Copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane: Reversible cross-propagation

Simon Harrisson; Thomas P. Davis; Richard A. Evans; Ezio Rizzardo

doi:10.1021/ma0020584

Copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane: Reversible cross-propagation

Simon Harrisson, Thomas P. Davis, Richard A. Evans, Ezio Rizzardo

Research output: Contribution to journal › Article › Research › peer-review

34 Citations (Scopus)

Abstract

The copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane (MDTO) with a range of common comonomers has been investigated and found to be highly unusual. The resulting copolymers contained blocks of homo-poly(MDTO), even at low MDTO feed ratios. Changes in temperature and monomer concentration have a significant effect on the copolymer composition of methyl methacrylate-MDTO and styrene-MDTO mixtures and therefore on the apparent reactivity ratios. The magnitude of the concentration effect is independent of the solvent. A new copolymerization mechanism is proposed in which the addition of an MDTO radical to the comonomer is reversible while all other propagation reactions are effectively irreversible. To our knowledge, this is the first observation of such a mechanism. Parameters for MDTO-M₂ (M₂ = STY, MMA) according to this model are reported as (r_MDTO, r₂,k_-12/k₂₂) = (0.06, 7, 17; M₂ = STY) and (0.38, 3.2, 2.5; M₂ = MMA) at 60 °C.

Original language	English
Pages (from-to)	3869-3876
Number of pages	8
Journal	Macromolecules
Volume	34
Issue number	12
DOIs	https://doi.org/10.1021/ma0020584
Publication status	Published - 5 Jun 2001
Externally published	Yes

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title = "Copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane: Reversible cross-propagation",

abstract = "The copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane (MDTO) with a range of common comonomers has been investigated and found to be highly unusual. The resulting copolymers contained blocks of homo-poly(MDTO), even at low MDTO feed ratios. Changes in temperature and monomer concentration have a significant effect on the copolymer composition of methyl methacrylate-MDTO and styrene-MDTO mixtures and therefore on the apparent reactivity ratios. The magnitude of the concentration effect is independent of the solvent. A new copolymerization mechanism is proposed in which the addition of an MDTO radical to the comonomer is reversible while all other propagation reactions are effectively irreversible. To our knowledge, this is the first observation of such a mechanism. Parameters for MDTO-M2 (M2 = STY, MMA) according to this model are reported as (rMDTO, r2,k-12/k22) = (0.06, 7, 17; M2 = STY) and (0.38, 3.2, 2.5; M2 = MMA) at 60 °C.",

author = "Simon Harrisson and Davis, {Thomas P.} and Evans, {Richard A.} and Ezio Rizzardo",

year = "2001",

month = jun,

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doi = "10.1021/ma0020584",

language = "English",

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journal = "Macromolecules",

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T1 - Copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane

T2 - Reversible cross-propagation

AU - Harrisson, Simon

AU - Davis, Thomas P.

AU - Evans, Richard A.

AU - Rizzardo, Ezio

PY - 2001/6/5

Y1 - 2001/6/5

N2 - The copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane (MDTO) with a range of common comonomers has been investigated and found to be highly unusual. The resulting copolymers contained blocks of homo-poly(MDTO), even at low MDTO feed ratios. Changes in temperature and monomer concentration have a significant effect on the copolymer composition of methyl methacrylate-MDTO and styrene-MDTO mixtures and therefore on the apparent reactivity ratios. The magnitude of the concentration effect is independent of the solvent. A new copolymerization mechanism is proposed in which the addition of an MDTO radical to the comonomer is reversible while all other propagation reactions are effectively irreversible. To our knowledge, this is the first observation of such a mechanism. Parameters for MDTO-M2 (M2 = STY, MMA) according to this model are reported as (rMDTO, r2,k-12/k22) = (0.06, 7, 17; M2 = STY) and (0.38, 3.2, 2.5; M2 = MMA) at 60 °C.

AB - The copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane (MDTO) with a range of common comonomers has been investigated and found to be highly unusual. The resulting copolymers contained blocks of homo-poly(MDTO), even at low MDTO feed ratios. Changes in temperature and monomer concentration have a significant effect on the copolymer composition of methyl methacrylate-MDTO and styrene-MDTO mixtures and therefore on the apparent reactivity ratios. The magnitude of the concentration effect is independent of the solvent. A new copolymerization mechanism is proposed in which the addition of an MDTO radical to the comonomer is reversible while all other propagation reactions are effectively irreversible. To our knowledge, this is the first observation of such a mechanism. Parameters for MDTO-M2 (M2 = STY, MMA) according to this model are reported as (rMDTO, r2,k-12/k22) = (0.06, 7, 17; M2 = STY) and (0.38, 3.2, 2.5; M2 = MMA) at 60 °C.

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DO - 10.1021/ma0020584

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SN - 0024-9297

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JO - Macromolecules

JF - Macromolecules

IS - 12

ER -

Copolymerization behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane: Reversible cross-propagation

Abstract

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