D'hooge, Dagmar

Konkolewicz, D

Marin, Guy

Matyjaszewski, K

Reyniers, Marie-Françoise

Van Steenberge, Paul

Wang, Y

Zhong, M

English

Ghent University Academic Bibliography

MODEL BASED DETERMINATION OF LINEAR GRADIENT QUALITY OF  ATRP COPOLYMERSP.H.M. Van Steenberge1, D.R. D’hooge1, Y. Wang2, M. Zhong2, D. Konkolewicz2, M.-F. Reyniers1,*, K. Matyjaszewski2 and G.B. Marin11 Laboratory for Chemical Technology, Krijgslaan 281 (S5), 9000 Ghent, Belgiumhttp://www.lct.UGent.be          E-mail: MarieFrancoise.Reyniers@UGent.be2 Center for Macromolecular Engineering, Carnegie Mellon University 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, USABelgian-German [Macro]Molecular Meeting, Houffalize, 03/12/2012AcknowledgmentsThis work is supported by the Institute for the Promotion of Innovationthrough Science and Technology in Flanders (IWT Vlaanderen), the‘Long Term Structural Methusalem Funding by the Flemish Government’and the Science Foundation (CHE 10-26060)European Research Institute of CatalysisLinear gradient polymersLinear gradient copolymers exhibit a gradual linear shift in themonomer composition from one chain end to the other:Conventional simulation:Average polymer propertiesAtom transfer radical polymerizationControlled radical polymerization (CRP) allows the synthesisof macromolecules with predetermined chain length, lowpolydispersity, end-group functionality and controlledtopology. Radicals are temporarily deactivated by a mediatingagent. In atom transfer radical polymerization (ATRP), thisactivation/deactivation process is catalyzed by a transitionmetal complex. Under ideal conditions, all polymer chainsgrow concurrently and termination reactions are suppressed.Kinetic Monte Carlo (kMC) simulation flow sheetDetailed kMC simulation:sample of the polymer productlinearlowhighGradient evaluationCatalyst choice foroptimal gradient qualityLinear Gradient quality (xm)Dormant polymerDead polymerChemical composition – chain length distributionDeviation from ideal linear gradient decreases toward final conversion:relatively good linear gradient ConclusionsA new copolymer property, i.e. the linear gradient deviation (<GD>) isintroduced and applied to ATRP. For <GD> values lower than 0.3 thelinear gradient quality is good. For the ATRP of methacrylates andacrylates, batch ATRP conditions allow to prepare copolymers with agood linear gradient quality in case an appropriate ATRP catalyst ischosen. The developed methodology can be also applied to othercontrolled radical polymerization techniques such as nitroxide mediatedpolymerization and reversible addition-fragmentation chain transferpolymerization.No reaction eventPropagation with methacrylatePropagation with acrylateSlow exchange => unwanted A and B dormant homopolymerGood exchange => optimal gradientFast exchange => too much dead homopolymer Axm= monomer conversionMethacrylates and acrylates may form gradient polymers~gradual~gradualxm= 1badgoodxm= 1Importance of reactivity ratiosPDI (-)<GD> (-)

Model based determination of linear gradient quality of ATRP copolymers

https://biblio.ugent.be/publication/3159181/file/3159208.pdf

Model based determination of linear gradient quality of ATRP copolymers

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