Synthesis and analysis of phase segregation of polystyrene‐block‐poly(methyl methacrylate) copolymer obtained by Steglich esterification from semitelechelic blocks of polystyrene and poly(methyl methacrylate)

Abstract

Here, an alternative route to successfully synthesize polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) is reported. Steglich esterification was used as an effective, metal free approach for coupling carboxylic terminated PS and the hydroxyl end‐functionalized PMMA chains obtained by nitroxide‐mediated polymerization and atom transfer radical polymerization, respectively. α‐Functionalization was obtained using 4,4′‐azobis(4‐cyanovaleric acid) and 2,2,2‐tribromoethanol as initiators. The synthesis of PS‐b‐PMMA was confirmed by gel permeation chromatography and nuclear magnetic resonance (NMR), while the dependence of the diffusion coefficients of the polymers (PS, PMMA, PS/PMMA blend, and PS‐b‐PMMA) with their corresponding molecular weights was discussed based on the results of atomic force microscopy‐based infrared spectroscopy, differential scanning calorimetry, and spectra of diffusion‐ordered NMR spectroscopy. Differently from PS‐b‐PMMA, a partial segregation was observed for the PS/PMMA blend, affecting its thermal behavior and diffusion coefficient. The study here presented provides an easier and efficient strategy for the synthesis of PS‐b‐PMMA and new insights into the diffusion of polymers.

Achieving Less Than 100 ppb Total Metal Ion Concentration in ESCAP Resins Synthesized by Atom Transfer Radical Polymerization

“…Lai et al [35] and Misir et al [36] separately synthesized PS-b-PMMa block copolymers for use as photoresist resin by ATRP, with PDI of 1.28-1.75 and 1.09-1.42, respectively. Boni et al [37] synthesized PS-b-PMMA block copolymer by ATRP and NMP, with a PDI of 1.10. However, the industrial application of photoresist resin synthesized via ATRP has not been achieved.…”

Non‐activated Esters as Reactive Handles in Direct Post‐Polymerization Modification

“…[37] Unfortunately, activated ester monomers have seen comparatively little application outside radical polymerization methods, and the implementation of the activated ester methodology on non-radically prepared polymers typically involves multiple steps, or is obsolete due to well-established Steglich esterification and amide coupling alternatives. [38][39][40][41][42][43][44][45] Due to these limitations and the rather high costs associated to activated ester monomers limiting commercial applications, several research groups have investigated the possibility to use non-activated esters directly as a substrate. In contrast to their activated counterparts, non-activated esters are relatively inert and well-tolerated by a wide range of polymerization mechanisms.…”

Effect of Molecular Weight on Phase Equilibrium in the Polystyrene–Poly(methyl methacrylate) System

“…Will they tend to form a homogeneous mixture or form separate phases and create stress on chemical bonds between blocks at the phase boundary? Copolymers of styrene and methyl methacrylate are widely used, and here it is important to understand not only the most optimal conditions for their synthesis, but also the relationship between the obtained structure and the required properties [ 17 , 18 ]. But, to understand this relationship, an accurate comprehension of the thermodynamics of mixing homopolymers of different molecular weights is necessary.…”