Well-defined epoxide-containing styrenic polymers and their functionalization with alcohols

Abstract

Polymers containing electrophilic moieties, such as activated esters, epoxides, and alkyl halides, can be readily modified with a variety of nucleophiles to produce useful functional materials. The modification of epoxide-containing polymers with amines and other strong nucleophiles is welldocumented, but there are no reports on the modification of such polymers with alcohols. Using phenyloxirane and glycidyl butyrate as low molecular weight model compounds, it was determined that the acid-catalyzed ring-opening of arylsubstituted epoxides by alcohols to form b-hydroxy ether products was significantly more efficient than that of alkylsubstituted epoxides. An aryl epoxide-type styrenic monomer, 4-vinylphenyloxirane (4VPO), was synthesized in high yield using an improved procedure and then polymerized in a controlled manner under reversible addition-fragmentation chaintransfer (RAFT) polymerization conditions. A successful chain extension with styrene proved the high degree of chain-end functionalization of the poly4VPO-based macro chain transfer agent. Poly4VPO was modified with a library of alcohols and phenols, some of which contained reactive functionalities, e.g., azide, alkyne, allyl, etc., using either CBr 4 (in PhCN at 90 8C for 2-3 days) or BF 3 (in CH 2 Cl 2 at ambient temperature over 30 min) as the catalyst. The resulting b-hydroxy ether-functionalized homopolymers were characterized using size exclusion chromatography, 1 H NMR and IR spectroscopy, and thermal gravimetric analysis.

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 ).…”

Photoinitiated Seeded RAFT Dispersion Polymerization: A Facile Method for the Preparation of Epoxy‐Functionalized Triblock Copolymer Nano‐Objects

“…One significant advantage of this method is that the obtained triblock copolymer nano‐objects contain a large number of epoxy groups, a feature that is particularly beneficial for further functionalization or cross‐linking. It is well‐known that the epoxy group can react with thiols, amines, carboxylic acid groups, and hydroxy groups . As a proof of concept experiment, mPEG 45 ‐PGlyMA 70 ‐PMMA 100 worms and mPEG 45 ‐PGlyMA 200 ‐PMMA 200 vesicles were treated with ethylene diamine (EDA) at a molar ratio of epoxy/amine of 1/2 for 24 h at room temperature.…”

“…It is well-known that the epoxy group can react with thiols, amines, carboxylic acid groups, and hydroxy groups. [62][63][64][65] As a proof of concept experiment, mPEG 45 -PGlyMA 70 -PMMA 100 worms and mPEG 45 -PGlyMA 200 -PMMA 200 vesicles were treated with ethylene diamine (EDA) at a molar ratio of epoxy/amine of 1/2 for 24 h at room temperature. The samples were purified by several centrifugation-redispersion cycles to remove unreacted EDA.…”

Photoinitiated Polymerization‐Induced Self‐Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy‐Functionalized Block Copolymer Nano‐Objects

“…Glycidyl methacrylate (GMA) is a commodity monomer that has been widely used in the areas of coating, catalysis, biomedical analysis, biomolecular separation, gene delivery, etc . The epoxy moiety can be functionalized with alcohols, thiols, amines, or proteins . However, it is really surprising that using GMA as the core‐forming monomer of PISA has never been reported before.…”

“…[34][35][36][37][38][39] The epoxy moiety can be functionalized with alcohols, thiols, amines, or proteins. [40][41][42] However, it is really surprising that using GMA as the core-forming monomer of PISA has never been reported before. We assume this may be attributed to the high reaction temperature (typically 70 °C) for most PISA formulations, which restricts the efficient packing of PGMA chains, since the glass transition temperature (T g ) of PGMA (45 °C) is much lower than the reaction temperature.…”