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An equation driven quality classification of (a)symmetric gradient, gradient-block, block-gradient-block and block copolymers

Robert Conka (UGent) , Yoshi Marien (UGent) , Paul Van Steenberge (UGent) , Richard Hoogenboom (UGent) and Dagmar D'hooge (UGent)
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Abstract
The control of the A/B comonomer distribution over individual chains targeting block and/or gradient monomer distributions is essential to control the macroscopic properties of the resulting copolymers. Matrix-based kinetic Monte Carlo simulations allow to compare each chain of a representative copolymer sample with the desired (mathematical) composition, as defined by monomer inclusion probabilities (PA/B) taking the B-functionalization degree (B-Func) as maximally 50%. A so-called average deviation (SD* value) results per chain, with a close to 0 average (normalized) structural deviation 〈SD〉 corresponding to an almost perfect structure and a 〈SD〉 close to 1 representing the worst case scenario of a B-homopolymer. The previously assigned 〈SD〉 transitions from excellent to good and from good to poor are, however, somewhat arbitrary, e.g. for both symmetric gradient and block copolymers a threshold 〈SDGood/Poor〉 of 0.3 is currently utilized and only for specific asymmetric cases (30% B-Func block, block-gradient, and gradient) 〈SDExc/Good〉 and 〈SDGood/Poor〉 values have been reported. The present work puts forward an equation driven method to obtain 〈SD〉 threshold values, minimizing the arbitrary nature of the quality classification for a given copolymer type and more importantly aligning the quality assessment for any copolymer type containing block and/or gradient elements. Emphasis is on the complete SD distribution (instead of only its average) for (a)symmetric AB gradient, block A-gradient AB, block A-gradient AB-block B, and AB block copolymers by introducing the overall gradient and block fractions (fGr/Bl) as a novel parameter alongside the targeted degree of polymerization (target DP) and B-Func. Ideal theoretical structures with equal chain length and a perfect implementation of the desired PA/B profiles are dealt with, as they represent the best case an actual synthesis recipe could deliver in the limit. It is shown that the log-normal distribution can be reliably used to approximate the SD distribution, as coefficients of determination (R2) very close to one follow for (a)symmetric copolymers . It is further showcased that threshold values for gradient dominant structures must be higher than those for block-like structures and that well-defined symmetric structures are more difficult to achieve than asymmetric ones. It is also recommended to report 〈SD〉 together with its standard deviation σSD.
Keywords
Organic Chemistry, Polymers and Plastics, Materials Chemistry, Polymer Reaction Engineering, Copolymers, Compositional distributions, Gradient deviation, Kinetic, Monte Carlo, CONTROLLED RADICAL POLYMERIZATION, GLASS-TRANSITION TEMPERATURE, POLY(N-BUTYL ACRYLATE), AMPHIPHILIC GRADIENT, RAFT POLYMERIZATION, COMPATIBILIZATION, SEQUENCE, BLENDS, PHASE, MICELLIZATION

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Citation

Please use this url to cite or link to this publication:

MLA
Conka, Robert, et al. “An Equation Driven Quality Classification of (a)Symmetric Gradient, Gradient-Block, Block-Gradient-Block and Block Copolymers.” EUROPEAN POLYMER JOURNAL, vol. 185, 2023, doi:10.1016/j.eurpolymj.2022.111769.
APA
Conka, R., Marien, Y., Van Steenberge, P., Hoogenboom, R., & D’hooge, D. (2023). An equation driven quality classification of (a)symmetric gradient, gradient-block, block-gradient-block and block copolymers. EUROPEAN POLYMER JOURNAL, 185. https://doi.org/10.1016/j.eurpolymj.2022.111769
Chicago author-date
Conka, Robert, Yoshi Marien, Paul Van Steenberge, Richard Hoogenboom, and Dagmar D’hooge. 2023. “An Equation Driven Quality Classification of (a)Symmetric Gradient, Gradient-Block, Block-Gradient-Block and Block Copolymers.” EUROPEAN POLYMER JOURNAL 185. https://doi.org/10.1016/j.eurpolymj.2022.111769.
Chicago author-date (all authors)
Conka, Robert, Yoshi Marien, Paul Van Steenberge, Richard Hoogenboom, and Dagmar D’hooge. 2023. “An Equation Driven Quality Classification of (a)Symmetric Gradient, Gradient-Block, Block-Gradient-Block and Block Copolymers.” EUROPEAN POLYMER JOURNAL 185. doi:10.1016/j.eurpolymj.2022.111769.
Vancouver
1.
Conka R, Marien Y, Van Steenberge P, Hoogenboom R, D’hooge D. An equation driven quality classification of (a)symmetric gradient, gradient-block, block-gradient-block and block copolymers. EUROPEAN POLYMER JOURNAL. 2023;185.
IEEE
[1]
R. Conka, Y. Marien, P. Van Steenberge, R. Hoogenboom, and D. D’hooge, “An equation driven quality classification of (a)symmetric gradient, gradient-block, block-gradient-block and block copolymers,” EUROPEAN POLYMER JOURNAL, vol. 185, 2023.
@article{01GS84TER9K8PM11W0YMT15MQJ,
  abstract     = {{The control of the A/B comonomer distribution over individual chains targeting block and/or gradient monomer distributions is essential to control the macroscopic properties of the resulting copolymers. Matrix-based kinetic Monte Carlo simulations allow to compare each chain of a representative copolymer sample with the desired (mathematical) composition, as defined by monomer inclusion probabilities (PA/B) taking the B-functionalization degree (B-Func) as maximally 50%. A so-called average deviation (SD* value) results per chain, with a close to 0 average (normalized) structural deviation 〈SD〉 corresponding to an almost perfect structure and a 〈SD〉 close to 1 representing the worst case scenario of a B-homopolymer. The previously assigned 〈SD〉 transitions from excellent to good and from good to poor are, however, somewhat arbitrary, e.g. for both symmetric gradient and
block copolymers a threshold 〈SDGood/Poor〉 of 0.3 is currently utilized and only for specific asymmetric cases (30% B-Func block, block-gradient, and gradient) 〈SDExc/Good〉 and 〈SDGood/Poor〉 values have been reported. The present work puts forward an equation driven method to obtain 〈SD〉 threshold values, minimizing the arbitrary nature of the quality classification for a given copolymer type and more importantly aligning the quality assessment for
any copolymer type containing block and/or gradient elements. Emphasis is on the complete SD distribution
(instead of only its average) for (a)symmetric AB gradient, block A-gradient AB, block A-gradient AB-block B, and
AB block copolymers by introducing the overall gradient and block fractions (fGr/Bl) as a novel parameter alongside the targeted degree of polymerization (target DP) and B-Func. Ideal theoretical structures with equal
chain length and a perfect implementation of the desired PA/B profiles are dealt with, as they represent the best
case an actual synthesis recipe could deliver in the limit. It is shown that the log-normal distribution can be
reliably used to approximate the SD distribution, as coefficients of determination (R2) very close to one follow for (a)symmetric copolymers . It is further showcased that threshold values for gradient dominant structures must be higher than those for block-like structures and that well-defined symmetric structures are more difficult to
achieve than asymmetric ones. It is also recommended to report 〈SD〉 together with its standard deviation σSD.}},
  articleno    = {{111769}},
  author       = {{Conka, Robert and Marien, Yoshi and Van Steenberge, Paul and Hoogenboom, Richard and D'hooge, Dagmar}},
  issn         = {{0014-3057}},
  journal      = {{EUROPEAN POLYMER JOURNAL}},
  keywords     = {{Organic Chemistry,Polymers and Plastics,Materials Chemistry,Polymer Reaction Engineering,Copolymers,Compositional distributions,Gradient deviation,Kinetic,Monte Carlo,CONTROLLED RADICAL POLYMERIZATION,GLASS-TRANSITION TEMPERATURE,POLY(N-BUTYL ACRYLATE),AMPHIPHILIC GRADIENT,RAFT POLYMERIZATION,COMPATIBILIZATION,SEQUENCE,BLENDS,PHASE,MICELLIZATION}},
  language     = {{eng}},
  pages        = {{16}},
  title        = {{An equation driven quality classification of (a)symmetric gradient, gradient-block, block-gradient-block and block copolymers}},
  url          = {{http://doi.org/10.1016/j.eurpolymj.2022.111769}},
  volume       = {{185}},
  year         = {{2023}},
}

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