Effect of Cu(II) on the kinetics of the homogeneous atom transfer radical polymerization of methyl methacrylate

H. Zhang, B. Klumperman, W. Ming, Hanns Fischer, R. Linde, van der

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Abstract

The kinetics of CuBr-mediated homogeneous atom transfer radical polymn. (ATRP) of Me methacrylate (MMA) using 2-hydroxyethyl-2-bromoisobutyrate (HEBIB) as initiator and N-(n-hexyl)pyridylmethanimine (NHPMI) as ligand was investigated. The exptl. results showed that initially added Cu(II) can have strong effects on the kinetics of the ATRP depending on the [Cu(II)]0/[Cu(I)]0 ratio. When ?10% Cu(II) relative to Cu(I) was added at the beginning of the polymn., the kinetics can be well described by Fischer's equation (ln([M]0/[M]) ~ t2/3). The obtained reaction orders for initiator, Cu(I) and Cu(II), are quite close to or the same as those in Fischer's equation, verifying the applicability of Fischer's equation in ATRP systems. On the other hand, when [Cu(II)]0/[Cu(I)]0 >= 0.1, the kinetics can be well interpreted by Matyjaszewski's equation (ln([M]0/[M]) ~ t). The polymn. rate shows almost first order with respect to the concns. of initiator and Cu(I) and inverse first order with respect to the concn. of Cu(II), suggesting that the \"self-regulation\" and radical termination becomes unimportant for the ATRP process when enough Cu(II) is added at the beginning of the reaction. This result is of great potential importance for better control of ATRP systems. Besides, the equil. const. Keq and termination const. kt of the ATRP system at 90 DegC were detd. to be 7.2 * 10-8 and 8.9 * 107 M-1 s-1, resp. [on SciFinder (R)]
Original languageEnglish
Pages (from-to)6169-6173
JournalMacromolecules
Volume34
Issue number18
DOIs
Publication statusPublished - 2001

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Methacrylates
Atom transfer radical polymerization
Kinetics
Ligands
Atoms

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Zhang, H. ; Klumperman, B. ; Ming, W. ; Fischer, Hanns ; Linde, van der, R. / Effect of Cu(II) on the kinetics of the homogeneous atom transfer radical polymerization of methyl methacrylate. In: Macromolecules. 2001 ; Vol. 34, No. 18. pp. 6169-6173.
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title = "Effect of Cu(II) on the kinetics of the homogeneous atom transfer radical polymerization of methyl methacrylate",
abstract = "The kinetics of CuBr-mediated homogeneous atom transfer radical polymn. (ATRP) of Me methacrylate (MMA) using 2-hydroxyethyl-2-bromoisobutyrate (HEBIB) as initiator and N-(n-hexyl)pyridylmethanimine (NHPMI) as ligand was investigated. The exptl. results showed that initially added Cu(II) can have strong effects on the kinetics of the ATRP depending on the [Cu(II)]0/[Cu(I)]0 ratio. When ?10{\%} Cu(II) relative to Cu(I) was added at the beginning of the polymn., the kinetics can be well described by Fischer's equation (ln([M]0/[M]) ~ t2/3). The obtained reaction orders for initiator, Cu(I) and Cu(II), are quite close to or the same as those in Fischer's equation, verifying the applicability of Fischer's equation in ATRP systems. On the other hand, when [Cu(II)]0/[Cu(I)]0 >= 0.1, the kinetics can be well interpreted by Matyjaszewski's equation (ln([M]0/[M]) ~ t). The polymn. rate shows almost first order with respect to the concns. of initiator and Cu(I) and inverse first order with respect to the concn. of Cu(II), suggesting that the \{"}self-regulation\{"} and radical termination becomes unimportant for the ATRP process when enough Cu(II) is added at the beginning of the reaction. This result is of great potential importance for better control of ATRP systems. Besides, the equil. const. Keq and termination const. kt of the ATRP system at 90 DegC were detd. to be 7.2 * 10-8 and 8.9 * 107 M-1 s-1, resp. [on SciFinder (R)]",
author = "H. Zhang and B. Klumperman and W. Ming and Hanns Fischer and {Linde, van der}, R.",
year = "2001",
doi = "10.1021/ma0104736",
language = "English",
volume = "34",
pages = "6169--6173",
journal = "Macromolecules",
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Zhang, H, Klumperman, B, Ming, W, Fischer, H & Linde, van der, R 2001, 'Effect of Cu(II) on the kinetics of the homogeneous atom transfer radical polymerization of methyl methacrylate', Macromolecules, vol. 34, no. 18, pp. 6169-6173. https://doi.org/10.1021/ma0104736

Effect of Cu(II) on the kinetics of the homogeneous atom transfer radical polymerization of methyl methacrylate. / Zhang, H.; Klumperman, B.; Ming, W.; Fischer, Hanns; Linde, van der, R.

