Monte Carlo Approach to the Simulation of Ethylene Oxide and Propylene Oxide Polymerization and Copolymerization

Tesser, Riccardo; Santacesaria, E.

doi:10.1021/acs.iecr.1c01272

Cited by 4 publications

(18 citation statements)

References 24 publications

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“…A fed-batch polymerization reactor has been simulated in the present work with a scheme reported elsewhere. 4 The reactor is initially loaded with a predefined amount of the starter GLY, EO, and/or PO are then fed through a controller that keeps constant the pressure by regulating in ON/OFF mode the feed of alkoxides. The flow rate can be regulated to obtain homopolymers (by feeding a single alkoxide, EO, or PO, to the reactor), random copolymers (by using a simultaneous feed of EO and PO), or block copolymers (by an alternate feed of EO and PO).…”

Section: Polymerization Reactor Setupmentioning

confidence: 99%

“…When the alkoxide feed is stopped, the reaction proceeds until the complete consumption of the monomer. As reported in a previous work, 4 the reactor modeling has been based on the following assumptions:…”

Section: Polymerization Reactor Setupmentioning

confidence: 99%

“…When the purpose of the simulation is shifted toward copolymers, with block or random structures, we have adopted a different strategy, as described in another recently published paper. 4 According to this strategy we have presented the possibility to simulate the copolymer MWD and microstructure by using only the two monomers (EO and PO) consumption rates and then build any single polymer chain on a statistical basis with character encoding instead of considering all the reaction rates involving any chemical species. This novel approach allowed, at the price of a reasonable approximation, to obtain a CBC description of the system and consequently the MWD and sequence length distribution (SLD) of the desired product.…”

Section: Introductionmentioning

confidence: 99%

“…In the present work, the polymerization of the most representative among the mentioned products will be simulated for different operative conditions and the obtained results will be compared with the available data of literature. The simulations, performed with the MC approach, already described in a previous work, 4 will consider the following aspects: the time evolution of the alkoxide/substrate molar ratio; the occurrence of the PO to allyl group side reaction with related consequences, and the MWDs. Moreover, the KMC model gives also detailed information on the microstructure of the individual chain through character encoding.…”

Section: Introductionmentioning

confidence: 99%

“…The number of molecules in the chosen volume must be high enough for the statistical purpose but small, as much as possible, for reducing the overall calculation time. The developed application of the stochastic model has already been described in detail in a previously published work 4 in which the EO/PO homo-and copolymerization, using ethylene glycol as starter and KOH as the catalyst, were simulated.…”

Section: Introductionmentioning

confidence: 99%

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Monte Carlo Simulation of Glycerol Poly-alkoxylation: A Novel Application of a Stochastic Algorithm

Tesser

Santacesaria²

2021

Ind. Eng. Chem. Res.

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Propylene oxide (PO) homopolymer and PO/ethylene oxide (EO) copolymers, initiated by the starter glycerol (GLY), are the most popular polyols employed in the production of elastic polyurethanes. The molecular weight (MW) of these polymers falls in the range 2000–6500 Da. The simulation of polymerization and copolymerization of EO and PO to obtain high-molecular-weight polymers can hardly be made by using a deterministic model that requires the solution of a system of many differential and algebraic equations (many thousands in some cases) with a high calculation time. A new application of a stochastic model has recently been proposed by the authors that can simulate EO and PO homo- and copolymerization in a few minutes of calculation time that results much efficient especially in the case of copolymer simulation. In other words, while deterministic and stochastic approaches can be considered almost equivalent for homopolymerization, we found that for complex alkoxylated copolymers the Monte Carlo (MC) method is preferred. The method, already described in our previous work, was employed to simulate the behavior of a bifunctional starter as ethylene glycol (EG), giving not only the description of the time profile of all the occurring reactions but also the microstructure of the polymers obtained. In this work, the developed MC kinetic model has been extended to the simulation of EO and PO homo- and copolymerization using the trifunctional starter GLY. Different systems will be considered as examples of simulation, such as the GLY-PO homopolymerization, the GLY-EO-PO random copolymerization, and the GLY-EO-PO block copolymerization. Results will be presented for the mentioned systems by considering the effect of the different EO/PO molar ratios, the time evolution of the alkoxide/substrate molar ratio, the occurrence of the PO to allyl group side reaction with related consequences, and the molecular weight distribution. Moreover, the model is also able to give detailed information on the single-chain microstructure in terms of sequence length distribution. A detailed description will be given, in this work, about the selection of the most reliable kinetics parameters.

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Section: Polymerization Reactor Setupmentioning

confidence: 99%

Section: Polymerization Reactor Setupmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Monte Carlo Simulation of Glycerol Poly-alkoxylation: A Novel Application of a Stochastic Algorithm

Tesser

Santacesaria²

2021

Ind. Eng. Chem. Res.

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Revealing the Monomer Gradient of Polyether Copolymers Prepared Using N‐Heterocyclic Olefins: Metal‐Free Anionic versus Zwitterionic Lewis Pair Polymerization

Kersten

Linker

Blankenburg

et al. 2023

Macro Chemistry & Physics

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N‐Heterocyclic olefin (NHO)‐based polymerization pathways for the copolymerization of ethylene oxide (EO) and propylene oxide (PO) are investigated in detail. Employing in situ 1H NMR spectroscopy, both an organocatalytic, anionic polymerization setup (system A) and a zwitterionic, Lewis pair‐type approach (system B) are studied comparatively. The obtained kinetics data are fitted to the non‐terminal model (Jaacks and Ideal Integrated) and terminal Mayo–Lewis model (Meyer Lowry) to determine the reactivity ratios, revealing striking differences in copolyether microstructure and achievable molar masses. While for the metal‐free catalysis (system A) reactivity ratios of rEO = 3.4 and rPO = 0.30 are found, indicating a soft gradient structure, the presence of Mg(HMDS)2 (system B) entails exclusively zwitterionic propagation. This results in enhanced selectivity, displaying corresponding parameters of rEO = 7.9 and rPO = 0.13, in line with the proposed monomer‐activated mechanism. The block‐like, strongly tapered copolyether microstructure is also reflected in the thermal properties, showing a melting point for the latter sample and much higher molar masses (Mn >50 000 g mol−1). Notably, this study not only identifies capable polymerization systems for EO/PO, but also underlines that via in situ 1H NMR kinetics key questions regarding the polymerization mechanism can be illuminated quickly and reliably, simplifying access to essential structure‐property relations.

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A novel approach to inulin depolymerization: A Monte Carlo based model

Russo

Grénman

Salmi

et al. 2022

Chemical Engineering Science

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Monte Carlo Approach to the Simulation of Ethylene Oxide and Propylene Oxide Polymerization and Copolymerization

Cited by 4 publications

References 24 publications

Monte Carlo Simulation of Glycerol Poly-alkoxylation: A Novel Application of a Stochastic Algorithm

Monte Carlo Simulation of Glycerol Poly-alkoxylation: A Novel Application of a Stochastic Algorithm

Revealing the Monomer Gradient of Polyether Copolymers Prepared Using N‐Heterocyclic Olefins: Metal‐Free Anionic versus Zwitterionic Lewis Pair Polymerization

A novel approach to inulin depolymerization: A Monte Carlo based model

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