RAFT-polymerized poly(hexafluoroisopropyl methacrylate)s as precursors for functional water-soluble polymers

Abstract

Post-polymerization modification of well-defined precursor polymers is a versatile tool to obtain multifunctional water-soluble polymers that cannot be synthesized by common polymerization techniques. For the first time, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) based homo and block copolymers were synthesized via RAFT polymerization to provide precise precursors for the postpolymerization modification of the 1,1,1,3,3,3-hexafluoroisopropyl ester side chains with water-soluble amines (methoxy tri(ethylene glycol) amine, 2-hydroxypropyl amine and 3-(dimethylamino)-1propylamine). Sequential aminolysis using Oregon Green cadaverine first followed by 2-hydroxypropyl amine enables access to dye-labelled poly(2-hydroxypropyl methacrylamide) and aminolysis with 3-(dimethylamino)-1-propylamine provides homo and block co-catiomers that complex pDNA in PBS. To this respect, poly(1,1,1,3,3,3-hexafluoroisopropyl methacrylate)s P(HFIPMA)s as precursor polymers may become an alternative route for the synthesis of multifunctional water-soluble polymers for advanced applications.

New Perspectives of HPMA‐based Copolymers Derived by Post‐Polymerization Modification

“…Interestingly, this approach leads to amphiphilic HPMA statistical or block copolymers with unique properties that have not been accessible before (Figure ). More recently, we expanded the concept of reactive ester polymers and were able to introduce 1,1,1,3,3,3‐hexafluorophenyl methacrylate as novel precursor for RAFT polymerization and subsequent conversion into poly(HPMA) by aminolysis, too …”

“…More recently, we expanded the concept of reactive ester polymers and were able to introduce 1,1,1,3,3,3-hexafluorophenyl methacrylate as novel precursor for RAFT polymerization and subsequent conversion into poly-(HPMA) by aminolysis, too. [53]…”

Polyurethane/poly(ethylene‐co‐ethyl acrylate) and functional carbon black‐based hybrids: Physical properties and shape memory behavior

“…Incidentally, poly(ethylene ‐co‐ ethyl acrylate) is an important polymer for blending . Introduction of large pendant groups may decrease the backbone interaction and strength of polyacrylates . However, functional polyacrylate show fine miscibility with polyacetates or other polymers compared with the nonfunctional one.…”

Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials

“…[6][7][8] In light of this, post-modification of a reactive polymer precursor provides an attractive approach to overcoming this limitation, enabling synthesis of diversely functional materials, without subjecting them to detrimental polymerization conditions. [9][10][11][12][13] A variety of post-polymerization methods have previously been explored, [6][7][8][9] including copper-catalysed azide/alkyne click (CuAAC), [14][15][16] Diels-Alder cycloadditions [17][18][19][20] and active ester couplings. 10,[21][22][23] These methods enable the introduction of complex functional groups targeting applications ranging from drug delivery to organic electronics.…”

“…[9][10][11][12][13] A variety of post-polymerization methods have previously been explored, [6][7][8][9] including copper-catalysed azide/alkyne click (CuAAC), [14][15][16] Diels-Alder cycloadditions [17][18][19][20] and active ester couplings. 10,[21][22][23] These methods enable the introduction of complex functional groups targeting applications ranging from drug delivery to organic electronics. 19,24,25 In addition to these more established post-modification methods, is a simple yet relatively un-explored reaction -nucleophilic substitution of alkyl halides.…”