New initiator systems for radical polymerization of vinyl monomers

Otsu, Takayuki; Yamaguchi, Masami K.; Takemura, Yasuhiro; Kusuki, Yoshihiro; Aoki, Shuzo

doi:10.1002/pol.1967.110050816

Cited by 28 publications

(16 citation statements)

References 13 publications

(3 reference statements)

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“…Inspired by this issue, we noted the recently reported LRP catalyzed by a combination of copper(II) and zero‐valent metals including zinc wire, magnesium ribbon, and iron wire 23–25. Originally, the systematic studies on the reactions between some pure metals and organic halides were carried out by Ostu's and Bamford's groups early in the 1960s 26–28. Ostu and Matyjaszewski respectively attempted to realize “living” radical polymerization using the different combinations of metals with organic halides 29, 30.…”

Section: Introductionmentioning

confidence: 99%

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

Yu¹,

Liu²,

Di³

et al. 2013

J. Polym. Sci. A Polym. Chem.

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Zn(0)/ppm concentrations of CuBr2 from 10 to 50 ppm was firstly used to catalyze radical polymerization of acrylonitrile at ambient temperature. The polymerization displayed typical living radical polymerization (LRP) characteristics, as evidenced by pseudo first‐order kinetics of polymerization, linear increase of number‐average molecular weight, and low polydispersity index (PDI) value. Effects of solvent, copper concentration, and initiator concentration on the polymerization reaction and molecular weight as well as PDI were investigated in detail. EC excelled NMP, DMF, and DMSO in terms of rate of polymerization as well as control of molecular weight and PDI. The increase of the copper concentration from 2.5 to 50 ppm leads to a higher rate of polymerization and a better control over the polymerization reaction. 1H NMR and GPC analyses as well as chain extension reaction confirmed the very high chain‐end functionality of the resultant polymer. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

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Section: Introductionmentioning

confidence: 99%

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

Yu¹,

Liu²,

Di³

et al. 2013

J. Polym. Sci. A Polym. Chem.

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“…Previously, Otsu et al [30] reported that a similar system, Fe Table 3. As regards results, the GASP of MMA with the simple system, Fe(0)/MBPA, proceeded smoothly to produce highmolecular-weight PMMAs with wide-ranging PDI values (runs 3-1 to 3-4).…”

Section: Gasp With a Simple Initiating System Fe(0)/initiatormentioning

confidence: 99%

Gas‐Phase Assisted Surface Polymerization of Vinyl Monomers with Fe‐Based Initiating Systems

Andou

Yasutake

Jeong

et al. 2005

Macro Chemistry & Physics

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Summary: Gas‐phase assisted surface polymerization (GASP) of methyl methacrylate (MMA) and styrene (St) was investigated with Fe‐based radical initiating systems, FeCl2/2,2′‐bipyridine (Bpy)/methyl α‐bromophenylacetate (MBPA), etc. GASP with these initiating systems proceeded to produce corresponding polymers on substrate surfaces. The resulting PMMA had very high PDI values, suggesting an uncontrolled reaction. In an attempt to control the GASP, polymerization with a simple initiating system, Fe(0)/MBPA, was examined on Fe(0)‐metal surfaces, resulting in significant polymerization activity to produce high‐molecular‐weight PMMA. The results of time‐course tests on GASP of MMA and St suggested that a change had taken place to produce physically controlled propagation sites on the Fe(0) powder surfaces.

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“…9 The reaction of the reduced nickel with carbon tetrachloride giving a nickel ion according to eq 1 must be faster than that with tert-butyl chloride and with benzyl chloride on the basis of their dissociation energies of C-Cl bonds. 1 It was considered that nickel chloride produced in situ has an initiating effect in the cationic polymerization, though a commercial anhydrous nickel chloride did not show any activity.…”

Section: Polymerization Of Ibve With Nijr-xmentioning

confidence: 99%

Metal-Containing Initiator Systems. XXX. Selective Initiation of Polymerization with Reduced Nickel/Organic Halides:Cationic Polymerization of Styrene and Isobutyl Vinyl Ether

Aoki

Shirafuji

Otsu

1971

Polym J

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ABSTRACT:It was found that the binary system composed of reduced nickel and alky 1 halides, such as tert-buty 1 chloride and carbon tetrachloride, initiates both radical and cationic polymerizations of vinyl monomers. From the effects of inhibitors the polymerization of styrene with this initiator was confirmed to proceed through both radical and cationic intermediates. Nickel halides produced by the reaction of the reduced nickel with the alkyl halides are proposed as the active species for the cationic initiation. Nickel sesquioxide reacted with tert-butyl chloride giving nickel chloride which was active for the initiation of the cationic polymerization of styrene and isobutyl vinyl ether. The binary system composed of nickel carbonyl and carbon tetrachloride, which is known as a radical initiator, also showed cationic activity in the polymerization of isobutyl vinyl ether. The activity of the reduced nickel as a catalyst in the FriedelCrafts reaction was also investigated. The condensation of benzyl chloride, giving polybenzyl, resulted from heating with the reduced nickel.

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New initiator systems for radical polymerization of vinyl monomers

Cited by 28 publications

References 13 publications

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

Gas‐Phase Assisted Surface Polymerization of Vinyl Monomers with Fe‐Based Initiating Systems

Metal-Containing Initiator Systems. XXX. Selective Initiation of Polymerization with Reduced Nickel/Organic Halides:Cationic Polymerization of Styrene and Isobutyl Vinyl Ether

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