Synthesis and characterization of cyclohexene oxide functional poly(ε‐caprolactone) macromonomers and their use in photoinitiated cationic homo‐ and copolymerization

Abstract

A novel well‐defined macromonomer of cyclohexene oxide (CHO) functional poly(ε‐caprolactone) (PCL) has been synthesized. For this purpose 3‐cyclohexene‐1‐methanol was used as the “initiator” for the stannous‐2‐ethylhexanoate [Sn(Oct)2] catalyzed living ring‐opening polymerization of ε‐caprolactone (CL). Epoxidation of the obtained polymer by using 3‐chloroperoxybenzoic acid results in CHO end‐functional macromonomer of PCL. The GPC and H NMR studies revealed that PCL with low polydispersity and desired end functionality was obtained. The photoinduced cationic homo‐ and copolymerization of this macromonomer with CHO gave poly(macromonomer) and graft copolymers with PCL side chains, respectively. Photoinduced cationic polymerizations were achieved by using diphenyliodonium hexafluorophosphate in the presence and absence of a radical source such as 2,2‐dimethoxy‐2‐phenylacetophenone or sensitizer such as anthracene.

Copolymerization of cyclohexene-3-yl methyl methacrylate with styrene: synthesis, characterization, monomer reactivity ratios, and thermal properties

“…They obtained macromonomers with cyclohexene oxide functionality with potential for applications in photoinitiated cationic polymerization. [7][8][9] The most important feature of methacrylate type monomers is their optical clarity. Due to their high light transmittance, and good mechanical and thermal resistance, they have a fairly wide area of usage.…”

Synthesis, characterization, and hydrolytic degradation of graft copolymers of polystyrene and aliphatic polyesters

“…This methodology affords possibility to incorporate functional groups into polyesters provided that in addition to the hydroxyl groups, the initiator contains desired functionality. Previously, we have prepared thermal- [21][22][23][24][25][26][27], photo- [28,29], and electro-functional [30] polymers of biocompatible polymers by taking advantage of the functional initiator approach [31].…”

Well‐Defined Cyclohexene Oxide Mid‐Chain Functional Polystyrene Macromonomer: Synthesis, Characterization and Photoinitiated Cationic Homo‐ and Copolymerization

“…[1] In most cases, the polymerizable groups are vinyl type, [2][3][4][5][6] which can participate in radical or ionic polymerizations, heterocycles active [7][8][9][10] in ring-opening polymerizations and other functional groups [11][12][13] that can participate in polycondensation reactions. There are two general methods proposed for the preparation of macromonomers: (a) polymerization from a monomer-based initiator [14,15] or chain transfer agent [16] and (b) terminal functional group transformation of polymer chains, [17,18] such as end-capping of living polymers, [19,20] to introduce monomer functionalities.…”

“…Such macromonomers are important precursors for supermolecular construction and have been used broadly in the synthesis of branched macromolecular architectures and a variety of polymeric materials. [1,8,[21][22][23] During the last decade, controlled/living radical polymerization (CRP) techniques, such as atom transfer radical polymerization (ATRP), nitroxide-mediated radical polymerization (NMP), and reversible addition-fragmentation chain transfer (RAFT) polymerization, have been shown to be efficient techniques for the preparation of various types of functional polymeric materials. [24][25][26] CRP provides the capability to design polymers with controlled molecular weight and molecular weight distribution, in addition to controlled chemical composition, chain-sequence distribution, site-specific functionality and pre-determinable topology.…”