In: Macromolecules, Vol. 34, No. 18, 2001, p. 6169-6173.

Research output: Contribution to journalArticleAcademicpeer-review

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T1 - Effect of Cu(II) on the kinetics of the homogeneous atom transfer radical polymerization of methyl methacrylate

AU - Zhang, H.

AU - Klumperman, B.

AU - Ming, W.

AU - Fischer, Hanns

AU - Linde, van der, R.

PY - 2001

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N2 - The kinetics of CuBr-mediated homogeneous atom transfer radical polymn. (ATRP) of Me methacrylate (MMA) using 2-hydroxyethyl-2-bromoisobutyrate (HEBIB) as initiator and N-(n-hexyl)pyridylmethanimine (NHPMI) as ligand was investigated. The exptl. results showed that initially added Cu(II) can have strong effects on the kinetics of the ATRP depending on the [Cu(II)]0/[Cu(I)]0 ratio. When ?10% Cu(II) relative to Cu(I) was added at the beginning of the polymn., the kinetics can be well described by Fischer's equation (ln([M]0/[M]) ~ t2/3). The obtained reaction orders for initiator, Cu(I) and Cu(II), are quite close to or the same as those in Fischer's equation, verifying the applicability of Fischer's equation in ATRP systems. On the other hand, when [Cu(II)]0/[Cu(I)]0 >= 0.1, the kinetics can be well interpreted by Matyjaszewski's equation (ln([M]0/[M]) ~ t). The polymn. rate shows almost first order with respect to the concns. of initiator and Cu(I) and inverse first order with respect to the concn. of Cu(II), suggesting that the \"self-regulation\" and radical termination becomes unimportant for the ATRP process when enough Cu(II) is added at the beginning of the reaction. This result is of great potential importance for better control of ATRP systems. Besides, the equil. const. Keq and termination const. kt of the ATRP system at 90 DegC were detd. to be 7.2 * 10-8 and 8.9 * 107 M-1 s-1, resp. [on SciFinder (R)]

AB - The kinetics of CuBr-mediated homogeneous atom transfer radical polymn. (ATRP) of Me methacrylate (MMA) using 2-hydroxyethyl-2-bromoisobutyrate (HEBIB) as initiator and N-(n-hexyl)pyridylmethanimine (NHPMI) as ligand was investigated. The exptl. results showed that initially added Cu(II) can have strong effects on the kinetics of the ATRP depending on the [Cu(II)]0/[Cu(I)]0 ratio. When ?10% Cu(II) relative to Cu(I) was added at the beginning of the polymn., the kinetics can be well described by Fischer's equation (ln([M]0/[M]) ~ t2/3). The obtained reaction orders for initiator, Cu(I) and Cu(II), are quite close to or the same as those in Fischer's equation, verifying the applicability of Fischer's equation in ATRP systems. On the other hand, when [Cu(II)]0/[Cu(I)]0 >= 0.1, the kinetics can be well interpreted by Matyjaszewski's equation (ln([M]0/[M]) ~ t). The polymn. rate shows almost first order with respect to the concns. of initiator and Cu(I) and inverse first order with respect to the concn. of Cu(II), suggesting that the \"self-regulation\" and radical termination becomes unimportant for the ATRP process when enough Cu(II) is added at the beginning of the reaction. This result is of great potential importance for better control of ATRP systems. Besides, the equil. const. Keq and termination const. kt of the ATRP system at 90 DegC were detd. to be 7.2 * 10-8 and 8.9 * 107 M-1 s-1, resp. [on SciFinder (R)]

U2 - 10.1021/ma0104736

DO - 10.1021/ma0104736

M3 - Article

VL - 34

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JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

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