Amphiphilic gradient copolymer of [poly(ethylene glycol) methyl ether] methacrylate and styrene via atom transfer radical polymerization

Abstract

Well-defined amphiphilic gradient copolymers of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and styrene were successfully synthesized using atom transfer radical polymerization. The relative reactivity ratio of PEGMA to styrene was determined using the Jaacks method. The initial feed ratio of the two monomers had a significant effect on the copolymer's gradient composition. The resultant copolymers were characterized by nuclear magnetic resonance and Fourier transform-infrared spectroscopy to confirm their structures and monomer compositions. The lower critical solution temperature behavior of the copolymers was investigated using ultraviolet-visual spectroscopy. The micellization behavior of the PEGMA and styrene copolymers in aqueous solution was observed by transmission electron microscopy and dynamic laser scattering.

Synthesis of Fluorinated Amphiphilic Block Copolymers Based on PEGMA, HEMA, and MMA via ATRP and CuAAC Click Chemistry

“…The appearance of signals at 2.3-2.5 ppm and 3.38 ppm was attributed to -CH 2 and CH 3 O-protons arising from PEGMA units [39][40][41]. The methyl protons for -OCH 3 in MMA units were at 3.55 ppm, while -CH 2 O protons in PEGMA units appeared at 3.65 ppm [24,32,34].…”

“…The methyl protons for -OCH 3 in MMA units were at 3.55 ppm, while -CH 2 O protons in PEGMA units appeared at 3.65 ppm [24,32,34]. Methylene protons of -CH 2 OH in HEMA and -CH 2 in PEGMA gave a sharp signal around 4.2 ppm [38][39][40][41]. Figure 6 shows the DSC curves of P(HEMA-co-MMA) copolymers (1b and 1d), recorded between 0-180 ∘ C. A substantial decrease in the glass transition temperature with increasing HEMA content was observed, which agreed with the literature [38] : the number average molecular weight; : the weight average molecular weight.…”

Asymmetric Copolymers: Synthesis, Properties, and Applications of Gradient and Other Partially Segregated Copolymers

“…Many techniques have been used for the preparation of asymmetric copolymers, including anionic and cationic polymerizations, C1 polymerization, catalyst transfer polycondensation, catalyzed copolymerization of olefins and epoxides, ring‐opening metathesis polymerization (ROMP) and various RDRP techniques (e.g., atom transfer radical polymerization (ATRP), nitroxide‐mediated polymerization (NMP), organometallic‐mediated radical polymerization (OMRP), and reversible addition–fragmentation chain transfer (RAFT)).…”

“…Similarly, a wide range of monomers have been used, including acrylates and methacrylates, acrylamides/methacrylamides, styrenics, olefins, vinyl esters, and epoxides . Both monomers must be compatible with the chosen polymerization technique and should ideally propagate rapidly and terminate relatively slowly in order to allow long chains to be prepared while maintaining acceptable levels of termination.…”

“…Spontaneous gradient copolymers have been obtained via catalyst transfer polycondensation, catalyzed copolymerization of olefins and epoxides, diverse RDRP methods (ATRP, NMP, OMRP, RAFT,) as well as cationic ring opening polymerization . Also, the gradient‐composition backbone can be used as macroinitiators to synthesize high‐molecular‐weight brushes .…”