Initiation in the polymerization of acrylonitrile

Bevington, J. C.; Eaves, D. E.

doi:10.1039/tf9595501777

Cited by 39 publications

(15 citation statements)

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“…(17), (19), and (20) can be neglected, because CEVE can neither homopolymerize nor copolymerize with St under these conditions. (17), (19), and (20) can be neglected, because CEVE can neither homopolymerize nor copolymerize with St under these conditions.…”

Section: Effects Of Electron-donor Additives On the Copolymerizationmentioning

confidence: 99%

“…How- k13 kzi kzz ever, MAn, which can not homopolymerize easily was introduced into the terpolymer a little higher than the donor monomers, as is shown in Table 3 and Fig. (17), (19), and (20) Table 3, k31/k32, which are the reactivity ratios of m3 to Mi and Mz, were determined using Eqs. Therefore, the Eq.…”

Section: Effects Of Electron-donor Additives On the Copolymerizationmentioning

confidence: 99%

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Discussion on the mechanism of alternating copolymerization of styrene and maleic anhydride

1971

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To clear up the detailed mechanism of the alternating copolymerization of styrene (St) and maleic anhydride (MAn) concerning the initiation species, the propagation species, the tendency of the chain transfer reaction as well as the directional tendency of the reaction between copolymer radicals and monomer complexes, the role of the charge transfer complexes, characterization of end groups and additional donor effects were examined.The equilibrium constant of the St/MAn (1 : 1) complex was determined to be 0.31 by NMR spectroscopy, that suggested considerable amounts of complexes existing in the system. As expected, a small quantity of initiator (1%-azobisisobutyronitrile (AIBN)) was incorporated into the St/MAn copolymer. Chlorine atoms were scarcely incorporated into the copolymer synthesized in CCl4 with AIBN or benzoyl peroxide (BPO) as an initiator. Hence the copolymerization was considered to be induced only by attacke of initiator radicals to the monomer or the complexes, contrary to the usual conception of telomerization.When the electron donor monomer was added to the system, the terpolymerization could be treated as a copolymerization of the two complexes, i e . , St/MAn and Donor/MAn. By adding naphthalene the rate maximum point shifted from higher concentration of MAn to the equivalent concentration of St and MAn. Degradative chain transfer to N.N-dimethylaniline was observed, confirming the existance of poly-MAn radicals.It was suggested from these results that the charge transfer complex and uncomplexed MAn took part in the copolymerization of S t and MAn. This was proved kinetically. The whole mechanism was discussed. ZUSAMMENFASSUNG: Um den Mechanismus der alternierenden Copolymerisation von Styrol (St) und Maleinsaureanhydrid (MAn) in bezug auf die Art der Initiierung und des Wachstums, die Neigung zu Ketteniibertragungsreaktionen und Richtungstendenzen der Reaktion zwischen den Copolymerradikalen und den Monomerkomplexen aufzuklaren, wurden die Rolle der Elektronendonator/-akzeptor-Komplexe, die Charakterisierung der Endgruppen und Donatoreffekte untersncht. Die Gleichgewichtskonstante des St/MAn(l : 1)-Komplexes wurde durch NMR-Spektroskopie zu 0,31 bestimmt. Das bedeutet, dal3 betrachtliche Mengen von Komplexen in dem System existieren. Eine kleine Menge des Initiators (1%-Azoisobuttersaiuredinitril (AIBN)) wurde, wie erwartet, in das St/MAn-Copolymere eingebaut. Chloratome wurden so gut wie nicht in das mit AIBN oder Dibenzoylperoxid (BPO) als Initiator in C C 4 synthetisierte 265 E. TSUCHIDA and T. TOMONO Copolymere eingebaut. Es wurde daher die Copolymerisation nur als durch den AngrifT der Initiatorradikale auf das Monomere oder die Komplexe gestartet betrachtet, im Gegensatz zum iiblichen Konzept der Telomerisation. Wenn ein Elektronendonator-Monomeres dem System hinzugefiigt wurde, konnte die Terpolymerisation als Copolymerisation der beiden Komplexe St/MAn und Donator/MAn betrachtet werden. Bei Zugabe von Naphthalin wurde die maximale Copolymerisationsgeschwindigkeit von hoheren MAn-...

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Section: Effects Of Electron-donor Additives On the Copolymerizationmentioning

confidence: 99%

Section: Effects Of Electron-donor Additives On the Copolymerizationmentioning

confidence: 99%

Discussion on the mechanism of alternating copolymerization of styrene and maleic anhydride

1971

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“…A fairly reliable value for k,/k:'* (in British convention) was measured as 0.078 L'/2/mo1"2. s"' at 60OC. Bevington and Eaves (1959) also reported a value for k,/k:" in DMF at 6OOC. The original value of 0.12 L'/2/mo1'/2-~1/2 was revised to 0.08485 to correspond with the British convention for k,.…”

Section: Homogeneous Polymerizationmentioning

confidence: 95%

“…The true value of the initiator efficiency is much less than 1 as other research groups estimated. Bevington and Eaves ( 1959) used labeled ''C-azoisobutyronitrile to initiate the polymerization in DMF at 60OC. The average value of the initiator efficiency was measured to be 0.47 by plotting the specific activity of polymer over monomer against the rate of polymerization at a fixed monomer concentration.…”

Section: Homogeneous Polymerizationmentioning

confidence: 99%

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A Comprehensive Simulator/Database Package for Reviewing Free-Radical Homopolymerizations

Gao

Penlidis

1996

Journal of Macromolecular Science, Part C: Polymer Reviews

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Radical Polymerization

Vana¹,

Barner‐Kowollik²,

Davis³

et al. 2003

Encyclopedia of Polymer Science and Technology

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The present article summarizes the fundamental principles and recent advances in free radical polymerization systems. Each individual reaction step in the polymerization process—initiation, propagation, transfer, and termination—is discussed in detail with regard to the underlying first principles and to the latest rate coefficient data. Novel methodologies, including living free radical polymerization, are also introduced within this context. In addition, the article gives an up‐to‐date overview of current state‐of‐the‐art experimental techniques for obtaining reliable kinetic and mechanistic information, embedded in an extensive coverage of the rates of radical polymerization, thermodynamics, and the chain‐length distribution. Such techniques range from now quasi‐classic experiments, such as pulsed laser polymerization, size exclusion chromatography, and the chain‐length distribution method for transfer constant determination, to cutting edge methodologies, such as the use of living free radical processes for chain‐length‐dependent rate coefficient determination. The fundamental differential equations governing free‐radical polymerization and the chemistry involved are both extensively covered along with ample tabular material, giving the practicing polymer chemist up‐to‐date and easily accessible data material backed up by over 500 references.

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Initiation in the polymerization of acrylonitrile

Cited by 39 publications

References 1 publication

Discussion on the mechanism of alternating copolymerization of styrene and maleic anhydride

Discussion on the mechanism of alternating copolymerization of styrene and maleic anhydride

A Comprehensive Simulator/Database Package for Reviewing Free-Radical Homopolymerizations

Radical Polymerization

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