Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

Chen, Jing; Zhao, Xiaoning; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

doi:10.1002/pola.27582

Cited by 11 publications

(6 citation statements)

References 54 publications

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“…The largest M n obtained was 104,000 g mol −1 at a ratio of [M] 0 /[CTA] 0 = 3000/1. This result compares very favorably with literature data where a pressurized reactor and a ratio [M] 0 /[CTA] 0 = 10,000/1 was used yielding a M n of 123,000 g mol −1 , a dispersity of 1.28 with a 37% conversion, while using our approach we obtained a much higher conversion of 97% for a polymer with a similar M n , albeit with a higher dispersity of 1.83.…”

Section: Introductionsupporting

confidence: 89%

“…Chen et al have shown the MADIX polymerization of vinyl acetate under 5 or 1 kbar pressure with a high pressure reaction system using ethyl acetate as the solvent at 35 °C. They used a range of xanthates with differing R and Z groups in order to synthesize high‐molecular‐weight PVAc (>100,000 g mol −1 ), however, the monomer conversions were typically around 35%. Congdon et al have reported the polymerization of PVAc in bulk using S ‐benzyl‐ O ‐ethyl dithiocarbonate as the MADIX agent, with molecular weights of up to 30,050 g mol −1 although the monomer conversions were incomplete ranging from 68% to 83% conversion .…”

Section: Introductionmentioning

confidence: 99%

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MADIX polymerization of vinyl acetate using ethyl acetate as a green solvent; near-complete monomer conversion with molecular weight control

Levere

Chambon

Rannard

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Section: Introductionsupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

MADIX polymerization of vinyl acetate using ethyl acetate as a green solvent; near-complete monomer conversion with molecular weight control

Levere

Chambon

Rannard

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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show abstract

“…The solution of multivariate PBEs is a highly complex problem, for which seldom solution approaches have been developed. Reported methods include the numerical fractionation technique, the fixed pivot technique, or the moment distribution method [94][95][96]. Regarding applications to NMP processes, one of the few reported works is the one by Fortunatti et al [67].…”

Section: Multivariate Distributionsmentioning

confidence: 99%

Deterministic Approaches for Simulation of Nitroxide-Mediated Radical Polymerization

Asteasuain

2018

International Journal of Polymer Science

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Since its development in the last decades, controlled radical polymerization (CRP) has become a very promising option for the synthesis of polymers with controlled structure. The design and production of tailor-made materials can be significantly improved by developing models capable of predicting the polymer properties from the operating conditions. Nitroxide-mediated polymerization (NMP) was the first of the three main variants of CRP to be discovered. Although it has lost preference over the years against other CRP alternatives, NMP is still an attractive synthesis method because of its simple experimental implementation and environmental friendliness. This review focuses on deterministic methods employed in mathematical models of NMP. It presents an overview of the different techniques that have been reported for modelling NMP processes in homogeneous and heterogeneous media, covering from the prediction of average properties to the latest techniques for modelling univariate and multivariate distributions of polymer properties. Finally, an outlook of model-based design studies of NMP processes is given.

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“…One of these methods is the numerical fractionation technique. It was used for predicting the bivariate MWD-LBCD (Chen et al, 2015;Pladis & Kiparissides, 1998), the bivariate MWDnumber of active sites distribution (Lazzari & Storti, 2014) and the single MWD of branched polymers (Kizilel et al, 2007;Papavasiliou & Teymour, 2003). It consists of dividing the total population of polymer chains into classes according to the number of branching points.…”

Section: Introductionmentioning

confidence: 99%

Improved numerical inversion methods for the recovery of bivariate distributions of polymer properties from 2D probability generating function domains

Brandolin

Balbueno

Asteasuain

2016

Computers & Chemical Engineering

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Please cite this article as: Brandolin, Adriana., Balbueno, Ayslane Assini., & Asteasuain, Mariano., Improved numerical inversion methods for the recovery of bivariate distributions of polymer properties from 2D probability generating function domains.Computers and Chemical Engineering http://dx. GRAPHICAL ABSTRACTIn this work two 2D pgf inversion methods are developed, for which the pgf is regarded as a complex variable. These methods provide an outstanding accuracy in the inversion, thus allowing extending the 2D pgf technique for modeling bivariate distributions without restrictions in the range of values of its independent domains HIGHLIGHTS  Advanced modeling of polymer processes.  Prediction of bivariate (2D) distributions of polymer molecular properties.  Improvement of the pgf modeling method.  Development of new pgf inversion methods that use complex and/or real pgf.  Accurate modeling of 2D distributions with domains of different orders of magnitude. AbstractThe 2D probability-generating function technique is a powerful method for modeling bivariate distributions of polymer properties. It is based on the transformation of bivariate population balance equations using 2D probability generating functions (pgf) followed by a recovery of the distributions from the transform domain by numerical inversion. A key step of this method is the inversion of the pgf transforms. Available numerical inversion methods yield excellent results for pgf transforms of distributions with independent dimensions with similar orders of magnitude, for example bivariate molecular weight distributions in copolymerization systems.However, numerical problems are found for 2D distributions in which the independent dimensions have very different ranges of values, such as the molecular weight distributionbranching distribution in branched polymers. In this work, two new 2D pgf inversion methods are developed, which regard the pgf as a complex variable. The superior accuracy of these innovative methods makes them suitable for recovering any type of bivariate distribution. This enhances the capabilities of the 2D pgf modeling technique for simulation and optimization of polymer processes. An application example of the technique in a polymeric system of industrial interest is presented.

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Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

Cited by 11 publications

References 54 publications

MADIX polymerization of vinyl acetate using ethyl acetate as a green solvent; near-complete monomer conversion with molecular weight control

MADIX polymerization of vinyl acetate using ethyl acetate as a green solvent; near-complete monomer conversion with molecular weight control

Deterministic Approaches for Simulation of Nitroxide-Mediated Radical Polymerization

Improved numerical inversion methods for the recovery of bivariate distributions of polymer properties from 2D probability generating function domains

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