Synthesis, structure, and property of well‐defined polymethylene‐based diblock copolymers by a combination of living polymerization of ylides and atom transfer radical polymerization

Abstract

A combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) was used successfully in the design and synthesis of well‐defined polymethylene‐b‐poly(methyl methacrylate) (PM‐b‐PMMA) and polymethylene‐b‐poly(n‐butyl acrylate) (PM‐b‐Pn‐BuA). Tripolymethylene borane were firstly synthesized by living polymerization of dimethylsulfoxonium methylides and then oxidated quantitatively through trimethylamine‐N‐oxide dihydrate to provide a series of low‐polydispersity hydroxyl‐terminated polymethylenes (PM‐OHs) with different molecular weight. Subsequently, such polymers were converted into polymethylene‐based macroinitiators (PM‐MIs, Mn(GPC) = 1900–10,400 g/mol; Mw/Mn = 1.12–1.23) in ∼100% conversion. ATRPs of methyl methacrylate and n‐butyl acrylate were successfully conducted using PM‐MI to produce well‐defined diblock copolymers of PM‐b‐PMMA and PM‐b‐Pn‐BuA, respectively. The GPC traces indicated the successful extension of PMMA and Pn‐BuA segment (Mn(GPC) of PM‐b‐PMMA = 3980–10,100 g/mol; Mw/Mn = 1.16–1.22; Mn of PM‐b‐Pn‐BuA = 7400–9200 g/mol; Mw/Mn = 1.14–1.18). Atomic force microscopy (AFM) was used to characterize the structures of the precipitated PM‐b‐PMMA micelles, which were formed in toluene. The blend of LDPE/PMMA was prepared with PM‐b‐PMMA as compatibilizer. The scanning electron microscopy (SEM) results showed that the compatibilization of the LDPE/PMMA was improved greatly by the incorporation of PM‐b‐PMMA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5671–5681, 2009

Well‐defined polyolefin/poly(ε‐caprolactone) diblock copolymers: New synthetic strategy and application

“…First, two PM‐OHs with different molecular weight and narrow molecular weight distribution were synthesized via living polymerization of ylides with a subsequent oxidation of tris‐organoborane using trimethylamine‐ N ‐oxide dihydrate as described by Shea et al26–30 and in our previous work 35–37…”

Polymethylene‐Based Copolymers by Polyhomologation or by Its Combination with Controlled/Living and Living Polymerizations

“…A series of narrow‐dispersed PM–Br macroinitiators (PDI < 1.19) with molecular weight from 2150 to 10 000 g mol −1 were synthesized by bromination of hydroxyl‐terminated PM as shown in Scheme . By using ATRP with CuBr/PMDETA as catalyst system, a series of PM‐ b ‐PMMA has been synthesized with molecular weights, ranging from 3980 to 10 100 g mol −1 and PDI less than 1.22, as well as PM‐ b ‐P n BA copolymers whose molecular weights ranged from 7400 to 10 230 g mol −1 and with PDI less than 1.18 (Scheme ) . The content of PM was found to be in the range of 49% to 72.6% in PM‐ b ‐PMMA and 48.9% to 82.4% in PM‐ b ‐P n BA.…”

Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry

“…The resulting star is subsequently oxidized/hydrolyzed to afford hydroxyl-end-capped linear PEs. [30][31][32][33] The hydroxylfunctionalized PE can be used directly as initiator for (ROP) [34][35] of cyclic ethers/esters or indirectly, after chemical modification, for (ATRP), [36][37][38][39] (RAFT) 40 and ring-opening metathesis polymerization (ROMP). [41][42][43] In this work, we report the synthesis of novel polyethylene-based graft terpolymers via the "grafting onto" strategy by combining NMP, polyhomologation and CuAAC "click" chemistry.…”