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

Asami, Ryuzo; Hasegawa, Kunihiro; Asai, Nobukazu; Moribe, Isamu; Doi, Atsumi

doi:10.1295/polymj.8.74

Cited by 8 publications

(3 citation statements)

References 13 publications

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“…Discussion of the transition state for cationic polymerization of phenylbutadienes will be given in detail in the following paper on copolymerization. 14…”

Section: The Reactivity Of Phenylbutadienes To Ph3csnclmentioning

confidence: 99%

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

Asami

Hasegawa

1976

Polym J

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Initiation in cationic polymerization of phenyl-substituted 1,3-butadienes with triphenylmethylstannic pentachloride as catalyst was studied. The rates of consumption of Ph3CSnCls with !-phenyl-substituted butadienes are represented by the following equation-d[Ph3CSnCls]ldt=k/[PhaCSnClo][M] , where M means monomer. On the other hand, in the case of 2-phenyl-substituted butadienes the rate is represented as follows-d[PhsCSnClsldt=k/[PhaCSnCls][M] + k[PhsCSnCls]([M]o-[M]) and the formation of a rr-complex between the monomer and a carbonium ion is suggested. The initiation rate constants decreased according to the following order: 1-phenyl-1,3-butadiene > 2-phenyl-1,3-butadiene > 1, 1-diphenyl-1 ,3-butadiene > 1 ,2-diphenyl-1 ,3-butadiene > 2,3-diphenyl-1 ,3-butadiene. 1,4-Diphenyl-1,3-butadiene did not react with PhsCSnCls at all. The high reactivity of phenylbutadienes toward PhsCSnCls in comparison with that of vinyl monomers could be ascribed to the stabilization of allyl-type cations which were formed by an attack of a trityl cation onto the 4-position and the !-position carbon for 1-phenylbutadienes and 2-phenylbutadiene, respectively.

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“…Discussion of the transition state for cationic polymerization of phenylbutadienes will be given in detail in the following paper on copolymerization. 14…”

Section: The Reactivity Of Phenylbutadienes To Ph3csnclmentioning

confidence: 99%

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

Asami

Hasegawa

1976

Polym J

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“…A similar temperature effect was observed in the copolymerization of 1-PB with styrene in polar solvents such as nitroethane and methylene chloride. 1 From the activation parameters determined using the monomer reactivity ratios in the temperature range from -78 to 0°C, 2-PB is shown to be less -reactive than styrene in the enthalpy term but more reactive in the entropy one (Table II). The reactivity of monomers toward a styryl cation decreased in the following order: 1-PB > styrene> 2-PB.…”

Section: Methodsmentioning

confidence: 99%

Cationic Polymerization of Phenylbutadienes. V. Cationic Copolymerization of Monophenyl-1,3-butadienes

