Stable Free Radical Polymerization of Styrene:  Controlling the Process with Low Levels of Nitroxide

MacLeod, Paula J.; Veregin, Richard P. N.; Odell, Peter G.; Georges, Michaël K.

doi:10.1021/ma961510+

Cited by 29 publications

(22 citation statements)

References 4 publications

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“…Increasing the concentration of the nitroxide mediator resulted in a decrease in the resulting monomer conversion rate. [15][16][17] This result was consistent with the current mechanistic model of the SFRP system. [18,19] Goto and Fukuda investigated the use of added radical initiator to accelerate the rate of stable free radical polymerization.…”

Section: Introductionsupporting

confidence: 91%

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

Lizotte

Long

2004

Macro Chemistry & Physics

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Summary: The homopolymerization and copolymerization of various alkyl acrylate monomers was studied under stable free radical polymerization (SFRP) conditions using in situ FTIR spectroscopy to monitor polymerization kinetics. The IR absorbance corresponding to the CH deformation of the monomer (968 cm−1) was measured to determine monomer conversion in real‐time fashion. The monomer disappearance profiles were subsequently converted to pseudo‐first order kinetic plots. Altering the alkyl ester chain length and configuration did not reveal a significant trend in the resulting polymerization kinetics. However, addition of 2‐hydroxyethyl acrylate (HEA) to a polymerization of n‐butyl acrylate (nBA) substantially accelerated the rate of total monomer conversion, increasing the observed rate constant almost two times. 1H NMR spectroscopy also showed that the resulting HEA/nBA copolymers were enriched with the HEA monomer. Moreover, a similar but enhanced effect was also observed upon the addition of small amounts of dodecanol to an n‐butyl acrylate homopolymerization resulting in more than a doubling of the observed rate constant.Resonance forms associated with the DEPN nitroxide and stabilization resulting from hydrogen bonding.magnified imageResonance forms associated with the DEPN nitroxide and stabilization resulting from hydrogen bonding.

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Section: Introductionsupporting

confidence: 91%

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

Lizotte

Long

2004

Macro Chemistry & Physics

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“…Subsequently, MacLeod et al (1997) published a report showing a series of styrene polymerizations performed with varying ratios of [TEMPO]/[BPO], from 1.35 to 0.5. Results were presented in a table showing number‐average molecular weights, polydispersity and conversion after 5 h at 135°C.…”

Section: Resultsmentioning

confidence: 99%

“…It was shown that as the ratio was lowered from 1.35 to 0.5, the polydispersity increased, and molecular weights and conversion level increased. Results from MacLeod et al (1997) have been plotted as polydispersity values versus [TEMPO]/[BPO] ratio (Figure 17a). As can be seen, the minimum value is around ratio 1.2, which is in agreement with our data at 120 and 130°C (see Figure 17b and c).…”

Section: Resultsmentioning

confidence: 99%

“… Polydispersity as a function of [TEMPO]/[BPO] ratio for NMRP of styrene: (a) after 5 h at 135°C (MacLeod et al, 1997), (b) at 50% conversion at 120°C, and (c) at 50% conversion at 130°C. …”

Section: Resultsmentioning

confidence: 99%

“…For instance, the conversion versus time data points reported in the past only capture the first few hours of the experiment and low to medium conversion (see, e.g., Veregin et al, 1996a,b; Dollin et al, 2007). Average molecular weight data are usually not readily available (Veregin et al, 1996a,b) and, if available, are presented as number‐average molecular weight points evaluated at a limited number of conversion levels (usually, low‐medium‐high conversion; see, e.g., MacLeod et al 1997; Dollin et al, 2007). Weight‐average molecular weight data are hardly ever reported (with the usual argument that the polydispersity index, PDI, is usually low and close to 1.1–1.2).…”

Section: Introductionmentioning

confidence: 99%

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A replicated investigation of nitroxide‐mediated radical polymerization of styrene over a range of reaction conditions

et al. 2008

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A comprehensive experimental investigation of nitroxide-mediated radical polymerization (NMRP) of styrene using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as controller is presented. Polymerizations with a bimolecular initiator (benzoyl peroxide; BPO) were carried out at 120 and 130 • C, with TEMPO/BPO molar ratios ranging from 0.9 to 1.5. Results indicate that increasing temperature increases the rate of polymerization while the decrease in molecular weights is only slight. It was also observed that increasing the ratio of TEMPO/BPO decreased both the rate of polymerization and molecular weights. Probably for the first time in the history of such investigations, the paper contains a comprehensive database, appropriate for parameter estimation in aid of future modelling studies, since it comes from a systematic data collection containing independent replication.On présente uneétude expérimentale approfondie de la polymérisation radicalaire basée sur les nitroxydes (NMRP) du styrèneà l'aide de tétraméthyl-2,2,6,6 pipéridinyloxy-1 (TEMPO) comme agent de contrôle. Des polymérisationsà l'aide d'un initiateur bimoléculaire (peroxyde de benzoyle, BPO) ontété menéesà 120 et 130 • C, avec des rapports molaires de TEMPO/BPO variant entre 0,9à 1,5. Les résultats indiquent que l'augmentation de température accroît la vitesse de polymérisation tandis que la baisse des masses moléculaires n'est que légère. On aégalement observé que l'augmentation du rapport de TEMPO/BPO diminueà la fois la vitesse de polymérisation et les masses moléculaires. Probablement pour la première fois dans l'histoire de ce type de recherches, l'article contient une base de données complète, convenantà l'estimation de paramètres en vue d'études de modélisation futures,étant issue d'une collecte de données systématique.

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Effects of reaction conditions on poly(methyl methacrylate) polymerized by living radical polymerization with iniferter

Kongkaew

Wootthikanokkhan

2000

J. Appl. Polym. Sci.

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Living radical polymerization of methyl methacrylate (MMA) through the use of benzyl diethyl dithiocarbamate (BDC) was studied. The aim was to investigate the role of the concentration, BDC-to-MMA mol ratio, and reaction time upon the molecular weight, polydispersity, and conversion of the product. It was found that the molecular weight and the conversion increase with increase of the concentration at the expense of low polydispersity. The reaction time also played a significant role, especially at a relatively long reaction time where molecular weight, polydispersity, and conversion increased with increasing reaction time. In terms of the mol ratio effect, it was found that there was a critical mol ratio for maximum conversion. The results indicate that the kinetics of polymerization of MMA through the use of a BDC inifeter is different from that in the presence of a conventional initiator.

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Stable Free Radical Polymerization of Styrene: Controlling the Process with Low Levels of Nitroxide

Cited by 29 publications

References 4 publications

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

A replicated investigation of nitroxide‐mediated radical polymerization of styrene over a range of reaction conditions

Effects of reaction conditions on poly(methyl methacrylate) polymerized by living radical polymerization with iniferter

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