Ceric ion‐reducing agent redox initiated vinyl polymerisation

Subramanian, S. V.; Santappa, M.

doi:10.1002/macp.1968.021120101

Cited by 43 publications

(8 citation statements)

References 12 publications

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“…Applying the steady-state principle to the primary radicals R° and the growing polymeric radicals RMn° and making the usual assumption that the radical reactivity is independent of radical size 7…”

Section: → °+°mentioning

confidence: 99%

“…According to the complex mechanism, unimolecular disproportionation of complex yields a cerrous ion, a proton, and a free radical on the alcohol substrate 2,3 . Ce(IV) ion either alone or in combination with various organic reducing agents such as alcohols 4 , acids 5 , amides 6 , aldehydes 7 and ketones 8 has been used to initiate vinyl polymerization. The polymerization of acrylonitrile by Ce(IV)-glucose system was studied by Padhi and Singh 9,10 .…”

Section: Introductionmentioning

confidence: 99%

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Polymerization of Acrylonitrile Initiated by Cerium(IV) / p-Aminoacetophenone Redox System - A Kinetic Study

2016

Chem Sci Trans

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The kinetics of aqueous polymerization of acrylonitrile initiated by the Ce(IV)/p-aminoacetophenone (Ce(IV) -AAP) redox system in aqueous solution of sulfuric acid medium has been studied under nitrogen atmosphere in the temperature range 30-80 °C. The rate of polymerization (Rp) and the disappearance of Cerium(IV) have been measured at various concentrations of monomer, initiator, activator and sulfuric acid. The temperature dependence of the rate was studied and the activation parameters were computed using Arrhenius plot. A mechanism consistent with the experimental data is proposed and discussed.

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Section: → °+°mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymerization of Acrylonitrile Initiated by Cerium(IV) / p-Aminoacetophenone Redox System - A Kinetic Study

2016

Chem Sci Trans

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“…It is well known that polymerizations of vinyl monomers are initiated by system consisting of ceric ion and a reducing agent such as alcohols [12], aldehydes [13], and amines [14]. Ceric ion/alcohol systems have been used for the graft polymerization of vinyl monomers to polymers having hydroxyl groups [ 151.…”

Section: Initiation Of Polymerization By Ceric Lon/baso-hs Systemmentioning

confidence: 99%

Surface Grafting onto Barium Sulfate: Polymerization of Acrylamide Initiated by the System Consisting of Alcoholic Hydroxyl Groups on the Surface and Ceric Ion

Tsubokawa

Seno

1994

Journal of Macromolecular Science, Part A

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To modify the surface of barium sulfate, the grafting of polymers onto the surface by the polymerization of acrylamide (AAm) initiated by the system consisting of ceric ion and alcoholic hydroxyl groups on the surface was investigated. Barium sulfate modified by 12-hydroxystearate (BaS0,-HS) was prepared by the reaction of barium chloride with sodium sulfate containing a small amount of sodium 12-hydroxystearate. The presence of 12-hydroxystearate groups on the BaSO, surface was confirmed by XPS analysis and infrared spectra. It was found that the graft polymerization of AAm is initiated by the system consisting of ceric ion and BaS0,-HS to give poly(AAm)-grafted BaSO,. This indicated that the grafted polymer chains are propagated from surface radicals formed by the redox reaction of ceric ion with 12-hydroxystearate groups on the surface. The polymerization rate (R,) of AAm initiated by the redox system was given by R, = k[AAm] [Ce(IV)][BaSO,-HS] where k is constant, [ A h ] is AAm concentration, [Ce(IV)] is ceric ion concentration, and [BaSO,-HS] is BaS0,-HS concentration. The result suggested that in such an initiating system, the unimolecular termination 1135

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“…The decrease in conversion of acrylamide by nitric acid is caused by the decrease in value of K, as well as increase k;, for ceric salt will become more reactive with the aid of the acid. SUBRAMANIAN et al 15) reported the reduction of degree of polymerization on acrylonitrile. The similar consideration was previously reported by MINO et al 12).…”

Section: Effect Of Nitric Acid On Propagationmentioning

confidence: 99%

Studies of the polymerization of vinyl compounds in the presence of metal salts. 7. Effect of nitric acid on the polymerization of acrylamide initiated by ceric salt

1972

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The polymerization of acrylamide initiated by ammonium cerium(1V) nitrate was investigated. The rate was found to vary with concentration of nitric acid. One factor for the variation is the change of concentration of active species of ceric ion by the acid and another factor is the decrease in activity of acrylamide, because the equilibrium constant for the complex of acrylamide with ceric ion decreased with increasing concentration of acid. The rate of initiation was decided by the increasing of activity of ceric ion and by decreasing of that of monomer. The rate of termination was found to increase with increasing activity of ceric ion. From these results, the structure of the complex was proposed; the ceric ion is considered to be coordinated to carbonyl oxygen rather than double bond in acrylamide. ZUSAMMENFASSUNG:Es wurde die Polymerisation von Acrylamid durch Initiierung mittels Ammoniumcer(1V)-nitrat untersucht. Die Geschwindigkeit der Polymerisation andert sich mit der Konzentration der Salpetersaure. Diese Erscheinung beruht erstens auf der dnderung der aktiven Spezies der Cerionen durch die Saure und zweitens auf der Abnahme der Aktivitat des Acrylamids, weil die Gleichgewichtskonstante des aus Acrylamid und Cerion zusammengesetzten Komplexes mit zunehmender Saurekonzentration abnimmt. Die Geschwindigkeit der Initiierung hangt von der Zunahme der Aktivitat der Cerionen und der Abnahme der Aktivitat des Monomeren ab. Die Geschwindigkeit der Terminierung nimmt mit der Zunahme der Aktivitat der Cerionen zu. Aus diesen Ergebnissen wurde abgeleitet, daS das Cerion starker am Carbonyl-Sauerstoff als an der Doppelbindung von Acrylamid koordiniert ist. * ) For the previous papcr of this series see H. NARITA and S. MACHIDA, Chem. High Polymers [Tokyo] 28 (1971) 389.

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Ceric ion‐reducing agent redox initiated vinyl polymerisation

Cited by 43 publications

References 12 publications

Polymerization of Acrylonitrile Initiated by Cerium(IV) / p-Aminoacetophenone Redox System - A Kinetic Study

Polymerization of Acrylonitrile Initiated by Cerium(IV) / p-Aminoacetophenone Redox System - A Kinetic Study

Surface Grafting onto Barium Sulfate: Polymerization of Acrylamide Initiated by the System Consisting of Alcoholic Hydroxyl Groups on the Surface and Ceric Ion

Studies of the polymerization of vinyl compounds in the presence of metal salts. 7. Effect of nitric acid on the polymerization of acrylamide initiated by ceric salt

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