Free radical grafting of monomers to polydienes. III. Kinetics and mechanism of styrene grafting to polyisoprene

Cameron, G. Gordon; Qureshi, M. Younus

doi:10.1002/pol.1980.170180710

Cited by 38 publications

(17 citation statements)

References 3 publications

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“…Thus, it is important to distinguish between the reactivity of all the radical species relative to their tendency to react with the monomer. For the polyisoprene molecule, the two methylene groups in the isoprene residue are not equivalent and it seems likely that the attack occurs preferentially at carbon 4, so that the methyl group exerts the greatest stabilizing influence on the resulting allylic radical 34…”

Section: Resultsmentioning

confidence: 99%

Transition Metal Complexes of a Salen–Fullerene Diad: Redox and Catalytically Active Nanostructures for Delivery of Metals in Nanotubes

Lebedeva

Chamberlain

Davies

et al. 2013

Chemistry A European J

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A covalently-linked salen-C60 (H2L) assembly binds a range of transition metal cations in close proximity to the fullerene cage to give complexes [M(L)] (M=Mn, Co, Ni, Cu, Zn, Pd), [MCl(L)] (M=Cr, Fe) and [V(O)L]. Attaching salen covalently to the C60 cage only marginally slows down metal binding at the salen functionality compared to metal binding to free salen. Coordination of metal cations to salen-C60 introduces to these fullerene derivatives strong absorption bands across the visible spectrum from 400 to 630 nm, the optical features of which are controlled by the nature of the transition metal. The redox properties of the metal-salen-C60 complexes are determined both by the fullerene and by the nature of the transition metal, enabling the generation of a wide range of fullerene-containing charged species, some of which possess two or more unpaired electrons. The presence of the fullerene cage enhances the affinity of these complexes for carbon nanostructures, such as single-, double- and multiwalled carbon nanotubes and graphitised carbon nanofibres, without detrimental effects on the catalytic activity of the metal centre, as demonstrated in styrene oxidation catalysed by [Cu(L)]. This approach shows promise for applications of salen-C60 complexes in heterogeneous catalysis.

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Section: Resultsmentioning

confidence: 99%

Transition Metal Complexes of a Salen–Fullerene Diad: Redox and Catalytically Active Nanostructures for Delivery of Metals in Nanotubes

Lebedeva

Chamberlain

Davies

et al. 2013

Chemistry A European J

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“…For the polyisoprene molecule, the two methylene groups in the isoprene residue are not equivalent and it seems likely that the attack occurs preferentially at carbon 4, so that the methyl group exerts the greatest stabilizing influence on the resulting allylic radical. 34 In the grafting system, the attack of the alkoxy radical on cis-polyisoprene most likely occurred by chain transfer to form the polyisoprenyl radical. The reactivity of the polystyryl radical is about the same as that of the polyisoprenyl radical (both are stabi- lized by resonance).…”

Section: Graft Copolymer Compositionsmentioning

confidence: 99%

Process variables and their effects on grafting reactions of styrene and methyl methacrylate onto natural rubber

Arayapranee

Prasassarakich

Rempel

2003

J of Applied Polymer Sci

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ABSTRACT:The graft copolymerization of styrene and methyl methacrylate onto natural rubber latex was studied under various reaction conditions using a cumene hydroperoxide redox initiator. The monomer conversion, graft copolymer compositions, and grafting efficiency were determined. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance ( 1 H-NMR) analysis and differential scanning calorimetry (DSC). A 2 IV 6-2 fractional factorial experimental design was applied to study the main effects on the grafting. The variables investigated in this work were the amount of the initiator and emulsifier, the presence or absence of a chaintransfer agent, the styrene-to-methyl methacrylate ratio, the monomer-to-rubber ratio, and the reaction temperature. The measured response for the experimental design was the grafting efficiency. The analysis of the results from the design showed the sequence of the main effects on the observed response of the grafting of styrene and methyl methacrylate onto natural rubber, in ascending order. The amount of the chain-transfer agent and the reaction temperature in the range of the test had significant effects and one marginally significant effect was the monomer-to-rubber ratio.

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“… a, b, c, d Adjusted in this work between the following literature limits: 80 < k p SS < 480 L mol s −1 ; 290 < k p MM < 900 L mol s −1 ; 0.0016 < k fg S < 0.096 L mol s −1 ; 0.14 < k fg SM < 0.44 L mol s −1 for cis ‐2‐butene, as proposed by Cameron and Qureshi 14…”

Section: Model Adjustment and Simulation Resultsmentioning

confidence: 99%

“…Many publications4–47 have investigated on the homopolymerizations of MMA or St in the presence of PB rubbers. In the case of high‐impact polystyrene (HIPS), both experimental15–30 and theoretical31–47 articles have been reported.…”

Section: Introductionmentioning

confidence: 99%

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Solution and quasi‐bulk copolymerizations of styrene and methyl methacrylate in the presence of polybutadiene: Mathematical model

Gutierrez

Estenoz

Gugliotta

et al. 2010

J of Applied Polymer Sci

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A mathematical model was developed for simulating the batch copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of polybutadiene (PB). It was adjusted to the measurements of three reactions carried out at 65 C, with initial comonomers ratio at the azeotropic condition, THF as solvent, and benzoyl peroxide as initiator. The measurements included: (a) conversions and grafting efficiencies by gravimetry; (b) molecular weight distributions (MWDs) by size exclusion chromatography; and (c) global mass fractions of St in the co-and terpolymer, by UV-Vis spectroscopy. The model predicts the MWDs of the three polymeric components of MBS: free St-MMA copolymer, St-MMA-g-PB graft terpolymer (GT), and residual PB. In addition, it predicts the bivariate chain length distributions of the different GT topologies, with each topology characterized by the number of branches per molecule. V C 2010Wiley Periodicals, Inc. J Appl Polym Sci 117: 2010

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Free radical grafting of monomers to polydienes. III. Kinetics and mechanism of styrene grafting to polyisoprene

Cited by 38 publications

References 3 publications

Transition Metal Complexes of a Salen–Fullerene Diad: Redox and Catalytically Active Nanostructures for Delivery of Metals in Nanotubes

Transition Metal Complexes of a Salen–Fullerene Diad: Redox and Catalytically Active Nanostructures for Delivery of Metals in Nanotubes

Process variables and their effects on grafting reactions of styrene and methyl methacrylate onto natural rubber

Solution and quasi‐bulk copolymerizations of styrene and methyl methacrylate in the presence of polybutadiene: Mathematical model

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