Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

Isabelle Ydens; Philippe Degée; David M. Haddleton; Philippe Dubois

doi:10.1016/j.eurpolymj.2005.04.012

Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

Isabelle Ydens, Philippe Degée, David M. Haddleton, Philippe Dubois

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

Abstract

Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80°C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (r_MMA = 0.62 ± 0.04; r_HEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, M_n = 475 g mol^-1) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r _MMA = 0.75 ± 0.07; r_PEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr₂(PPh₃) ₂) were observed by ¹H NMR spectroscopy.

Original language	English
Pages (from-to)	2255-2263
Number of pages	9
Journal	European Polymer Journal
Volume	41
Issue number	10
DOIs	https://doi.org/10.1016/j.eurpolymj.2005.04.012
Publication status	Published - 1 Oct 2005
Externally published	Yes

Keywords

2-hydroxyethyl methacrylate
Controlled radical polymerization
Copolymers
Jaacks method
Nickel-mediated polymerization
Reactivity ratios

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10.1016/j.eurpolymj.2005.04.012

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title = "Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers",

abstract = "Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80°C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (rMMA = 0.62 ± 0.04; rHEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, Mn = 475 g mol-1) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r MMA = 0.75 ± 0.07; rPEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr2(PPh3) 2) were observed by 1H NMR spectroscopy.",

keywords = "2-hydroxyethyl methacrylate, Controlled radical polymerization, Copolymers, Jaacks method, Nickel-mediated polymerization, Reactivity ratios",

author = "Isabelle Ydens and Philippe Deg{\'e}e and Haddleton, {David M.} and Philippe Dubois",

year = "2005",

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doi = "10.1016/j.eurpolymj.2005.04.012",

language = "English",

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T1 - Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

AU - Ydens, Isabelle

AU - Degée, Philippe

AU - Haddleton, David M.

AU - Dubois, Philippe

PY - 2005/10/1

Y1 - 2005/10/1

N2 - Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80°C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (rMMA = 0.62 ± 0.04; rHEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, Mn = 475 g mol-1) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r MMA = 0.75 ± 0.07; rPEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr2(PPh3) 2) were observed by 1H NMR spectroscopy.

AB - Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80°C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (rMMA = 0.62 ± 0.04; rHEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, Mn = 475 g mol-1) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r MMA = 0.75 ± 0.07; rPEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr2(PPh3) 2) were observed by 1H NMR spectroscopy.

KW - 2-hydroxyethyl methacrylate

KW - Controlled radical polymerization

KW - Copolymers

KW - Jaacks method

KW - Nickel-mediated polymerization

KW - Reactivity ratios

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U2 - 10.1016/j.eurpolymj.2005.04.012

DO - 10.1016/j.eurpolymj.2005.04.012

M3 - Article

AN - SCOPUS:23444460989

SN - 0014-3057

VL - 41

SP - 2255

EP - 2263

JO - European Polymer Journal

JF - European Polymer Journal

IS - 10

ER -

Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

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