Nitroxide mediated free radical polymerization process – autopolymerization

Georges, Michaël K.; Kee, R. Andrew; Veregin, Richard P. N.; Hamer, Gordon K.; Kazmaier, Peter M.

doi:10.1002/poc.610080413

Cited by 78 publications

(51 citation statements)

References 5 publications

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“…Several studies have been done about this topic, [24][25][26][27][28][29][30][31][32][33][34][35][36] which have identified additional reactions and phenomena related to the TEMPO radical. The work of Sald ıvar-Guerra et al [29] considers a mechanism involving dimer formation and the consequent consumption of TEMPO.…”

Section: Resultsmentioning

confidence: 99%

Mathematical Modeling of NMRP of Styrene–Divinylbenzene over the Pre‐ and Post‐Gelation Periods Including Cyclization

Aguiar

Gonçalves

Pinto

et al. 2013

Macro Reaction Engineering

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Nitroxide-mediated polymerization of styrene-divinylbenzene has been modeled using generating functions of length distributions, pseudo-kinetic propagations, and numerical fractionation with the crosslinking rate depending on generation. Cyclization reactions are tackled by balances of sequences, yielding fair predictions of the measured pendant double bond concentration. With reduction in crosslinking, agreement for the experiments at 90 8C between predicted and measured weight-average, molecular weight, and weight fraction of gel is observed. A much higher relative crosslinking reactivity is observed at 130 8C as compared to 90 8C, likely an effect of the chain mobility.

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Section: Resultsmentioning

confidence: 99%

Mathematical Modeling of NMRP of Styrene–Divinylbenzene over the Pre‐ and Post‐Gelation Periods Including Cyclization

Aguiar

Gonçalves

Pinto

et al. 2013

Macro Reaction Engineering

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show abstract

“…8,9 To suppress the thermal polymerization of styrene, several organic acids have been used, e.g., camphorsulfonic acid (CSA), 10 which has demonstrated to have an effective control over the thermal initiation of styrene, even in the presence of nitroxides. 11 It has been pointed out that CSA increases the polymerization rate in NMRP while broadening the molecular weight distribution 12 ; this effect was attributed to nitroxide consumption as a result of nitroxide disproportionation by the acid molecule, which shifts the equilibrium to the formation of active radicals. 13 In addition, CSA can react with a nitroxide molecule to form hydroxylamine, leading to a poor control over the polymerization and in consequence broadening the molecular weight distribution.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of polystyrene oligomers by nitroxide‐mediated radical polymerization using diethylketone triperoxide as a multifunctional radical initiator

Anda

Santos

Morales

2011

J of Applied Polymer Sci

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Styrene oligomers (M n , 2500-3000 g/mol) with low polydispersity index and containing peroxidic groups within their structure were synthesized using a novel trifunctional cyclic radical initiator, diethylketone triperoxide (DEKTP), through nitroxide-mediated radical polymerization (NMRP), using OH-TEMPO. During the synthesis of the polystyrene (PS) oligomers, camphorsulfonic acid (CSA) was used to inhibit the thermal autoinitiation of styrene at the evaluated temperatures (T ¼ 120-130 C). The polymerization rate, which can be related to the slope of the plot of monomer conversion with reaction time, was monitored as a function of OH-TEMPO, DEKTP, and CSA concentrations. The experimental results showed that all the synthesized polymers presented narrow molecular weight distributions, and the monomer conversion and the molecular weight of the polymers increased as a function of reaction time.

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“…11 There are three kinds of synthetic methods generally: nitroxide-mediated polymerization (NMP); 12 atom transfer radical polymerization; 13 and reversible addition-fragmentation chain transfer polymerization.…”

Section: Introductionmentioning

confidence: 99%

Preparation and mechanical properties of poly(vinyl chloride)/bamboo flour composites with a novel block copolymer as a coupling agent

Kim

Peck

Hwang

et al. 2008

J of Applied Polymer Sci

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To improve the interfacial adhesion between poly(vinyl chloride) (PVC) and bamboo flour in PVC/bamboo flour composites, a novel coupling agent, poly(styrene-co-maleic anhydride)-block-poly(styrene-coacrylonitrile) {P[(SMA)-b-(SAN)]}, was synthesized through living free-radical polymerization in a one-pot reaction. P[(SMA)-b-(SAN)] was synthesized by a nitroxide-mediated polymerization technique in the presence of 2,2,6,6-tetramethylpiperidin-l-oxyl with azobisisobutyronitrile. The conversion of maleic anhydride (>99%) and styrene (>65%) was relatively high and yielded P[(SMA)-b-(SAN)] with a narrow molecular weight distribution (weight-average molecular weight/number-average molecular weight <1.38). PVC was blended with bamboo flours in the presence of the synthesized coupling agent with a two-roll mill. P[(SMA)-b-(SAN)] was added to the PVC matrix at a concentration of 55 or 20 wt %. As the content of P[(SMA)-b-(SAN)] in the wood-polymer composite increased, improved morphological and mechanical behaviors were observed.

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Nitroxide mediated free radical polymerization process – autopolymerization

Cited by 78 publications

References 5 publications

Mathematical Modeling of NMRP of Styrene–Divinylbenzene over the Pre‐ and Post‐Gelation Periods Including Cyclization

Mathematical Modeling of NMRP of Styrene–Divinylbenzene over the Pre‐ and Post‐Gelation Periods Including Cyclization

Synthesis of polystyrene oligomers by nitroxide‐mediated radical polymerization using diethylketone triperoxide as a multifunctional radical initiator

Preparation and mechanical properties of poly(vinyl chloride)/bamboo flour composites with a novel block copolymer as a coupling agent

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