Free-radical chain-substitution reactions of alkylmercury halides

Russell, Glen A.; Tashtoush, Hasan

doi:10.1021/ja00343a069

Cited by 127 publications

(60 citation statements)

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“…In fact, alkyl selenides are well known to undergo homolytic bimolecular substitution reaction (SH2 reaction) which corresponds to a chain transfer reaction in polymerization chemistry. 31 The chain transfer constant of benzyl phenyl selenide for the polymerization of styrene with 2,2' -azobisisobutyronitrile (AIBN) at 60°C has been estimated as 1.04 32 which is larger than value of diphenyl disulfide (0.147). 33 To investigate the end structure of polystyrene, 2 was used as a photoiniferter.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Polystyrene and Poly(methyl methacrylate) Each with a Phenyl Seleno Group at Terminal Chain End by Radical Polymerization in the Presence of Benzyl Phenyl Selenide as a Photoiniferter

Kwon

Kondo

Kunisada

et al. 1998

Polym J

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ABSTRACT:The photopolymerization of styrene with benzyl phenyl selenide proceeded smoothly to give polystyrene having benzyl and phenylsclcno groups at a-and w-chain ends, respectively, and the degree of functionality was 0.95. In a limited range of conversion, both the polymer yields and number average of molecular weights (M.) increased with the reaction time and the M. linearly increased with yield. The addition of styrene to the polystyrene with irradiation increased the molecular weight of the polymer. In the photopolymerization of methyl methacrylate, similar polymerization behavior was observed. The tacticity of the poly(methyl methacrylatc) was in good agreement with that prepared by radical mechanism. Photoirradiation of polystyrene having phenylseleno group at the w-end in the presence of methyl methacrylate effectively afforded a block copolymer of styrene and methyl methacrylate.KEY WORDS Radical Polymerization / Benzyl Phenyl Selenide / p-Methoxybenzyl p-Trimethylsilylphenyl Selenide / Photoiniferter / Polymeric Photoiniferter / Block Copolymer / End functional polymers are useful precursors for novel block, graft and star polymers. The synthesis of end functional polymers are conventionally prepared by anionic, cationic, and radical polymerization. 1 -11 Preparation by radical polymerization with iniferter method is quite convenient and hence widely used. 12 -16 Otsu and coworkers 1 7 -19 proposed iniferter for the design of the polymer chain end structure. An iniferter is an initiator which also functions as chain transfer agent and/or primary radical terminator. It is attractive for preparing simple block copolymers and more complex polymer architectures using various monomers which do not polymerize by an ionic mechanism. 20 -23 Iniferters mainly use organic sulfur compounds such as tetraalkylthiuram disulfides, dithiocarbamates, and tetramethylene disulfide.We recently reported that photopolymerization of styrene in the presence of di phenyl diselenide, 24 similar to the case of tetraalkylthiuram disulfides 25 to afford polystyrene carrying phenylseleno groups at both chain ends (P-A) (eq I). By the irradiation of light to the polymers with selenide moieties (P-A) in styrene, polystyrene with higher molecular weight (P-B) was obtainOse-Se-Q + n P-A + m CH2=3

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Section: Resultsmentioning

confidence: 99%

Synthesis of Polystyrene and Poly(methyl methacrylate) Each with a Phenyl Seleno Group at Terminal Chain End by Radical Polymerization in the Presence of Benzyl Phenyl Selenide as a Photoiniferter

Kwon

Kondo

Kunisada

et al. 1998

Polym J

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“…30 The effect of the ditelluride was also observed in the presence of azo initiators, and the polymerization of MMA and 3 in the presence of AIBN and dimethyl ditelluride proceeded under mild thermal conditions and afforded well-controlled poly(methyl methacrylate) (PMMA; entries 14 and 15). The effect of ditellurides could be attributed to their excellent radical-capturing ability; 36 they react with the polymer-end radicals to deactivate the dormant organotellurium species. The rapid deactivation shifts the equilibrium from the radical species to the dormant organotellurium species, which leads to the higher controllability of the polymerization as discussed in the Mechanism section.…”

