@article{01KKPE2KM4HNEM7YVFE79SPT4A,
  abstract     = {{Gradient copolymers, which feature a gradual transition in monomer composition along the polymer backbone, uniquely combine tunable material properties with inherent stochasticity at the molecular level, bridging the structure-property landscape between block and random copolymers. Their broad glass transition temperature range, self-assembly potential, and amphiphilic behavior, if they consist of hydrophilic and hydrophobic comonomer units, enable applications in damping materials, drug delivery, and cosmetics. Moreover, they are interesting potential substitutes for block copolymers based on their much simpler and cheaper production process. However, gradient copolymers are not as simple as often presumed because they emerge from less trivial monomer inclusion probability profiles that are determined by monomer reactivity ratios and/or feeding profiles. As a result, gradient copolymers exhibit significant compositional heterogeneity, even under idealized conditions (fast chain initiation; no side reactions; and no diffusional limitations). This perspective highlights the critical importance of compositional control and structural evaluation in gradient (tapered) copolymer synthesis, highlighting the relevance of calculating a set of structural deviation (SD) metrics using coupled matrix-based Monte Carlo (CMMC) simulations to assess structural quality. In parallel to experimental protocol development and design, SD metrics such as the average SD (< SD >), SD standard deviation (sigma SD), SD skewness ( mu 3 , S D ), and coefficient of variation (CVSD) can be used to assess whether improved synthesis protocols are worthwhile or not. For a given synthesis recipe, a simultaneous SD evaluation with respect to block, gradient, block-gradient, and block-gradient-block targets is recommended based on a framework calibrated on the individual chain level. This facilitates the identification of the application scope of both exploratory and systematic research on gradient copolymer synthesis approaches.}},
  author       = {{Conka, Robert and Marien, Yoshi and Van Geem, Kevin and Van Steenberge, Paul and Hoogenboom, Richard and D'hooge, Dagmar}},
  issn         = {{2694-2453}},
  journal      = {{ACS POLYMERS AU}},
  keywords     = {{gradient copolymers,structural deviation,compositional distribution,kinetic monte carlo simulations,poly(2-alkyl/aryl-2-oxazoline)s,cationic ring opening polymerization,GLASS-TRANSITION TEMPERATURE,RADICAL POLYMERIZATION,SIZE DISTRIBUTION,CHAIN-LENGTH,ICAR ATRP,BLOCK,SOLVENT,STYRENE,DESIGN}},
  language     = {{eng}},
  number       = {{2}},
  pages        = {{506--519}},
  title        = {{Gradient copolymers : a complex comonomer incorporation reality behind the perfect ideal}},
  url          = {{http://doi.org/10.1021/acspolymersau.5c00147}},
  volume       = {{6}},
  year         = {{2026}},
}

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