Modeling of Functional Group Distribution in Copolymerization: A Comparison of Deterministic and Stochastic Approaches

Parsa, Mohammad Ali; Kozhan, Iurii; Wulkow, Michael; Hutchinson, Robin A.

doi:10.1002/mats.201300156

Cited by 62 publications

(102 citation statements)

References 20 publications

(27 reference statements)

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“…Similarly, for statistical FRP copolymerization involving one functional comonomer in a low overall amount (5 mol%), Ali Parsa et al [36] recently found by means of deterministic and stochastic simulations that half of the polymer chains do not contain this functional comonomer under starved-feed conditions. Importantly, such mismatch between the expected and actual copolymer composition would not be captured by a kinetic model description without an explicit differentiation between polymer chains possessing a given number of functional comonomer units.…”

Section: Batch Proceduresmentioning

confidence: 96%

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

et al. 2014

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Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000), optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP). Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr 2 /PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation () polymer property. Careful selection or fed-batch addition of the conventional radical initiator I 2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1) . Fed-batch addition of not only I 2 , but also comonomer and deactivator (50 ppm) under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

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Section: Batch Proceduresmentioning

confidence: 96%

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

et al. 2014

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“…The values of required reaction rate constants were extracted from the literature and are summarized in Table 3 . [ 10 ] …”

Section: Copolymerization Temperature 138°cmentioning

confidence: 97%

“…(1) Initiator dissociation Reaction scheme applied to copolymerization. [ 10 ] Initiator molecular weight 132 g mol −1…”

Section: Model Development and Simulationmentioning

confidence: 99%

“…[ 10,16 ] The target microstructure is depicted in Table 1 (Cases I and II) and defi ned as a linear binary copolymer with chain length of 20 ending in a B comonomer. Case I corresponds to batch operation, whereas Case II is a starvedfeed semibatch policy.…”

Section: Model Development and Simulationmentioning

confidence: 99%

“…However, experimental efforts hardly ever have such complete information, and this makes the practical implementation (of whatever techniques one may devise in order to compensate for this lack of information) quite complicated (e.g., see the procedures, main concepts, and background assumptions put forward in ref. [1][2][3][4][5][6][7][8][9][10] ).…”

Section: Introductionmentioning

confidence: 98%

See 2 more Smart Citations

Molecular Architecture Manipulation in Free Radical Copolymerization: An Advanced Monte Carlo Approach to Screening Copolymer Chains with Various Comonomer Sequence Arrangements

Saeb

Mohammadi²,

Pakdel

et al. 2016

Macro Theory & Simulations

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A Kinetic Monte Carlo (KMC) simulation approach has been adopted in this study to capture evolutionary events in the course of free radical copolymerization, through which batch and starved‐feed semibatch processes are compared. The implementation of the KMC code developed in this work: (i) enables satisfactory control of the molecular weight of the copolymer by tracking the profiles of concentrations of macroradicals, monomers, and polymer as well as degree of polymerization, polydispersity, and chain length distribution; (ii) captures the bivariate distribution of chain length and copolymer composition; (iii) comprehensively tracks and analyzes detailed information on the molecular architecture of the growing chains, thus distinguishing between sequence length and polydispersity of chains produced in batch and starved‐feed semibatch operations; (iv) makes possible the screening of products, based on such details as the number and weight fractions of products having different comonomer units located at various positions along the copolymer chains. The aforementioned characteristics are achieved by stochastic calculations through code developed in‐house. This KMC simulator becomes a very useful tool for the development of tailored copolymers through free radical polymerization, with blocks separated with single units of a different type.

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Copolymers

Ballard

2023

Kirk-Othmer Encyclopedia of Chemical Technology

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This article provides an overview of the preparation, properties, use, and characterization of synthetic copolymers. The range of different copolymer structures that can be synthesized using current methods is detailed and the current IUPAC‐recommended nomenclature for naming these structures is explained. Techniques for the production of copolymers are discussed, with an emphasis on the types of copolymers and copolymer structures attainable through each polymerization technique. Industrially important random, alternating, block, graft, star, and hyperbranched copolymers are described in terms of the processes used to produce them and the properties achieved. Their main uses and major producers are also detailed.

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Modeling of Functional Group Distribution in Copolymerization: A Comparison of Deterministic and Stochastic Approaches

Cited by 62 publications

References 20 publications

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

Molecular Architecture Manipulation in Free Radical Copolymerization: An Advanced Monte Carlo Approach to Screening Copolymer Chains with Various Comonomer Sequence Arrangements

Copolymers

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