Solid acid clay mediated copolymerization of methyl acrylate and 1‐octene: 2D NMR substantiation of predominant alternating comonomer sequence

Abstract

Montmorillionite K10 powder presence during radically initiated copolymerization of methyl acrylate (M) and 1‐octene (O) gave copolymers with higher incorporation of alkene unit. Highly viscous and transparent copolymers showed alternation irrespective of the copolymer composition. Increasing the amount of K10 powder increased the total percentage conversion, as well as 1‐octene incorporation. The monomodal curves obtained in gel permeation chromatography (GPC) substantiated that true copolymers were formed. The alternation in the copolymers was authenticated through Heteronuclear Multiple Quantum Correlation (HMQC) experiments in conjugation with Total Correlated Spectroscopy (TOCSY). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2156–2162, 2009

Improved photo-induced cobalt-mediated radical polymerization in continuous flow photoreactors

“…Table 2 Copolymerization of VAc and 1-Oct using various comonomer ratios and initiated by R-Co(acac) 2 in a 19.5 µL flow microreactor and experimental and calculated comonomer fractions in poly(VAc-co- Also in line with the present observation, Gupta et al demonstrated by the use of 13 C-NMR analysis that methyl acrylate/ 1-Oct copolymers (high 1-Oct content) obtained from radical polymerization featured an almost entirely alternating acrylate/ 1-Oct copolymer sequence. 93,94 The use of a RAFT 95 or telluriummediated radical polymerization (TERP) 96 process to synthesize copolymers of 1-Oct with acrylate or methacrylate comonomers resulted likewise in low 1-Oct incorporation and low molar mass copolymers with a moderate dispersity. Importantly, by employing CMRP, copolymers containing up to 50 mol% of 1-Oct can be produced by adjusting the VAc/1-Oct monomer feed ratio (see Fig.…”

Achieving high molecular weight alternating copolymers of 1-octene with methyl acrylate via Lewis acid catalyzed copolymerization

“…Neither the chemical shi of MA-MA sequence at 35 ppm nor the chemical shi of octene-octene sequence at 43 ppm were observed, clearly demonstrate the formation of the sequence structure in this case. 44,51,56 We further analyzed the molecular weight and its distribution (PDI) of the resultant alternating copolymer by GPC, and the result was listed in Table 1. The M n of the resultant 1-octene-MA copolymer is 1.79 × 10 4 g mol −1 with a PDI of 1.79, which is far enough to satisfy the practical requirements as a high-performance polymer.…”

Visible-Light-Induced Living/Controlled Radical Copolymerization of 1-Octene and Acrylic Monomers Mediated by Organocobalt Complexes

“…On the other hand, copolymers with large molecular weight required low concentration of initiator and mediator, resulting in a large PDI. To increase MF­(olefin), the methods of adding Lewis acids, ,− such as scandium triflate, AlCl 3 , and Al 2 O 3 , as well as Brønsted acids, ,, such as pyridinium triflate, were developed in free radical copolymerization and living/controlled radical copolymerization. Yamago et al prepared the copolymers with high MF­(olefin) under a controlled manner in TERP using Brønsted acids and found the electron-withdrawing groups of (meth)­acrylates could also raise the MF­(olefin) of copolymers. , …”