     
         2 . The process of  claim 1 , wherein the system further comprises an excess of one or more uncomplexed ligand.  
     
     
         3 . The process of  claim 2 , wherein the uncomplexed ligand is at least one of a donating solvent and a ligand substitute.  
     
     
         4 . The process of  claim 1 , further comprising initiating the polymerization of nonionic monomers and wherein the mole ratio of ionic monomers to non-ionic monomers is greater than 0.1 mole %.  
     
     
         5 . The process of  claim 4 , wherein at least a portion of the nonionic monomers are polar monomers.  
     
     
         6 . The process of  claim 1 , wherein the initiator is a macroinitiator.  
     
     
         7 . The process of  claim 6 , wherein the macroinitiator is water soluble.  
     
     
         8 . The process of  claim 1 , wherein the ionic monomer is anionic.  
     
     
         9 . The process of  claim 1 , wherein the ionic monomer is cationic.  
     
     
         10 . The process of  claim 1 , wherein the system further comprises a solvent.  
     
     
         11 . The process of  claim 10 , wherein the solvent is water.  
     
     
         12 . The process of  claim 10 , wherein the solvent is a mixture of solvents comprising water.  
     
     
         13 . The process of  claim 12 , wherein the solvent is a mixture of water and at least one of pyridine and methanol.  
     
     
         14 . The process of  claim 10 , wherein at least a portion of the solvent forms a complex with at least a portion of the transition metal.  
     
     
         15 . The process of  claim 1 , wherein the initiator comprises a second functional group.  
     
     
         16 . The process of  claim 15 , wherein the second functional group is a primary azide.  
     
     
         17 . The process of  claim 15 , wherein the second functional group is an ionic functional group.  
     
     
         18 . A controlled polymerization process for the preparation of water soluble block copolymers comprising: 
 polymerizing radically (co)polymerizable monomers in the presence of a system initially comprising:    a water soluble macroinitiator, and    a transition metal complex comprising one or more ligands.    
     
     
         19 . The process of  claim 18 , wherein the water soluble macroinitiator is prepared by a controlled radical polymerization process.  
     
     
         20 . The process of  claim 18 , wherein the water soluble macroinitiator is prepared by a process comprising: 
 reacting a macromolecule with a pendent or terminal hydroxy group with a molecule comprising a free carboxylic acid using catalytic amounts of dicyclohexylcarbodiimide and a base as condensing agent.    
     
     
         21 . The process of  claim 18 , wherein water is present as a solvent.  
     
     
         22 . The process of  claim 18 , wherein the radically (co)polymerizable monomer comprises an ionic functionality.  
     
     
         23 . The process of  claim 18 , wherein the radically (co)polymerizable monomer comprises an ionic functionality.  
     
     
         24 . The process of  claim 18 , wherein the radically (co)polymerizable monomers comprise functionality that can be converted into ionic functionality.  
     
     
         25 . A polymer prepared by the process of  claim 18 .  
     
     
         26 . A HEMA-b-DMAEMA polymer prepared by the process of  claim 18 .  
     
     
         27 . A PEO-b-DMAEMA polymer prepared by the process of  claim 18 .  
     
     
         28 . A PEO-b-vinylbenzoate polymer prepared by the process of  claim 18 .  
     
     
         29 . A PEO-b-MAOETMAT polymer prepared by the process of  claim 18 .  
     
     
         30 . A PEO-b-TMAEMT polymer prepared by the process of  claim 18 .  
     
     
         31 . A block copolymer, consisting of water soluble polymeric blocks.