Selectivity of the reaction of free radicals with styrene

Moad, Graeme; Rizzardo, Ezio; Solomon, David H.

doi:10.1021/ma00231a042

Cited by 247 publications

(157 citation statements)

References 20 publications

(41 reference statements)

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“…A curiosity on free radical polymerization has been stimulated to a great extent by the impressive progress made in several methods such as atom transfer radical polymerization (ATRP), nitroxyl radical-mediated polymerization (NMP), and reversible addition fragmentation transfer polymerization (RAFT). These methods and approaches were successfully introduced into polymerization process by different research groups [29][30][31][32][33]. Polymerization of MMA was effectively performed in ATRP [34,35], NMP [36] and RAFT [37,38].…”

Section: Introductionmentioning

confidence: 99%

Multi-site phase transfer catalyzed radical polymerization of methyl methacrylate in mixed aqueous–organic medium: a kinetic study

et al. 2017

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This work establishes the kinetics of radical polymerization of methyl methacrylate in an aqueous-organic two-phase system using 1,4-bis (triethylmethylammonium) benzene dichloride (TEMABDC) as multi-site phase transfer catalyst and potassium peroxydisulphate (K 2 S 2 O 8 ) as water-soluble initiator at 60 ± 1°C under nitrogen atmosphere. The role of concentrations of monomer, initiator, catalyst, acid and ionic strength, temperature and volume fraction of aqueous phase on the rate of polymerization (R p ) was investigated. . The rate of polymerization increases with an increase in the concentration of monomer, initiator, catalyst and temperature. A generalized reaction model was developed to explain the phase transfer catalyzed polymerization reaction. Based on the kinetic results, radical mechanism has been derived. The activation energy and other thermodynamic parameters were calculated. The FT-IR spectroscopy validates a band of 1732 cm -1 of ester group of the obtained polymer. The viscosity average molecular weight of the PMMA was found 1.6955 9 10 4 g/mol.

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Section: Introductionmentioning

confidence: 99%

Multi-site phase transfer catalyzed radical polymerization of methyl methacrylate in mixed aqueous–organic medium: a kinetic study

et al. 2017

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“…In several systems we observed molecules with more than one monomer residue. [22,26] Whereas we did not favour the mechanism for their formation as being a reversing of the trapped alkoxyamine with one monomer residue followed by insertion of a second monomer unit, we certainly thought about this possibility. We considered these dimer products formed by the slow trapping of the first formed radical.…”

Section: Termination In Copolymerizationsmentioning

confidence: 84%

“…However, the reaction scheme for the initiation of styrene with benzoyloxy radicals is shown in Scheme 8 and gives a range of products. [22,23] Several products in Scheme 8 require comment [22] :…”

Section: T-butoxymentioning

confidence: 99%

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On the Origins of Nitroxide Mediated Polymerization (NMP) and Reversible Addition–Fragmentation Chain Transfer (RAFT)

Rizzardo¹,

Solomon²

2012

Aust. J. Chem.

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The early experiments on radical polymerization, which were to lead to a study of nitroxide trapping of the initiation step and the interest in defect groups, particularly the macromonomers formed by termination by disproportionation, are discussed. Results from the nitroxide trapping clearly show that the initiation step ranges from simple clean addition to the head of the monomer, to complex addition/abstraction reactions. Careful selection of the monomer/initiation system is emphasized with particular reference to two common monomers, styrene and methyl methacrylate, and two initiating radicals, t-butoxy and benzoyloxy. The discovery of nitroxide mediated polymerization (NMP) from observations made during the nitroxide trapping work is reported and the ability to have a living radical system demonstrated with numerous examples. Similarly, the study of the copolymerization of macromonomers, formed by disproportionation of the propagating chains, is discussed with the discovery of b-scission and an early form of addition-fragmentation reported. The evolution of reversible addition-fragmentation chain transfer (RAFT) to a highly versatile and commercially attractive radical system is reported and the detailed chemistry behind the discovery of this living radical system discussed. Both NMP and RAFT enable the synthesis of structures not previously possible by radical polymerization and in some cases not possible by any other process.

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“…Nitroxide-mediated polymerisation (NMP), 3,4 atom transfer radical polymerisation (ATRP), 5,6 (RAFT), 7 single electron transfer polymerisation "living" radical polymerisation (SET-LRP) 8 are well-known approaches to synthesise a variety of polymeric structures using modified free radical polymerisation in a controlled manner, tuning their molecular weights, composition and architectures. Other processes, for example catalytic chain transfer polymerisation, CCTP, 9,10 have been designed to effectively reduce the molecular weight of produced polymers by introducing novel chain transfer agents, but not to necessary control their constitution and structure.…”

Section: Introductionmentioning

confidence: 99%

Methacrylic block copolymers by sulfur free RAFT (SF RAFT) free radical emulsion polymerisation

et al. 2017

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A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. We demonstrate the use of sulfur free reversible addition-fragmentation chain transfer polymerisation (RAFT as a versatile tool for the controlled synthesis of methacrylic block and comb-like copolymers. Sulfur free RAFT (SF-RAFT) utilises vinyl terminated macromonomers obtained via catalytic chain transfer polymerisation (CCTP) of methacrylates as a chain transfer agent (CTA), and thus precluding adverse aspects of the RAFT such as toxicity of dithioesters. We have synthesised a range of narrow dispersity block copolymers (Đ < 1.2) and comb-like macromolecules by employing emulsion polymerisation allowing for the preparation of relatively large quantities (~50 g) of the above mentioned copolymers promptly and straightforwardly. Copolymers were characterised using 1 H NMR, size exclusion chromatography (SEC), thermogravimetric analysis (TGA) and matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF-MS) techniques.

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Selectivity of the reaction of free radicals with styrene

Cited by 247 publications

References 20 publications

Multi-site phase transfer catalyzed radical polymerization of methyl methacrylate in mixed aqueous–organic medium: a kinetic study

Multi-site phase transfer catalyzed radical polymerization of methyl methacrylate in mixed aqueous–organic medium: a kinetic study

On the Origins of Nitroxide Mediated Polymerization (NMP) and Reversible Addition–Fragmentation Chain Transfer (RAFT)

Methacrylic block copolymers by sulfur free RAFT (SF RAFT) free radical emulsion polymerisation

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