Germanium- and Tin-Catalyzed Living Radical Polymerizations of Styrene

Goto, Atsushi; Zushi, H.; Kwak, Yungwan; Fukuda, Takeshi

doi:10.1021/bk-2006-0944.ch040

Cited by 21 publications

(19 citation statements)

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“…The large k act values obtained in all cases explain why low-polydispersity polymers were obtained from an early stage of polymerization with these catalysts. [4][5][6]8] Also noticeably, k act significantly differed among the catalysts (Figure 4). For the germanium catalysts GeI 4 and tolyl-GeI 3 , the substitution of a tolyl group decreased the catalyst activity by a factor of about 1/4.…”

Section: Determination Of K Act and Analysis Of R P For Polymerizatiomentioning

confidence: 90%

“…The k da values for them are also about 50-400 times larger than the k ex value (2.4 Â 10 3 M À1 Á s À1 ) [15] for St, meaning that the term C This explains why only a small amount of IA is required for these catalysts. [4][5][6]8] Figure 5 shows the temperature dependence of k da for GeI 4 , SnI 4 , PI 3 , and NIS at 60-100 8C. The difference in ln(k da ) was smaller at a higher temperature.…”

Section: Determination Of K Act and Analysis Of R P For Polymerizatiomentioning

confidence: 99%

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A Systematic Kinetic Study in Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) with Germanium, Tin, Phosphorus, and Nitrogen Catalysts

Goto¹,

Wakada²,

Fukuda³

et al. 2010

Macro Chemistry & Physics

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This paper reports a systematic kinetic study on the reversible activation processes and polymerization rates in the reversible chain transfer catalyzed living radical polymerizations (RTCPs) of styrene (St) and methyl methacrylate with germanium (Ge), tin (Sn), phosphorus (P), and nitrogen (N) catalysts. The pseudo‐first‐order activation rate constant kact significantly depended on monomers and the elements and substituents of the catalysts. For the St polymerization at 80 °C, kact increased in the order of PI3 (P catalyst) < p‐tolyl germanium triiodide (tolyl‐GeI3) (Ge catalyst) < N‐iodosuccinimide (NIS) (N catalyst) < SnI4 (Sn catalyst) < GeI4 (Ge catalyst) at the same catalyst concentration. The polymerization rate was somewhat retarded in the studied systems due to the cross‐termination between the propagating radical and the catalyst radical in situ formed in the polymerization.magnified image

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Section: Determination Of K Act and Analysis Of R P For Polymerizatiomentioning

confidence: 90%

Section: Determination Of K Act and Analysis Of R P For Polymerizatiomentioning

confidence: 99%

A Systematic Kinetic Study in Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) with Germanium, Tin, Phosphorus, and Nitrogen Catalysts

Goto¹,

Wakada²,

Fukuda³

et al. 2010

Macro Chemistry & Physics

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“…Some research groups also attempted to reach this goal by enhancing current available mechanisms [10][11][12]. Recently Goto et al [13] developed reversible chain transfer catalyzed polymerization (RTCP) as a new class of CRP. Similar to iodide mediated polymerization based on degenerative chain transfer, RTCP systems include monomer, an alkyl iodide and a conventional radical initiator.…”

Section: Introductionmentioning

confidence: 99%

“…Similar to iodide mediated polymerization based on degenerative chain transfer, RTCP systems include monomer, an alkyl iodide and a conventional radical initiator. However, in RTCP systems due to the low exchange frequency of degenerative chain transfer reactions, an iodide based catalyst (AI) such as tin (Sn) [1,13], germanium (Ge) [1,13,14], phosphorus (P) [1,14], nitrogen (N) [1,15], and oxygen (O) [16]-centered compounds is added. In the presence of AI catalyst (GeI 3 -I, etc.)…”

Section: Introductionmentioning

confidence: 99%

Simulation of reversible chain transfer catalyzed polymerization (RTCP): effect of different iodide based catalysts

et al. 2012

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“…We added a germanium (Ge) or tin (Sn) compound, e.g., GeI 4 , to the iodide-mediated polymerization. [6][7][8] GeI 4 works as a deactivator (XA) of Polymer , in situ producing GeI 3 (Scheme 1d). GeI 3 works as an activator (A ) of a polymeriodide (Polymer-I), producing Polymer and GeI 4 .…”

Section: Introductionmentioning

confidence: 99%

Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) of Styrene and Methyl Methacrylate with Phosphorus Catalysts

Goto

Hirai

Tsujii

et al. 2008

Macromolecular Symposia

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Phosphorus compounds were employed as catalysts in Reversible Chain Transfer Catalyzed Polymerization (RTCP), a novel class of living radical polymerization (LRP) which we had recently developed. Low-polydispersity polystyrene and poly(methyl methacrylate) with predicted molecular weights were obtained with a fairly high conversion in a fairly short time. These catalysts are particularly featured by their high reactivity hence small amounts being required, low toxicity, and low cost. Some phosphorus catalysts used in this work are among the least expensive catalysts/mediators of LRP developed so far.

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Germanium- and Tin-Catalyzed Living Radical Polymerizations of Styrene

Cited by 21 publications

References 0 publications

A Systematic Kinetic Study in Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) with Germanium, Tin, Phosphorus, and Nitrogen Catalysts

A Systematic Kinetic Study in Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) with Germanium, Tin, Phosphorus, and Nitrogen Catalysts

Simulation of reversible chain transfer catalyzed polymerization (RTCP): effect of different iodide based catalysts

Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) of Styrene and Methyl Methacrylate with Phosphorus Catalysts

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