4-Vinylphenyl Glycidyl Ether: Synthesis, RAFT Polymerization, and Postpolymerization Modifications with Alcohols

Abstract

4-Vinylphenyl glycidyl ether (4VPGE), an epoxide-containing styrenic monomer, was synthesized and then polymerized in a controlled fashion under reversible addition–fragmentation chain-transfer (RAFT) polymerization conditions using butyl 1-phenylethyl trithiocarbonate as the chain-transfer agent. The high degree of chain-end functionalization of the produced polymers was confirmed by chain extension reactions with styrene that afforded well-defined block copolymers. Phenyl glycidyl ether was utilized as a model compound to identify the optimal reaction conditions for alcoholysis of the glycidyl moiety using BF3 as a Lewis acid catalyst, and postpolymerization modifications were subsequently carried out on the epoxide groups of poly4VPGE with a library of structurally diverse alcohols to yield a number of β-hydroxy ether-functionalized polymers.

Reversible Deactivation Radical Polymerization of Monomers Containing Activated Aziridine Groups

“…Epoxides are often utilized as synthetic intermediates in the production of aziridines. A renewed interest in epoxide‐containing styrenic monomers and their applications in macromolecular design has recently resulted in several new high‐yielding methods for their production . One such monomer, 4‐vinylphenyloxirane (4VPO), proved to be especially convenient as a starting material for the synthesis of styrenic monomers containing activated aziridines (Scheme ).…”

Thermoresponsive Poly(N,N-diethylacrylamide-co-glycidyl methacrylate) Copolymers and Its Catalytically Active α-Chymotrypsin Bioconjugate with Enhanced Enzyme Stability

“…Epoxide functional polymers can be obtained by postmodification of double bond containing side or end group(s) of polymers [ 15 , 16 , 17 , 18 , 19 , 20 , 21 ], but such macromolecules can also be synthesized by copolymerizations with epoxy group containing monomers. Undoubtedly, glycidyl methacrylate (GMA) is the most investigated and used monomer to obtain functional macromolecules with epoxy side groups, but other epoxide-containing monomers were also studied, such as 4-vinylphenyl glycidyl ether [ 22 ]. Previously, the copolymerization of GMA with numerous monomers, e.g., 3-methylthienyl methacrylate [ 23 ], trimethylolpropane trimethacrylate [ 24 ], sulfobetaine methacrylate [ 25 ], ethylene–methyl acrylate [ 26 ], styrene [ 27 , 28 ], 2-hydroxyethyl methacrylate [ 29 ], by various polymerization techniques, such as free radical polymerization, ATRP, NMP, RAFT, etc., was widely investigated.…”

A Computational Study of 2-(chloromethyl)oxirane Ring Opening by Bromide and Acetate Anions Considering Electrophilic Activation with Cations of Alkali Metals

“…[1][2][3] The ring opening of the substituted oxiranes leads to a parallel formation of normal (n-P) and abnormal (a-P) products (Scheme 1), which are versatile intermediates in organic synthesis due to three reaction centers at contiguous carbon atoms. [4][5][6][7][8] Only normal product transformations allow obtaining the glycidyl esters, which are important compounds for polymer industry. [4][5][6][8][9][10] According to the Krasusky rule, [11] the formation of the n-P esters is favored [12][13][14] and is in good agreement with nucleophilic attack through SN2 mechanism with some contribution of "borderline" SN2-like mechanism.…”

“…[4][5][6][7][8] Only normal product transformations allow obtaining the glycidyl esters, which are important compounds for polymer industry. [4][5][6][8][9][10] According to the Krasusky rule, [11] the formation of the n-P esters is favored [12][13][14] and is in good agreement with nucleophilic attack through SN2 mechanism with some contribution of "borderline" SN2-like mechanism. [15] Scheme 1 exhibits the possible directions of attack by a nucleophilic reagent on both carbon atoms of the oxirane ring of 2-(chloromethyl)oxirane (epichlorohydrin, R Scheme 1.…”

“…Nucleophile particles in the "nucleophile-oxirane" reaction systems are usually attached to electrophiles; e.g., reactants carrying both nucleophilic and electrophilic center, such as alcohols, phenols, carboxylic acids, quaternary ammonium or alkali metals halides and carboxylates, are used in the synthesis of glycidyl esters. [1,6,7,20] An investigation of special aspects of n-P ester formation includes consideration of the joint effect of electrophile and nucleophile. [21][22][23] The ring opening of oxiranes by nucleophilic reagents (SN2-like mechanism) may proceed without (A) and with (B) preliminary activation of oxirane ring by electrophile (without and with electrophilic activation) (Scheme 2), and the last one has an energetic benefit.…”