Β-Ray INITIATION OF POLYMERIZATION OF STYRENE AND METHYL METHACRYLATE

Seitzer, W.H.; Goeckermann, R. H.; Tobolsky, A. V.

doi:10.1021/ja01099a518

Cited by 20 publications

(3 citation statements)

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“…On comparing eqs. (15) and (16), it is obvious that if AV; is small and positive, the degree of polymerization and hence the molecular weight should increase with pressure at a slightly faster rate than the rate of polymerization.…”

Section: Effect Of Pressure On Overall Rate Of Polymerizationmentioning

confidence: 99%

γ‐radiation‐initiated polymerization of bulk styrene at high pressure

Moore¹,

Ayscough²,

Clouston³

1977

J. Polym. Sci. Polym. Chem. Ed.

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The polymerization of styrene in bulk at pressures up to 273 MPa and temperatures between 3 and 49°C with the use of γ‐radiation as the initiator has been studied. The polymerization rate and the molecular weight of the polymer increased with increasing pressure; the molecular weight increased at a slightly faster rate. The difference in the rate is a theoretical expectation which has not previously been observed because chain‐transfer reactions obscure the effect in chemically initiated systems. A small but significant retardation of the initiation reaction occurs as the pressure is increased. The results of previous workers are critically reviewed. Chain transfer at 25°C for pressures below 220 MPa is negligible when γ‐radiation is the initiator. The activation energy for bulk polymerization decreased with increasing pressure from 28.1 kJ/mole at 0.1013 MPa to 22.3 kJ/mole at 203 MPa. Volumes of activation at 25°C for 0.1013 < p < 273 MPa were calculated to be Initiation, +4.0 < ΔV 1‡ < +4.4 cm3/mole; polymerization; −Δ pol‡ = −20.9 cm3/mole; degree of polymerization; ΔV DP–‡ = −25.3 cm3/mole; propagation/termination; −ΔV italicp/italict 1/2‡ = −22.7 cm3/mole.

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Section: Effect Of Pressure On Overall Rate Of Polymerizationmentioning

confidence: 99%

γ‐radiation‐initiated polymerization of bulk styrene at high pressure

Moore¹,

Ayscough²,

Clouston³

1977

J. Polym. Sci. Polym. Chem. Ed.

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“…Thus the polymerizations can be inhibited by oxygen and benzoquinone, and the products generally possess properties typical of polymers produced by free-radical chain processes, such as high molecular weights. In the case of styrene and methyl methacrylate, direct evidence from copolymerization studies has shown conclusively that the radiation-induced polymerization of these two monomers proceeds by a radical mechanism (27,31,384) and that the propagating radical is a monoradical (544).…”

Section: Vinyl Compoundsmentioning

confidence: 99%

“…Less detailed investigations have been made of the effects of various radiations on styrene (30,70,307,308,486,522,544), methyl methacrylate (30,110,116,308,309,486,502,522,544), vinyl acetate (70,110,116,307,308,309,486), acrylonitrile (116, 486, 522), vinyl chloride (110, 453), and methyl acrylate (110,522). In all the reports but one, polymerization resulted, and the products were not noticeably different from those obtained by non-radiation methods.…”

Section: Mixtures With Other Substancesmentioning

confidence: 99%

The Radiation Chemistry Of Organic Substances

Collinson¹,

Swallow²

1956

Chem. Rev.

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Über den einbau von chlor bei der polymerisation von methacrylsäuremethylester XV. Mitteil. Polymerisationen und polymerisationsinitiatoren

1967

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Bei der Polymerisation von Methacrylsäuremethylester in Gegenwart von methyleneaktiven Initiatoren sowie Chlorid und Luftsauerstoff wird Chlor in das Polymere eingebaut. Der Einbau wurde radiochemisch bestimmit. Der in Gegenwart von α‐Benzoyl‐propionitril gefundene, von der Chlorid‐Konzentration abhängige Chlor‐Einbau wird durch einen durch Chlorid bewirkten Zerfall des intermediär gebildeten Hydroperoxids gedeutet. In Gegenwart von N‐Äthyl‐bis‐(p‐toluolsulfonylmethyl)‐amin bzw. 1.3.5‐Trimethyl‐barbitursäure ist der Chlor‐Einbau von der Chlorid‐Konzentration unabhängig. Es wird ein bevorzugt thermischer Zerfall des intermediären Hydroperoxids angenommen.

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Β-Ray INITIATION OF POLYMERIZATION OF STYRENE AND METHYL METHACRYLATE

Abstract: COMMUNICATIONS TO THE EDITOR 755of the labeled reaction partner. These activities were measured on samples of barium sulfate, prepared from S, H2S and SO2 by oxidation, and were corrected for self-ab~orption.~ The results are given in Table I.

Cited by 20 publications

References 1 publication

γ‐radiation‐initiated polymerization of bulk styrene at high pressure

γ‐radiation‐initiated polymerization of bulk styrene at high pressure

The Radiation Chemistry Of Organic Substances

Über den einbau von chlor bei der polymerisation von methacrylsäuremethylester XV. Mitteil. Polymerisationen und polymerisationsinitiatoren

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