A novel polymerization by plasma‐fragmented species generated from nonpolymerized compounds

Kuzuya, Masayuki; Kawaguchi, Tohru; Daikyo, Toshiya; Okuda, Takuo

doi:10.1002/pol.1983.130210702

Cited by 13 publications

(3 citation statements)

References 2 publications

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“…Values obtained were similar for each of these fractions (see Table I) and close to that of the unfractionated initiator (10.9 kcal/mol). The activation energy for the control sample was 17 kcal/mol and corresponds to an activation energy for in- "The polymerization temperature was 50 °C. The plasma duration was 8 min, the initial plasma pressure was 8 torr, and 2 mL of MMA was added to each ampule after plasma exposure.…”

Section: Resultsmentioning

confidence: 99%

Initiation of methyl methacrylate polymerization by the non-volatile products of a methyl methacrylate plasma. 1. Polymerization kinetics

Paul¹,

Bell²,

Soong³

1985

Macromolecules

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It is concluded that plasma-initiated polymerization of methyl methacrylate occurs by the continuous unimolecular generation of initiating free radicals by a plasma-deposited oil. This conclusion was drawn from the observed dependence of the rate of polymerization on the 0.58 power of the oil concentration and the first power of the monomer concentration. The reaction kinetics were determined by monitoring the conversion of polymerization in sealed ampules with an oblique-line refractometer. The initiating species is not a single compound. Size exclusion chromatography of the oil produced a series of fractions, each of which was effective as an initiator. The activation energy for initiation is ~15 kcal/mol, independent of whether the whole oil or one of its fractions was used.

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Section: Resultsmentioning

confidence: 99%

Initiation of methyl methacrylate polymerization by the non-volatile products of a methyl methacrylate plasma. 1. Polymerization kinetics

Paul¹,

Bell²,

Soong³

1985

Macromolecules

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“…With the 12.4 kcal/mol value of E{ -Et and a value of 2.3 kcal/mol43 for the activation energy for termination of growing PMMA chains, Et is calculated to be 14.7 kcal/ mol. While this value is much lower than that expected for the rupture of a C-C bond (~85 kcal/mol), or even a peroxide linakge (~35 kcal/mol), activation energies in the range [5][6][7][8][9][10][11][12][13][14][15][16] kcal/mol have been reported for the thermal decomposition of plasma-produced films.19,44…”

Section: Resultsmentioning

confidence: 99%

Initiation of methyl methacrylate polymerization by the non-volatile products of a methyl methacrylate plasma. 4. An ESR study of the initiating radicals

Paul¹,

Bell²,

Soong³

1986

Macromolecules

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“…intensity started to decrease earlier. This may be because the spin adduct formed reacted further with the large excess of available radicals, as shown in reaction (11):…”

Section: Structural Dependence Of Pbn Spin-adduct Formationmentioning

confidence: 99%

Nature of radical reactivity of organic plasma-exposed glass surface studied by the electron spin resonance spin-trapping technique

Kuzuya¹,

Nakai²,

Okuda³

et al. 1987

J. Chem. Soc., Faraday Trans. 1

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In order to investigate the nature of radical ractivity of a plasma-exposed glass surface, we have carried out a number of reactions for phenyl-N-t-butylnitrone (PBN) spin-adduct formation in various organic plasmaexposed glass ampoules. Certain plasma-exposed glass surfaces where an ultrathin film was deposited afforded the PBN spin adduct in such reactions. Spin-adduct formation continued to occur fo; a long period of time if an appropriate solvent was chosen as an activator, demonstrating that such a glass surface can undergo a constant slow release of radical species. A kinetic study indicated that the rate-determining step for the formation of the spin adduct is the stage when an active radical species is leached out of the ultrathin film. Thus the mechanism by which the ultrathin film immobilizes the active radical species and permits its slow release is ascribed to the presence of weakened a-bonds in the film and their facile bond fission by physicomechanical action of the solvents used.

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A novel polymerization by plasma‐fragmented species generated from nonpolymerized compounds

Cited by 13 publications

References 2 publications

Initiation of methyl methacrylate polymerization by the non-volatile products of a methyl methacrylate plasma. 1. Polymerization kinetics

Initiation of methyl methacrylate polymerization by the non-volatile products of a methyl methacrylate plasma. 1. Polymerization kinetics

Initiation of methyl methacrylate polymerization by the non-volatile products of a methyl methacrylate plasma. 4. An ESR study of the initiating radicals

Nature of radical reactivity of organic plasma-exposed glass surface studied by the electron spin resonance spin-trapping technique

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