Improved Livingness and Control over Branching in RAFT Polymerization of Acrylates: Could Microflow Synthesis Make the Difference?

The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer (RAFT) solution polymerization of n‐butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies...

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Vydáno v:	Macromolecular rapid communications. Ročník 36; číslo 24; s. 2149 - 2155
Hlavní autoři:	Derboven, Pieter, Van Steenberge, Paul H. M., Vandenbergh, Joke, Reyniers, Marie-Francoise, Junkers, Thomas, D'hooge, Dagmar R., Marin, Guy B.
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	Germany Blackwell Publishing Ltd 01.12.2015 Wiley Subscription Services, Inc
Témata:	Acrylates Acrylic Resins - chemical synthesis Acrylic Resins - chemistry Acrylics Addition polymerization Batch reactors branching Chain transfer Chemical industry Chemical synthesis Cleavage Dilution Microreactors polymer kinetics Polymerization RAFT Rafts Reactors Reagents reversible addition-fragmentation chain transfer reversible addition–fragmentation chain transfer, RAFT Solution polymerization reversible addition-fragmentation chain transfer, RAFT branching acrylates microreactors polymer kinetics
ISSN:	1022-1336, 1521-3927, 1521-3927
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Abstract	The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer (RAFT) solution polymerization of n‐butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β‐scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer solution polymerization of n‐butyl acrylate due to isothermicity of the former. Importantly, detailed kinetic analysis also allows to determine unambiguously the different underlying causes for the effect of the microreactor conditions on the cumulative branching content and the degree of livingness.
AbstractList	The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer (RAFT) solution polymerization of n‐butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β‐scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer solution polymerization of n‐butyl acrylate due to isothermicity of the former. Importantly, detailed kinetic analysis also allows to determine unambiguously the different underlying causes for the effect of the microreactor conditions on the cumulative branching content and the degree of livingness. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer (RAFT) solution polymerization of n ‐butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β‐scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. image The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution polymerization of n-butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β-scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution polymerization of n-butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and beta -scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer solution polymerization of n-butyl acrylate due to isothermicity of the former. Importantly, detailed kinetic analysis also allows to determine unambiguously the different underlying causes for the effect of the microreactor conditions on the cumulative branching content and the degree of livingness. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution polymerization of n-butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β-scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA.The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution polymerization of n-butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and β-scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA. The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution polymerization of n-butyl acrylate with the aid of simulations, explicitly accounting for the chain length distribution of all macrospecies types. Since perfect isothermicity can be established in a microreactor, less side products due to backbiting and [beta]-scission are formed compared to the batch operation in which ineffective heat removal leads to an undesirable temperature spike. For a given RAFT chain transfer agent (CTA), additional microstructural control results under microflow conditions by optimizing the reaction temperature, lowering the dilution degree, or decreasing the initial molar ratio of monomer to RAFT CTA.
Author	Junkers, Thomas Van Steenberge, Paul H. M. D'hooge, Dagmar R. Reyniers, Marie-Francoise Marin, Guy B. Vandenbergh, Joke Derboven, Pieter
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Keywords	reversible addition-fragmentation chain transfer, RAFT branching acrylates microreactors polymer kinetics
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Snippet	The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition–fragmentation chain transfer (RAFT) solution... The superior capabilities of structured microreactors over batch reactors are demonstrated for reversible addition-fragmentation chain transfer (RAFT) solution...
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SubjectTerms	Acrylates Acrylic Resins - chemical synthesis Acrylic Resins - chemistry Acrylics Addition polymerization Batch reactors branching Chain transfer Chemical industry Chemical synthesis Cleavage Dilution Microreactors polymer kinetics Polymerization RAFT Rafts Reactors Reagents reversible addition-fragmentation chain transfer reversible addition–fragmentation chain transfer, RAFT Solution polymerization
Title	Improved Livingness and Control over Branching in RAFT Polymerization of Acrylates: Could Microflow Synthesis Make the Difference?
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