Modeling and Experimentation of RAFT Solution Copolymerization of Styrene and Butyl Acrylate, Effect of Chain Transfer Reactions on Polymer Molecular Weight Distribution

Jiang, Jie; Wang, Wenjun; Li, Bo‐Geng; Zhu, Shiping

doi:10.1002/mren.201700029

Cited by 6 publications

(3 citation statements)

References 49 publications

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“…Several kinetic models have been developed for RAFT homo- [ 56 , 57 , 58 ] and copolymerization of a few monomers [ 59 , 60 , 61 , 62 ]. As stated earlier, in our polymerization scheme we assumed that no branches to the adduct were produced, making it easier to model our RAFT copolymerization system using the terminal model [ 53 ], which is given by Equations (37)–(42).…”

Section: Resultsmentioning

confidence: 99%

Mathematical Description of the RAFT Copolymerization of Styrene and Glycidyl Methacrylate Using the Terminal Model

et al. 2022

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A mathematical model for the kinetics, composition and molar mass development of the bulk reversible addition-fragmentation chain transfer (RAFT) copolymerization of glycidyl methacrylate (GMA) and styrene (St), at several GMA molar feed fractions at 103 °C, in the presence of 2-cyano isopropyl dodecyl trithiocarbonate as the RAFT agent and 1,1′-azobis(cyclohexane carbonitrile), as the initiator, is presented. The copolymerization proceeded in a controlled manner and dispersities of the copolymers remained narrow even at high conversions. Experimental data and calculated profiles of conversion versus time, composition versus conversion and molar mass development for the RAFT copolymerization of St and GMA agreed well for all conditions tested, including high-conversion regions. The kinetic rate constants associated with the RAFT- related reactions and diffusion-controlled parameters were properly estimated using a weighted nonlinear multivariable regression procedure. The mathematical model developed in this study may be used as an aid in the design and upscaling of industrial RAFT polymerization processes.

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Section: Resultsmentioning

confidence: 99%

Mathematical Description of the RAFT Copolymerization of Styrene and Glycidyl Methacrylate Using the Terminal Model

et al. 2022

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“…[1][2][3][4][5][6][7][8][9][10] MWD of produced polymer usually depends on the polymerization mechanism and kinetics. [11][12][13][14][15][16][17][18][19][20] In general, living anionic polymerization produces chains with narrow MWD, while traditional free radical polymerization yields broadly distributed chains. [20] To better understand the connection between kinetics and MWD as well as to clarify which theory is correct or more proper, many efforts have been made to simulate MWD.…”

Section: Introductionmentioning

confidence: 99%

“…[20] To better understand the connection between kinetics and MWD as well as to clarify which theory is correct or more proper, many efforts have been made to simulate MWD. [11,12,16,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] Three methods, i.e., moments, Monte Carlo, and solving ordinary differential equations directly, have been developed. [14,16] Among them, the most used is the method of moments because it is not only based on clear reaction mechanism and kinetic equation, but also ratio (RR) of chain propagation to chain transfer can give an impact on the degree of uniformity of chain length.…”

Section: Introductionmentioning

confidence: 99%

Molecular Weight Distribution in Ring‐Opening Polymerization of Propylene Oxide Catalyzed by Double Metal Complex: A Model Simulation

Zhao

Fan

2021

Macro Theory & Simulations

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easy to calculate. Even though this method cannot show out the full MWD curves, it gathers the most important information such as monomer conversion (x), molecular weight (MW), and polydispersity index (PDI). [28] PDI quantifies the width of MWD.The ring-opening polymerization (ROP) of propylene oxide (PO) catalyzed by double metal complex (DMC) is generally considered to have the characteristics of living polymerization. For example, the MW increases with x, and block copolymers with ethylene oxide can be prepared. However, our recent experimental study shows that the MWD of products is not easy to keep very narrow even if the polymerization is carried out in batch or plug flow reactor. [34] According to the polymerization mechanism proposed by Huang et al., [35][36][37] it is generally believed that the chain transfer reaction between active chains and dormant chains is the key to narrow MWD. However, up to now, no one has quantitatively investigated the effect of this chain transfer reaction on the MWD.In this work, a kinetic model involving chain propagation and chain transfer is established; the method of moments is used to simulate PDI as well as x and number-average polymerization degree (Xn) under various reaction conditions. We hope that this work can facilitate the understanding of the polymerization mechanism behind various complex phenomena in the ROP catalyzed by DMC. Modeling Section Polymerization MechanismAs Huang et al. [35][36][37] and Kim et al. [38,39] have reported, ROP of PO catalyzed by DMC consists of induction, chain propagation, and transfer reaction. Herein, only the chain propagation and transfer reaction are considered since they are the main reactions that affect MWD. As shown in Scheme 1, chains with active center can be propagated; meanwhile, the active center can be transferred to dormant chains so that they are activated and propagated. It is the chain transfer between the active chain and dormant chain that results in the more uniform chain growth. Obviously, it can be thought that the instant rate In the present work, method of moments is used to model the molecular weight distribution (MWD) of polypropylene glycol (PPG) produced with ring-opening polymerization of propylene oxide catalyzed by double metal complex (DMC), and an explicit expression about the polydispersity index (PDI) of PPG is obtained. The simulated results indicate that decreasing the initial concentration ratio of monomer to total chains (K 1 ) or increasing the rate constant ratio of chain transfer to propagation (K 2 ) leads to smaller PDI. Reducing the concentration of DMC can induce larger PDI. When the PPG's initial PDI (i.e., PDI of initiator) increases, PDI of the final PPG grows up linearly. However, with the increase of monomer conversion, PDI increases first and then decreases, that is, there is a critical conversion. The possible lack of chain transfer at the beginning of polymerization and the insufficient chain transfer caused by increased K 1 , decreased concentration of catalyst, and decreased...

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Mathematical Modelling of RAFT Polymerization

López‐Domínguez

Zapata‐González²,

Saldívar‐Guerra

et al. 2021

RAFT Polymerization

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Modeling and Experimentation of RAFT Solution Copolymerization of Styrene and Butyl Acrylate, Effect of Chain Transfer Reactions on Polymer Molecular Weight Distribution

Cited by 6 publications

References 49 publications

Mathematical Description of the RAFT Copolymerization of Styrene and Glycidyl Methacrylate Using the Terminal Model

Mathematical Description of the RAFT Copolymerization of Styrene and Glycidyl Methacrylate Using the Terminal Model

Molecular Weight Distribution in Ring‐Opening Polymerization of Propylene Oxide Catalyzed by Double Metal Complex: A Model Simulation

Mathematical Modelling of RAFT Polymerization

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