Heterogeneity Index During Dead-End Polymerization

Tobolsky, A. V.; Gobran, Riad H.; Böhme, Reinhild; Schaffhauser, R.

doi:10.1021/j100805a019

Cited by 10 publications

(6 citation statements)

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“…Tobolsky et al 45 derived expressions for polydispersity indices in the case of chain transfer in the dead-end […”

Section: Theoretical Tdsls Signatures For Chain Growth Polymerizationmentioning

confidence: 99%

“…Tobolsky et al derived expressions for polydispersity indices in the case of chain transfer in the dead-end scenario, but did not mention the possibility of a divergent mass, nor did they perform experiments. Wooster generalized dead end polymerization theory to include reactions of different order that compete between propagation and termination reactions, and hence can deviate from Tobolsky's and the above treatment …”

Section: Theoretical Tdsls Signatures For Chain Growth Polymerization...mentioning

confidence: 99%

“…Tobolsky et al 45 derived expressions for polydispersity indices in the case of chain transfer in the dead-end [m](t) scenario, but did not mention the possibility of a divergent mass, nor did they perform experiments.…”

Section: Theoretical Tdsls Signatures For Chain Growth Polymerization...mentioning

confidence: 99%

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In Situ Time-Dependent Signatures of Light Scattered from Solutions undergoing Polymerization Reactions

et al. 2004

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Time-dependent static light scattering (TDSLS) signatures were used to characterize polymerization reactions in situ. The relationship between these signatures and intra-and interparticle characteristics of the growing polymer population, as the solution passes from the dilute to semidilute regime, is sought theoretically, and measured experimentally. As much information as possible is determined concerning polymer mass and polymerization kinetics. At the outset of the reactions the weightaverage molecular mass M w dominates the scattered intensity, but gives way to second and third virial coefficient (A2, A3) effects as polymer concentration increases. Since polymer mass, A2 and A3 are interrelated, it is possible to introduce plausible conversion kinetics to predict a variety of TDSLS signatures. These are calculated for free radical and controlled radical polymerization and compared to experimental TDSLS signatures for acrylamide free radical polymerization. These signatures are fit with only two eligible parameters; M w and the reaction rate constant R. Predictions concerning the evolution of Mw in a "dead-end" polymerization are also made and measured experimentally using an online monitoring method.

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“…Tobolsky et al 45 derived expressions for polydispersity indices in the case of chain transfer in the dead-end […”

Section: Theoretical Tdsls Signatures For Chain Growth Polymerizationmentioning

confidence: 99%

Section: Theoretical Tdsls Signatures For Chain Growth Polymerization...mentioning

confidence: 99%

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In Situ Time-Dependent Signatures of Light Scattered from Solutions undergoing Polymerization Reactions

et al. 2004

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“…20 This analysis included free radical polymerization for the cases of both constant and decreasing weight average molecular mass M w , during the reaction, as well as dead-end reactions. 21 Additionally, predictions were made concerning controlled radical polymerization (CRP), [22][23][24] when it resembles a living type reaction. Comparing experimental data to the various models, including crossover expressions, 25 it was determined that Zimm's virial coefficient expansion for light scattering 26 in the limit of q ) 0 (q is the amplitude of the scattering vector) was the most robust:…”

Section: Introductionmentioning

confidence: 99%

“…Recently, the groundwork for combining virial coefficient and dilute/semidilute crossover expressions for light scattering with different types of polymerization kinetics was published . This analysis included free radical polymerization for the cases of both constant and decreasing weight average molecular mass M w , during the reaction, as well as dead-end reactions . Additionally, predictions were made concerning controlled radical polymerization (CRP), − when it resembles a living type reaction.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous in-Situ Monitoring of Parallel Polymerization Reactions Using Light Scattering; A New Tool for High-Throughput Screening

et al. 2004

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A recently introduced technique, simultaneous multiple sample light scattering (SMSLS), was used to monitor parallel polymerization reactions in situ. SMSLS is designed for real-time, high-throughput screening and provides a time-dependent light scattering signature for each reaction, which contains both qualitative and semiquantitative information. Qualitatively, the signature immediately indicates whether the reaction occurs or not, whether there is an initial lag period, and how long the reaction takes until it stops. The signature also provides estimates of the reaction rate and weight average molecular mass M(w), and its shape can help identify mechanistic aspects, for example, controlled versus free radical polymerization, presence of impurities, etc. The method is inherently adapted to small sample volumes and requires no special sample preparation or postpolymerization characterization. The demonstration here involved the free radical polymerization of acrylamide under varying conditions and should be readily applicable to a wide variety of other reactions. Results were cross-checked with multi-detector gel permeation chromatography.

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Determination of kinetic parameters of ethyl methacrylate polymerization by using the dead‐end procedure

Çatalgil¹,

Baysal²

1987

Makromol. Chem.

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Kinetics of polymerization of ethyl methacrylate initiated by 2,2'-azoisobutyronitrile (AIBN) was studied applying the "dead-end" theory. This theory is appropriate to examine the solution polymerization of this monomer in benzene at 8 > 60°C. Radical polymerizations of ethyl methacrylate were carried out at 60 -110 "C. By using the procedures of the dead-end theory, the rate of decomposition and the initiator efficiency of AIBN were determined. Kinetic parameters of the solution polymerization of ethyl methacrylate were calculated and the results were compared with the literature values.

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Heterogeneity Index During Dead-End Polymerization

Cited by 10 publications

References 0 publications

In Situ Time-Dependent Signatures of Light Scattered from Solutions undergoing Polymerization Reactions

In Situ Time-Dependent Signatures of Light Scattered from Solutions undergoing Polymerization Reactions

Simultaneous in-Situ Monitoring of Parallel Polymerization Reactions Using Light Scattering; A New Tool for High-Throughput Screening

Determination of kinetic parameters of ethyl methacrylate polymerization by using the dead‐end procedure

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