Effect of Water and Oxygen on the Polymerization of Vinyl Acetate Initiated by Aluminum Alkyls, Bipyridyls, and Nitroxyl Radicals

White, Daniela; Matyjaszewski, Krzysztof

doi:10.1080/10601329708014949

Cited by 10 publications

(1 citation statement)

References 8 publications

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“…CRP of vinyl acetate was achieved using RAFT/MADIX with xanthates and dithiocarbamates − as polymerization mediators; however, in the presence of dithioesters, trithiocarbonates, and aromatic dithiocarbamates, the polymerization was strongly inhibited. Metal-mediated CRP of vinyl acetate was previously reported using an initiating system composed of Al( i Bu) 3 /2,2‘-bipyridine/TEMPO, but this system was very sensitive to moisture, oxygen, and impurities. − Poly(vinyl acetate) with the molecular weight predetermined by the ratio of the initial concentration of monomer to initiator, was prepared using CCl 4 as initiator, in the presence of Fe(OAc) 2 /PMDETA . The process was found to be a redox-initiated radical telomerization in which CCl 4 acted as both initiator and chain-transfer agent (INIFER), resulting in α-chloro and ω-CCl 3 functionalized polymers with M w / M n = 1.8−2.0.…”

Section: Introductionmentioning

confidence: 99%

Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides

2003

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Controlled/living radical polymerization of vinyl acetate was achieved by a degenerative transfer process using alkyl iodides as transfer agents. Poly(vinyl acetate) with predetermined molecular weight and relatively low polydispersity was successfully synthesized. Methyl 2-iodopropionate and ethyl iodoacetate were employed as transfer agents, whereas 2,2′-azobis(isobutyronitrile) and R-cumyl peroxyneodecanoate were used as initiators. Methyl 2-iodopropionate and ethyl iodoacetate are both efficient transfer agents, yielding polymers with good agreement between theoretical and observed molecular weights up to M n ) 20 000 and low polydispersities (Mw/Mn < 1.5). In contrast, ethyl iodide was inefficient as a transfer agent, although it retarded polymerization. The influence of temperature and the concentrations of transfer agent and initiator were studied. The structure of poly(vinyl acetate) end groups was investigated using 1 H NMR. The iodo-terminated chain ends were unstable and decomposed to aldehyde moieties and subsequently to colored, conjugated structures. The progressive conversion of secondary to primary alkyl iodides chain end groups was observed, which is indicative of head-to-head addition.

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Section: Introductionmentioning

confidence: 99%

Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides

2003

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Metal complexes in controlled radical polymerization

Qiu¹,

Matyjaszewski²

1997

Acta Polymerica

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Effect of Co and V complexes on polymerization of methyl methacrylate initiated by AlEt₂Br‐TEMPO catalyst

Ravikumar

Thevi

2009

J of Applied Polymer Sci

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2,2,6,6-Tetramethyl piperidinoxy (TEMPO) activated with diethyl aluminum bromide was employed as an initiator system for methyl methacrylate polymerization. Effect of addition of Co(acac) 3 and VO(acac) 2 complexes to the initiators system on methyl methacrylate polymerization were studied in benzene solvent. Various reaction parameters such as Al/TEMPO, monomer concentration, reaction temperature and time applied to the polymerization were investigated. The polymer yields, molecular weight and molecular weight distributions can be controlled with the addition of Co(acac) 3 to the initiator system. PMMA's of molecular weight distributions, as low as 1.10 was obtained under relatively mild conditions, in the temperature range 40-60 C in benzene solvent. However, Co and V complexes did not influence the micro structure of the PMMA's formed.

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Effect of Water and Oxygen on the Polymerization of Vinyl Acetate Initiated by Aluminum Alkyls, Bipyridyls, and Nitroxyl Radicals

Cited by 10 publications

References 8 publications

Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides

Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides

Metal complexes in controlled radical polymerization

Effect of Co and V complexes on polymerization of methyl methacrylate initiated by AlEt₂Br‐TEMPO catalyst

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Effect of Water and Oxygen on the Polymerization of Vinyl Acetate Initiated by Aluminum Alkyls, Bipyridyls, and Nitroxyl Radicals

Cited by 10 publications

References 8 publications

Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides

Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides

Metal complexes in controlled radical polymerization

Effect of Co and V complexes on polymerization of methyl methacrylate initiated by AlEt2Br‐TEMPO catalyst

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Effect of Co and V complexes on polymerization of methyl methacrylate initiated by AlEt₂Br‐TEMPO catalyst