Section: Applications To (Meth)acrylate Monomersmentioning

confidence: 99%

Development of organotellurium‐mediated and organostibine‐mediated living radical polymerization reactions

Yamago

2005

J. Polym. Sci. A Polym. Chem.

173

103

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Organotelluriummediated living radical polymerizations (TERPs) and organostibinemediated living radical polymerizations (SBRPs) provide well-defined polymers with a variety of polar functional groups via degenerative chain-transfer polymerization. The high controllability of these polymerizations can be attributed to the rapid degenerative-transfer process between the polymer-end radicals and corresponding dormant species. The versatility of the methods allows the synthesis of AB diblock, ABA triblock, and ABC triblock copolymers by the successive addition of different monomers. This review summarizes the current status of TERP and SBRP.

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“…There are several similar reports for the reactivity of group 16 elements. Sulfur radicals attack unsaturated bonds faster than selenic radicals 45 and the selenic radicals react with carbon radicals. 46 Different reactivity of the pnictogen radicals make it possible to construct a periodic vinylene-arsine-vinylene-stibine backbone.…”

Section: Terpolymerization Of Organoarsenic Homocyclementioning

confidence: 99%

Synthesis of Polymers Containing Group 15 Elements via Bismetallation of Acetylenic Compounds

Naka

2008

Polym J

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Carbon-element bond formation is a key point of synthetic methodology for incorporating a wide variety of metallic or metalloid elements in polymer main chains. Radical 'bismetallation' to carbon-carbon triple bonds based on homolytic cleavage of element-element single bonds is one of the most useful and highly atom-economical methods for carbon-element bond formation. Syntheses of novel polymers containing group 15 elements have been achieved by ring-collapsed radical alternating copolymerization (RCRAC) of homocyclic compounds with rings built exclusively of group 15 elements with acetylenic compounds. Poly(vinylene-arsine)s were successfully prepared by a radical reaction between pentamethylpentacycloarsine (cyclo-(MeAs) 5 ) or hexaphenylhexacycloarsine (cyclo-(PhAs) 6 ) and mono-substituted acetylenic compounds using 2,2 0 -azobisisobutyronitrile (AIBN) as a radical initiator or irradiation with xenon lamp at room temperature. Without any radical initiator at 25 C, cyclo-(MeAs) 5 caused cleavage of the arsenic-arsenic bond spontaneously and copolymerized with phenylacetylene to give poly(vinylene-arsine)s. The copolymers obtained showed fluorescence properties which were influenced by the substituents of the acetylenic compounds. Poly(vinylene-phosphine)s and poly(vinylene-stibine)s were also prepared by RCRAC of cyclo-(MeP) 5 and cyclo-(PhSb) 6 with alkynes, respectively. Different reactivity of pnictogen radicals made it possible to construct the periodic vinylene-arsine-vinylene-stibine backbone. The radical terpolymerization of cyclo-(MeAs) 5 , phenylacetylene, and a vinyl monomer and radical copolymerization of cyclic diarsine with vinyl monomers were also described.

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Free-radical chain-substitution reactions of alkylmercury halides

Cited by 127 publications

References 0 publications

Synthesis of Polystyrene and Poly(methyl methacrylate) Each with a Phenyl Seleno Group at Terminal Chain End by Radical Polymerization in the Presence of Benzyl Phenyl Selenide as a Photoiniferter

Synthesis of Polystyrene and Poly(methyl methacrylate) Each with a Phenyl Seleno Group at Terminal Chain End by Radical Polymerization in the Presence of Benzyl Phenyl Selenide as a Photoiniferter

Development of organotellurium‐mediated and organostibine‐mediated living radical polymerization reactions

Synthesis of Polymers Containing Group 15 Elements via Bismetallation of Acetylenic Compounds

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