D'hooge, Dagmar

Marin, Guy

Reyniers, Marie-Françoise

Toloza Porras, Carolina

Van Steenberge, Paul

English

Ghent University Academic Bibliography

Laboratory for Chemical Technology, Krijgslaan 281 (S5), 9000 Ghent, Belgium  http://www.lct.UGent.be          E-mail:MarieFrancoise.Reyniers@UGent.be  European Research Institute of Catalysis Annual Meeting of the Belgian Polymer Group, Houffalize, Belgium, 16-17/05/2013 One- and Two-Pot Synthesis of Well-defined Diblock Copolymers by ICAR ATRP: a theoretical exploration C. Toloza Porras, D. R. D’hooge, P. H. M. Van Steenberge, M.-F. Reyniers, G. B. Marin Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP) Ideal block profile ATRP has been extensively used for the synthesis of diverse macromolecular structures. Although ATRP allows unique polymer properties, the production of large volumes of ATRP based materials is being thwarted by the excessive concentrations of Cu-based catalysts that are usually necessary to achieve a fast and controlled polymerization.[1] The reduction of the catalyst concentration up to 50 ppm has been enable by the introduction of modified ATRP techniques, such as ICAR ATRP in which activator species are regenerated from the deactivator in the presence of a conventional radical initiator, avoiding therefore handling of the air-sensitive activator species and expensive purification operations.[2]             [1] D. F. Grishin et al., Russian Journal of Applied Chemistry 2011, 84, 2021-2028 [2] K. Matyjaszewski et al., Proceedings of the National Academy of Sciences of the United States of America 2006, 103, 15309-15314 One-Pot ICAR ATRP Two-Pot ICAR ATRP Kinetic Monte Carlo simulations indicate that well-defined poly(iBoA-b-Sty) diblock(-like) copolymers with an average chain length of circa 80 at an overall conversion of 0.80 can be synthesized by bulk ICAR ATRP using both one-pot semi-batch and two-pot batch approaches. In order to quantify the block copolymer quality, a block deviation value (<BD>), which ranges between 0 and 1, is introduced based on the calculation of the explicit copolymer composition. This value reflects the average deviation of a representative polymer sample with respect to perfect diblock reference copolymer chains.  Kinetic Monte Carlo Model Acknowledgements: The authors acknowledge financial support from the Long Term Structural Methusalem Funding by the Flemish Government, the Interuniversity Attraction Poles Programme – Belgian State – Belgian Science Policy, the Fund for Scientific Research Flanders (FWO), and the Institute for the Promotion of Innovation through Science and Technology in Flanders (IWT Vlaanderen).  Input: Intrinsic kinetic parameters: kchem, fchem Diffusion parameters for calculation of DAB Polymerization conditions: T, ttot  Number of molecules: 𝒏𝑨𝟎𝒏𝑩𝟎 Calculation of: -   Volume: V=f(T, 𝒏𝑨𝟎𝒏𝑩𝟎, … ) - Apparent Monte Carlo rate coefficients for all possible reactions v (kvapp, MC =f(kchem, DAB,V, NA)  Calculation of: - Apparent Monte Carlo reaction rates - 𝑹 𝒗 = 𝒌𝒂𝒑𝒑,𝑴𝑪𝒗 𝒏𝑨𝒏𝑩 - Time between 2 reactions (τ) - 𝝉 = −𝑳𝒏 𝒓𝟏  𝑹(𝒗)𝒗−𝟏 - Apparent reaction probabilities - 𝑷 𝒗 = 𝑹(𝒗)  𝑹(𝒗)𝒗−𝟏   Update: - Number of molecules 𝒏𝑨𝒏𝑩 -  Polymerization time t=t+τ Random selection of reaction event  𝑷 𝒗 ≤ 𝒓𝟐 ≤𝒗=𝝁−𝟏𝒗=𝟏 𝑷 𝒗𝒗=𝝁𝒗=𝟏  Based on reaction probabilities Update the copolymer composition matrix Dormant Dead Random selection of resulting chain length  from a chain length dependent reaction event Calculation of: Block deviation value <BD> per chain z   iyBABidealBAABidealAABiSSSSzBD12,,,,21)(t=tTot? No Yes End Diblock Quality Real block profile Conclusions:  • μ=1: 𝑰𝟐    𝒇 𝒌𝒅𝒊𝒔,𝒄𝒉𝒆𝒎     𝟐𝑰 • μ=2: 𝑹𝒊 +𝑴𝒌𝒂𝒑𝒑,𝑴𝑪𝒑𝑹𝒊+𝟏 • μ=3: 𝑹𝒊 +𝑴𝒕𝒏𝑿𝑳𝒌𝒂𝒑𝒑,𝑴𝑪𝒂𝑹𝒊𝑿 +𝑴𝒕𝒏+𝟏𝑿𝟐 𝑳  • μ=4: 𝑹𝒊𝑿+𝑴𝒕𝒏+𝟏𝑿𝟐 𝑳𝒌𝒂𝒑𝒑,𝑴𝑪𝒅𝒂𝑹𝒊 +𝑴𝒕𝒏𝑿𝑳 • μ=5: 𝑹𝒊 + 𝑹𝒋𝒌𝒂𝒑𝒑,𝑴𝑪𝒕𝑷𝒊+𝒋 400ppm Cu 200ppm Cu 200ppm Cu C. Toloza Porras et al., 2013, Macromol. React. Eng., in press, DOI 10.1002/mren.201200085. 

One- and two-pot synthesis of well-defined diblock copolymers by ICAR ATRP: a theoretical exploration

https://biblio.ugent.be/publication/4410146/file/4410463

One- and two-pot synthesis of well-defined diblock copolymers by ICAR ATRP: a theoretical exploration

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