Hasegawa

Asami

1976

Polym J

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ABSTRACT:To obtain information about the transition state for the cationic polymerization of monophenylbutadienes, the ring-substituent and the temperature effects on the copolymerizability were investigated. Judging from the magnitude of the p+ values for the copolymerizations of styrene with ring-substituted 1-and 2-phenylbutadienes, it is suggested that the propagation of monophenylbutadiene proceeds through the transition state which involves an cyclic carbonium ion intermediate. The same interpretation could be applied for the attack of a cinnamyl-type cation onto monophenylbutadiene. The reactivity of monomers toward a styryl cation decreased according to the following order: 1-phenylbutadiene>styrene>2-phenylbutadiene. The lower reactivity of 2-phenylbutadiene in comparison with styrene may be ascribed to the enthalpy increase which overweighs the entropy increase in the transition state.KEY WORDS 1-Phenylbutadiene / 2-Phenylbutadiene / Ring-Substituent Effect / Temperature Effect / Transition State / In a previous paper,1 the authors reported the cationic copolymerization of l-phenyl-1,3-butadiene (1-PB) with olefinic monomers such as isobutene, styrene, and a-methylstyrene. The reactivities of these monomers toward a I-PB propagating end in methylene chloride decreased in the following order: a-methylstyrene > 1-PB > isobutene > styrene. This order has been explained in terms of the nucleophilicity of the monomers and the stability of the resulting cations.In general, the kinetic feature of the propagation depends on the steric and the electronic effects of both the monomer and the propagating end. In addition, the propagation rate is sensitively influenced by a slight difference of the geometrical structures for the transition state.In this work, the transition state for the cationic polymerization of monophenylbutadienes will be discussed on the basis of the reactivity difference in the copolymerization. EXPERIMENTALMaterials 1-PB and 2-phenyl-1,3-butadiene (2-PB) were prepared as described in previous papers. 2 • 3 276 l-p-Methylphenyl-1,3-butadiene (p-CH3-l-PB) and l-p-chlorophenyl-1,3-butadiene (p-Cl-1-PB) were synthesized from the corresponding benzaldehydes by the same method as 1-PB.l-mChlorophenyl-1,3-butadiene (m-Cl-1-PB) was synthesized by Meerwein arylation between butadiene and the corresponding diazonium salt, and subsequent dehydrochlorination by potassium hydroxide. 4 These monomers were all trans isomers.Ring-substituted-2-phenyl-1,3-butadienes including p-methoxy, p-methyl, and p-chloro groups were prepared from the corresponding acetophenones and vinylmagnesium bromide by Grignard reaction and subsequent dehydration by potassium bisulfate. The boiling points of these monomers were as follows: p-CH3-l-PB 87°C (7 mm); p-Cl-1-PB 98°C (7 mm); m-Cl-1-PB 100°C (8 mm); p-CH3O-2-PB 76°C (4 mm); p-CH3-2-PB 61-62°C (7 mm); p-Cl-2-PB 67-69°C (5 mm). The purities of these monomers were more than 99% according to gas chromatography. Styrene, p-methylstyrene, catalysts, and methylene chloride were ...

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“…Though, there are few monomers such as styrene, diene, alpha (methyl styrene), isopropene, and butadiene, which are commercially available, but by changing the synthetic condition, their properties can be changed. Hence physical properties of block copolymers can be modified according to the requirement [Chambers, 1974;Asami et al, 1976;Jalics, 1977;Gandini et al, 1984]. Similarly, cationic polymerization is also applied for the synthesis of block copolymers [Uzawa et al, 2007].…”

Section: Ionic Polymerizationmentioning

confidence: 99%

Role of Block Copolymers in Tissue Engineering Applications

Malik

Sundarrajan

Hussain

et al. 2021

Cells Tissues Organs

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Research on synthesis, characterization, and understanding of novel properties of nanomaterials has led researchers to exploit their potential applications. When compared to other nanotechnologies described in the literature, electrospinning has received significant interest due to its ability to synthesize novel nanostructures (such as nanofibers, nanorods, nanotubes, etc.) with distinctive properties such as high surface-to-volume ratio, porosity, various morphologies such as fibers, tubes, ribbons, mesoporous and coated structures, and so on. Various materials such as polymers, ceramics, and composites have been fabricated using the electrospinning technique. Among them, polymers, especially block copolymers, are one of the useful and niche systems studied recently owing to their unique and fascinating properties in both solution and solid state due to thermodynamic incompatibility of the blocks, that results in microphase separation. Morphology and mechanical properties of electrospun block copolymers are intensely influenced by quantity and length of soft and hard segments. They are one of the best studied systems to fit numerous applications due to a broad variety of properties they display upon varying the composition ratio and molecular weight of blocks. In this review, the synthesis, fundamentals, electrospinning, and tissue engineering application of block copolymers are highlighted.

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

Cited by 8 publications

References 13 publications

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

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

Cationic Polymerization of Phenylbutadienes. V. Cationic Copolymerization of Monophenyl-1,3-butadienes

Role of Block Copolymers in Tissue Engineering Applications

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