Modeling the Distribution of Functional Groups in Semibatch Radical Copolymerization: An Accelerated Stochastic Approach

Nasresfahani, Amin; Hutchinson, Robin A.

doi:10.1021/acs.iecr.8b01943

Cited by 31 publications

(49 citation statements)

References 34 publications

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“…Kinetic Monte Carlo ( k MC) modeling allows to track several molecular characteristics along the synthesis 16,18,19,35–39 . In particular, k MC modeling allows to calculate the number of chains with a certain chain length (CL; equivalently the total number of monomer units) and a given number of functional comonomer units (FUNC value) so that in the context of the present work a bivariate functionality-chain length distribution (FUNC-CLD) can be constructed, with D highlighting the distributed nature of the variates in front 37,38 .…”

Section: Resultsmentioning

confidence: 99%

“…Quality assessment is currently performed based on simplified reaction schemes and average functionalization degrees so that the distributed nature of the functional monomer incorporation is significantly wiped out. Chain-to-chain deviations can nonetheless be expected based on recent theoretical studies, with a distribution both in chain length (CL) and composition (e.g., the number of functionalities FUNC) 14–19 . It is therefore crucial to develop a tool allowing to quantify the fraction of non-functionalized ( f nonfunctionalized ), single or even multiple functionalized chains for a broad range of functionalization chemistries.…”

Section: Introductionmentioning

confidence: 99%

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Visualization and design of the functional group distribution during statistical copolymerization

et al. 2019

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Even though functional copolymers with a low percentage of functional comonomer units (up to 20 mol%) are widely used, for instance for the development of polymer therapeutics and hydrogels, insights in the functional group distribution over the actual chains are lacking and the average composition is conventionally used to describe the functionalization degree. Here we report the visualization of the monomer distribution over the different polymer chains by a synergetic combination of experimental and theoretical analysis aiming at the construction of functionality-chain length distributions (FUNC-CLDs). A successful design of the chemical structure of the comonomer pair, the initial functional comonomer amount (13 mol%), and the temperature (100 °C) is performed to tune the FUNC-CLD of copoly(2-oxazoline)s toward high functionalization degree for both low (100) and high (400) target degrees of polymerization. The proposed research strategy is generic and extendable to a broad range of copolymerization chemistries, including reversible deactivation radical polymerization.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Visualization and design of the functional group distribution during statistical copolymerization

et al. 2019

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“…To overcome the design challenges in synthesizing engineered materials, mathematical models and simulators are essential in bridging kinetic and process conditions to the resulting structures. We have recently shown that coupling the so-called scaling method [24,25] with a volume correction approach significantly decreases the computational time required for kinetic Monte Carlo (KMC) simulation, approaching that of the deterministic method known as the method of moments [26]. The KMC output, however, provides detailed information not available from deterministic models, such as the placement of comonomer (often functional) units in the chains across the molar mass distribution [27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Extractable content of functional acrylic resins produced by radical copolymerization: A comparison of experiment and stochastic simulation

Nasresfahani

Idowu

Hutchinson

2019

Chemical Engineering Journal

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A comprehensive stochastic simulator that considers all probable secondary reactions essential for the description of high-temperature radical copolymerization of acrylate/methacrylate is implemented based on previously established accelerating techniques. The comparisons between the predictions and six experimental datasets are detailed for semi-batch copolymerization of 2-hydroxyethyl acrylate (HEA) with n-butyl methacrylate (BMA) under starved-feed condition. Macroscopic properties -free monomer and molar mass (MW) average profiles, final polymer molecular mass distributions, and the variation of acrylate composition with time-are reasonably well predicted over the range of initiator and comonomer levels studied. The simulation output also predicts the weight fraction and MW averages of the polymer chains that contain no HEA functionality, results that are compared to the experimental extractables obtained after crosslinking the copolymer resin. The general trends are well-captured, indicating that the model can be utilized in the future to optimize recipe and operating conditions to minimize the production of the non-functional material.

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“…More recently, a modification on the kMC implementation to reduce simulation times was proposed. [50] Recently, it has been proposed that the polymerization of some vinyl monomers (methyl methacrylate (MMA), styrene (Sty) and n-butyl acrylate (nBuA) initiated by a redox reaction with N-hydroxyphthalimide (NHPI) and xanthone (XT) leads to the production of materials with controlled microstructures. [51] The polymerization scheme for such novel system is shown in Table 1.…”

Section: Introductionmentioning

confidence: 99%

“…More recently, a modification on the kMC implementation to reduce simulation times was proposed. [ 50 ]…”

Section: Introductionmentioning

confidence: 99%

Modeling of Reversible Deactivation Radical Polymerization of Vinyl Monomers Promoted by Redox Initiation Using NHPI and Xanthone

López‐Domínguez

Clemente‐Montes

Vivaldo‐Lima

2020

Macro Reaction Engineering

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Two mathematical approaches for modeling of the kinetics and evolution of molar mass distributions in the reversible deactivation radical polymerization of vinyl monomers promoted by redox reaction with N-hydroxyphthalimide (NHPI) and xanthone (XT) are presented. In the first modeling approach, the polymerization scheme is implemented in the standard version of the Predici commercial software. In the second case, an accelerated, self-implemented version of the so called kinetic Monte Carlo (kMC) approach, considering binary trees, is used. The effect of concentrations of XT and monomer, as well as monomer type, on monomer conversion, NHPI efficiency, molar mass averages, molar mass dispersity, and full molar mass distributions are studied. The models are validated using literature available experimental data of polymerizations of methyl methacrylate (MMA) and styrene, in toluene, at 70 °C. The calculated results indicate that NHPI initiator efficiencies are low (<0.2); polymer end-group functionalities present a maximum value of about 0.8 with a subsequent decrease with monomer conversion; molar mass distributions are broad, exhibiting low molar mass tails. In addition, the hypothetical copolymerization of styrene and MMA is also considered. Copolymer composition distributions for short molecules are broader than those for large ones. 2000020 (2 of 12) www.advancedsciencenews.com www.mre-journal.de 2000020 (4 of 12) www.advancedsciencenews.com www.mre-journal.de Figure 7. Copolymer composition of active polymer radicals (plots a and d), dormant polymer (plots b and e), and dead polymer (plots c and f), at 3 and 10 h, respectively, for the reversible deactivation radical copolymerization of Sty and MMA using NHPI and XT.

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Modeling the Distribution of Functional Groups in Semibatch Radical Copolymerization: An Accelerated Stochastic Approach

Cited by 31 publications

References 34 publications

Visualization and design of the functional group distribution during statistical copolymerization

Visualization and design of the functional group distribution during statistical copolymerization

Extractable content of functional acrylic resins produced by radical copolymerization: A comparison of experiment and stochastic simulation

Modeling of Reversible Deactivation Radical Polymerization of Vinyl Monomers Promoted by Redox Initiation Using NHPI and Xanthone

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