Coordinated radical polymerization and redox polymerization of acrylamide by ceric ammonium nitrate

Takahashi, Tōru; Hori, Yasuhiko; Sato, Ichiro

doi:10.1002/pol.1968.150060807

Cited by 37 publications

(12 citation statements)

References 9 publications

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“…The existence of a complex between Ce(1V) and monomer has in fact been proved by IR and NMR in the case of acrylamide. 20 Oxidation of alcohols by ceric nitrate occurs through the formation of an intermediate complex and the reaction is first order, while ceric sulfate oxidizes alcohols probably directly and the reaction is second order. The well known ability of ceric nitrate to create a complex is corroborated by the results shown in Figure 9.…”

Section: Discussionmentioning

confidence: 99%

Graft copolymerization of cellulose initiated by ceric salts: Effect of reaction conditions on the consumption of ceric ion

Graczyk

Hornof

1988

J. Polym. Sci. A Polym. Chem.

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SynopsisA soluble monomer [methyl acrylate (MA)] and an insoluble monomer [butyl methacrylate (BMA)] were grafted onto cellulose by three types of ceric salts under both oxygen-free conditions and in the presence of oxygen. For comparison, Ce(IV) consumption during cellulose oxidation was also determined under similar reaction conditions. Slightly more Ce(1V) was consumed during cellulose oxidation in the presence of oxygen. During graft copolymerization of MA under oxygen-free conditions, the consumption of Ce(1V) was much lower than during cellulose oxidation regardless of the type of ceric salt employed. The opposite was observed in the presence of oxygen: much more Ce(1V) was consumed during grafting than during cellulose oxidation. The consumption of Ce(1V) in the graft copolymerization of BMA by ceric sulfate was nearly independent of reaction conditions and it was approximately the same as in cellulose oxidation. In the reaction initiated by ceric ammonium nitrate under oxygen-free conditions, less Ce(1V) was once again used up during grafting than during cellulose oxidation. However, the difference was much smaller than in the case of MA. Experiments carried out by Graczyk and Hornof

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Section: Discussionmentioning

confidence: 99%

Graft copolymerization of cellulose initiated by ceric salts: Effect of reaction conditions on the consumption of ceric ion

Graczyk

Hornof

1988

J. Polym. Sci. A Polym. Chem.

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“…The significance of the monomer-ceric ion interaction is clearly indicated in the ceric ion initiated homopolymerization of acrylamide and the graft copolymerization of acrylamide onto cellulose [32] .…”

Section: Ceric Ion Initiated Graft Copolymerizationmentioning

confidence: 99%

“…Infrared and NMR analyses of the ceric ion-acrylamide complex has indicated interaction of hydrated ceric ion with both the carbonyl group (ocomplex) and the carboncarbon double bond (n-complex) [32]. It has been concluded that the structure of the complexed monomer is that of a n-complex.…”

Section: Amentioning

confidence: 99%

A proposed new mechanism for catalyzed and uncatalyzed graft polymerization onto cellulose

Gaylord

1972

J. polym. sci., C Polym. symp.

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SYNOPSISGraft copolymerization of polar vinyl monomers onto cellulose in the presence of oxidizing agents, ceric ion, and radiation has been presumed to be solely the result of propagation from radical sites generated on the cellulose. The uncatalyzed polymerization and graft copolymerization of methyl methacrylate in the presence of cellulose and water has been presumed to involve the formation of a cellulose-water-monomer complex with the resultant generation of a covalently bonded monomer radical which then propagates in the usual manner. The formation of grafted alternating copolymer from the radiation induced polymerization of styrene-acrylonitrile and butadieneacrylonitrile, the radical catalyzed polymerization of styrene-methyl methacrylate and styrene-acrylonitrile-ZnC1, as well as the uncatalyzed polymerization of butadiene-methyl methacrylate in the presence of cellulose and water indicates the participation of comonomer charge transfer complexes in the graft copolymerization. It is proposed that cellulose acts as a complexing agent for the activation of acceptor monomers and as a matrix for the alignment of acceptor monomer complexes (AtYA-cellulosewater) and donor-acceptor comonomer complexes (P.:Acellulose-water). Polymerization of the complexes is initiated spontaneously or by radicals generated on the cellulose although the latter do not become incorporated into the polymer chain. Graft copolymerization results from termination of the growing polymer chains on cellulose by insertion into aldehyde groups.

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“…Sato and co‐workers reported that the homopolymerization of acrylamide in aqueous solution without nitric acid was initiated by a radical mechanism based upon an acrylamide–cerium complex. Infrared spectra suggested the presence of coordination consisting of both σ‐ and π‐type bonds 8, 12. From the kinetic analysis of the polymerization reactions of acrylonitrile, Ananthanarayanan and Santappa13 suggested that initiation took place through direct reaction between the ceric salt and acrylonitrile, while the results of Katai et al 14 pointed out that the polymerization of acrylonitrile was initiated both by ceric ion, Ce(IV), and primary radicals coming from the reducing agent.…”

Section: Introductionmentioning

confidence: 99%

N‐isopropylacrylamide–acrylamide copolymers initiated by ceric ammonium nitrate in water

Erbi̇l

Gökçeören

Polat

2007

Polymer International

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The polymerization and copolymerization of N-isopropylacrylamide (NIPAAm) and acrylamide (AAm) at different compositions, initiated by ceric ammonium nitrate alone, were studied in water at 60 • C. The dependence of the polymerization yield and molecular weight on the reaction temperature, nitrate ion concentration, presence of organic solvent and feed composition were examined by gravimetry, Fourier transform infrared (FTIR) spectroscopy and viscosity. The Viscotek system consists of three on-line detectors, namely right-angle light scattering, refractometer and viscometer, which were used to determine the number-average molecular weight (M n ) and hydrodynamic radius (R h ) of the NIPAAm-rich copolymers. It was observed that both M n and R h values of the copolymers decreased with increasing AAm content in the feed. The reactivity ratios of NIPAAm (2) and AAm (1) were computed by the extended Kelen-Tüdós method at high conversion, using FTIR analysis, and were found to be r 2 = 2.26 and r 1 = 0.34 for NIPAAm-rich copolymers, i.e. heterogeneous copolymers. From the determination of the lower critical solution temperature (LCST), i.e. phase transition of 2.0 wt% aqueous solutions of NIPAAm/AAm copolymers and NIPAAm homopolymer (PNIPAAm), using a UV-visible spectrometer, it was found that the hydrophilicity and LCSTs of the chains could be changed in a narrow temperature range by controlling the initial compositions. Turbidities (τ ) obtained from the absorbance values at three different wavelengths (λ; 400, 500 and 600 nm) were used to interpret the macromolecular phase transition from hydrophilic to hydrophobic structure. The effects of comonomer content and temperature on the coil-globule transition are discussed in terms of the slopes of the linear plots of log τ versus log λ.

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Coordinated radical polymerization and redox polymerization of acrylamide by ceric ammonium nitrate

Cited by 37 publications

References 9 publications

Graft copolymerization of cellulose initiated by ceric salts: Effect of reaction conditions on the consumption of ceric ion

Graft copolymerization of cellulose initiated by ceric salts: Effect of reaction conditions on the consumption of ceric ion

A proposed new mechanism for catalyzed and uncatalyzed graft polymerization onto cellulose

N‐isopropylacrylamide–acrylamide copolymers initiated by ceric ammonium nitrate in water

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