Intramolecular reactions in vinyl polymers as a means of investigation of the propagation step

Merz, E. H.; Alfrey, T.; Goldfinger, G.

doi:10.1002/pol.1946.120010202

Cited by 264 publications

(44 citation statements)

References 13 publications

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“…In this development, we use the terminal model 28 ; that is, only the terminal unit of a propagating radical and the unit adjacent to halogen atom of a dormant chain have influence on the comonomer reactivities. It should be noted that the penultimate effect can be significant in some copolymerization systems.…”

Section: Model Development Polymerization Scheme and Kinetic Equationsmentioning

confidence: 99%

Control of gradient copolymer composition in ATRP using semibatch feeding policy

et al. 2006

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in Wiley InterScience (www.interscience.wiley.com).Controlled/living radical copolymerization (CLRcoP) operated in a batch process is subject to composition drifting and thus produces spontaneous gradient copolymer. The composition distribution along the chain length of individual chains is solely determined by the reactivities of comonomers and the as-synthesized product is uncontrolled. Design of the composition vs. chain length profile provides a new route for developing polymer materials with tailor-made properties. Presented in this article is a theoretical mainframe used for the control over composition distribution along the chain length in atom transfer radical copolymerization. The control is based on a semibatch reactor technology with programmed comonomer feeding rates. Illustrated are three copolymerization model systems with representative reactivity ratios. The targeted composition distribution profiles are uniform, linear gradient, parabolic gradient, hyperbolic gradient, and di-block and tri-block distributions.

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Section: Model Development Polymerization Scheme and Kinetic Equationsmentioning

confidence: 99%

Control of gradient copolymer composition in ATRP using semibatch feeding policy

et al. 2006

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“…Since then, many copolymer systems of common acrylates and methacrylates, styrene, and functional acrylates as well as of other common monomers were studied applying both the terminal model (TM) [108] and the penultimate unit effect (PUE) [109,110] model [101,107,[111][112][113][114][115], which are detailed in Figure 2. A list of relevant computational results for the copolymer systems studied by the application of QM methods is presented in Table 3.…”

Section: Copolymerizationmentioning

confidence: 99%

“…Since then, many copolymer systems of common acrylates and methacrylates, styrene, and functional acrylates as well as of other common monomers were studied applying both the terminal model (TM) [108] and the penultimate unit effect (PUE) [109,110] Tables 1 and 2 respectively) of activation energy, E a , pre-exponential factor, lg(A), and rate constant at 50˝C, k, for the propagation reactions of various FRP systems. For each column, the number between square brackets indicates the literature source of the computational value adopted, with reference to the data in Table 2.…”

Section: Copolymerizationmentioning

confidence: 99%

On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

2015

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Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP) with growing interest. Nowadays, quantum chemistry (QC) can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.

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“…Under this assumption the eight reactions represented by the following equation are of importance (Merz et al (1946)). Under this assumption the eight reactions represented by the following equation are of importance (Merz et al (1946)).…”

Section: Penultimate Group Effects Copolymerization Modelmentioning

confidence: 99%

Estimation of parameters in monte carlo modelling

Duever

Reilly

1990

Can J Chem Eng

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This paper presents a general method for estimating model parameters from experimental data when the model relating the parameters and input variables to the output responses is a Monte Carlo simulation. From a statistical point of view a Bayesian approach is used in which the distribution of the parameters is handled in discretized form as elements of an array in computer storage. The stochastic nature of the Monte Carlo model allows only an estimate of the distribution to be calculated from which the true distribution must then be estimated. For this purpose an exponentiated polynomial function has been found to be useful. The method provides point estimates as well as joint probability regions. Marginal distributions and distributions of functions of the parameters can also be handled. The motivation for exploring this alternative parameter estimation technique comes from the recognition that for some systems, particularly when the underlying process is stochastic in nature, Monte Carlo simulation often is the most suitable way of modelling. As such, the Monte Carlo approach increases the range of problems which can be handled by mathematical modelling.The technique is applied to the modelling of binary copolymerization. Two models, the Mayo-Lewis and the Penultimate Group Effects models, are considered and a method for discriminating between these models in the light of sequence distribution data is proposed. ~ ~~~~~On prksente dans cet article une mkthode gentrale pour I'estimation de paramktres de modele B partir de donnees experimentales lorsque le modkle reliant les parametres et les variables d'entree aux reactions de sortie est une simulation de Monte Carlo. D'un point de vue statistique, on utilise une methode bayesienne, dans laquelle la distribution des parametres est traitee sous forme discrkte comme elements d'un tableau informatique. La nature stochastique du modele Monte Carlo permet uniquement l'estirnation de la distribution B calculer a partir de laquelle la veritable distribution peut Ctre estimbe. A cette fin, on a trouvk utile une fonction polynomiale exponentialisee. La methode donne des estimations de points ainsi que des zones de probabilitk communes. On peut egalement trait6 les distributions marginales et les distributions des fonctions de ces paramktres. L'exploration de cette autre technique d'estimation des paramktres est encouragee par le fait que pour certains systkmes, particulitrement lorsque le procedt sous-jacent est de nature stochastique, la simulation de Monte Carlo est souvent la meilleure facon de modeliser. Ainsi, la methode de Monte Carlo augmente I'kentail des problemes qui peuvent Ctre traitbs par la modelisation mathematique.La technique est appliquee a la modelisation de la copolymerisation binaire. Deux modeles, celui de Mayo-Lewis et celui des effets du groupe pCnulti&me, sont pris en consideration, et on propose une mtthode pour la discrimination entre ces modkles a la lurnikre des donnees de distribution des sequences.

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Intramolecular reactions in vinyl polymers as a means of investigation of the propagation step

Cited by 264 publications

References 13 publications

Control of gradient copolymer composition in ATRP using semibatch feeding policy

Control of gradient copolymer composition in ATRP using semibatch feeding policy

On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

Estimation of parameters in monte carlo modelling

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