Cationic Polymerization of Phenylbutadienes. II. Initiation Reaction in Cationic Polymerization of Phenylbutadienes Catalyzed by Triphenylmethylstannic Pentachloride

Asami, Ryuzo; Hasegawa, Kunihiro

doi:10.1295/polymj.8.53

Cited by 12 publications

(4 citation statements)

References 12 publications

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“…This fact will be supported by the result that the activation enthalpy of 1-PB was larger than that of styrene in the initiation with triphenylmethyl stannic pentachloride in the preceding paper. 12 Similar results noting that the high-reactive monomer is more incorporated than the lowreactive one as the temperature is raised in a cationic copolymerization have been reported in other studies. 13 ' 14 The monomer reactivity ratios were calculated for the above data by means of the intersection method and are summarized in Table VI.…”

Section: Cationic Copolymerization Of 1-phenylbutadiene With Styrene supporting

confidence: 81%

Cationic Polymerization of Phenylbutadienes. IV. Cationic Copolymerization of trans-1-Phenyl-1,3-butadiene with Olefinic Monomers

Asami

Hasegawa

Asai

et al. 1976

Polym J

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ABSTRACT:The copolymerization of 1-phenylbutadiene with olefinic monomers was performed by using isobutene, styrene, and a-methylstyrene as comonomers catalyzed by BFsOEtz or SnCl4-trichloroacetic acid. From the monomer reactivity ratios in these copolymerizations in methylene chloride, the following order of the reactivities of the monomers is indicated: a-methylstyrene > 1-phenylbutadiene > isobutene >styrene> isoprene> butadiene. This order of the reactivities will be explained by the stability of the cations formed from the monomers and by the nucleophilicity of the monomers. In the copolymerization of 1-phenylbutadiene with styrene catalyzed by BFsOEtz, the reactivity of 1-phenylbutadiene increased with increasing the polarity of the solvent in the order of nitroethane >methylene chloride> toluene. The temperature effect on the copolymerization was also recognized in such polar solvent as nitroethane. These results and the block character in the copolymerization of 1-phenylbutadiene with isobutene were interpreted on the basis of the two-step theory of propagation.KEY WORDS 1-Phenylbutadiene I Isobutene 1 Styrene 1 a-Methylstyrene I Solvent Effect I Temperature Effect 1In the preceding papers, 1 ' 2 we have already reported the kinetic results in the cationic homopolymerization of phenylbutadienes and the microstructure of the polymer obtained. EXPERIMENTAL Materials1-Phenylbutadiene (1-PB) was synthesized as described in the preceding paper 1 and the purity of the monomers was more than 99% according to gas chromatography. Styrene, a-methylstyrene, isobutene, catalysts, and solvents were used as commercially available, and purified by conventional methods.For this paper, the cationic copolymerization of 1-phenylbutadiene with nonpolar olefinic monomers was studied in order to make clear the relation between the reactivity and the structure of the monomer. Isobutene, styrene, and a-methylstyrene were selected as representative olefinic monomers. Monomer reactivity ratios were determined in several solvents and at different temperatures to study the solvent effect and the temperature effect in these cationic copolymerizations. We will discuss the reactivity of phenylbutadiene in cationic polymerization in comparison with that of other diene and vinyl monomers.

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Section: Cationic Copolymerization Of 1-phenylbutadiene With Styrene supporting

confidence: 81%

Cationic Polymerization of Phenylbutadienes. IV. Cationic Copolymerization of trans-1-Phenyl-1,3-butadiene with Olefinic Monomers

Asami

Hasegawa

Asai

et al. 1976

Polym J

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“…In general, the rate of initiation of 1-PB derivatives was much larger than that of 2-PB derivatives. 6 The reason why the order of the activity of catalyst in the polymerization of methyl-l-phenyl-1,3-butadiene series was different from that of methyl-2-phenyl-l,3-butadiene series may be ascribed to the initiation reaction.…”

Section: Resultsmentioning

confidence: 99%

“…In preceding papers, the authors have investigated the cationic polymerization of phenyl-1,3-butadienes2-6 and the initiation reaction of phenyl-1,3-butadienes with triphenylmethyl stannic pentachloride. 6 It has been described that the initiation rate constant decreased according to the following order: 1-phenyl-l,3-butadiene > 2-phenyl-1,3-butadiene > 1,1 -diphenyl-1,3-butadiene > 1,2-diphenyl-l,3-butadiene > 2.3-diphenyl-l,3-butadiene » 1,4-diphenyl-l,3-butadiene. This order has been explained in terms of the stability of allylic cations formed by the attack of trityl cation except for 1.4-diphenyl-l,3-butadiene.…”

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confidence: 99%

Cationic Polymerization of Phenylbutadienes. 6. Cationic Polymerization of Methylpheny-1,3-butadienes

Hasegawa¹,

Asami²,

Higashimura³

1977

Macromolecules

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“…9 Catalysts and solvents obtained commercially were further purified by distillation on calcium hydride in a vacuum line.…”

Section: Methodsmentioning

confidence: 99%

Cationic Polymerization of Phenylbutadienes. III. Cationic Polymerization of 2-Phenyl-1,3-butadiene

Asami

Hasegawa

1976

Polym J

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ABSTRACT:2-Phenylbutadiene was polymerized by SnC14, BFaOEt2, and PhsCSnCls in ethylene dichloride. The kinetic study showed a rapid initiation in the cases of SnC14 and BF30Et2, but a rather slow initiation in the case of PhaCSnCls. The initial rate of polymerization in the cases of SnCl4 and BFaOEt2 or the maximum rate in the case of PhaCSnCls was expressed as followsThe molecular weight of the polymers obtained in these cationic polymerizations was independent of concentrations of both monomer and catalyst; hence, the monomer chain transfer was proposed as a terminating reaction. By IR, UV, and NMR spectroscopies, it was shown that the microstructure of the polymers obtained in these cationic polymerizations was a 1,4-structure and about a half of the double bonds in the polymers was consumed by a novel cyclization whose scheme was proposed. The UV spectrum of the propagating species of 2-phenylbutadiene in the cationic polymerization was also found to be the same as in the case of 1-phenylbutadiene.

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Cationic Polymerization of Phenylbutadienes. II. Initiation Reaction in Cationic Polymerization of Phenylbutadienes Catalyzed by Triphenylmethylstannic Pentachloride

Cited by 12 publications

References 12 publications

Cationic Polymerization of Phenylbutadienes. IV. Cationic Copolymerization of trans-1-Phenyl-1,3-butadiene with Olefinic Monomers

Cationic Polymerization of Phenylbutadienes. IV. Cationic Copolymerization of trans-1-Phenyl-1,3-butadiene with Olefinic Monomers

Cationic Polymerization of Phenylbutadienes. 6. Cationic Polymerization of Methylpheny-1,3-butadienes

Cationic Polymerization of Phenylbutadienes. III. Cationic Polymerization of 2-Phenyl-1,3-butadiene

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