Fundamental insights into aminolysis postpolymerization modification reaction of polymers featuring α,α-Difluoroacetate Esters

Fast-Track Computational Access to Reaction Mechanisms Provides Comprehensive Insights into Aminolysis Postpolymerization Modification Reactions

“…Specifically, the reaction with nhexylamine afforded a 100% ester conversion in the postpolymerization step to provide the corresponding aminolyzed product. 21,22 As a proof of concept, we computationally analyzed this postpolymerization modification reaction using a realistic model structure consisting of a hexameric sequence (oligo-CF2CO2Et) and n-hexylamine as a reactant. We computed the four possible reaction pathways without further approximations such as ONIOM, 36 as depicted in Figures 6-9, and calculated the final reaction profiles at the DLPNO-CCSD(T) level of theory to gain an absolute insight into the reactivity.…”

Fast-track computational access to reaction mechanisms provides comprehensive insights into aminolysis postpolymerization modification reactions

“…Specifically, the reaction with n-hexylamine afforded a 100% ester conversion in the postpolymerization step to provide the corresponding aminolyzed product. 21,22 As a proof of concept, we computationally analyzed this postpolymerization modification reaction using a realistic model structure consisting of a hexameric sequence (oligo-CF 2 CO 2 Et) and n-hexylamine as a reactant. For the computations on the oligo-CF 2 CO 2 Et, the initial stable structure search is the important computational task, which is usually very difficult for large molecules because of huge molecular freedom.…”

“…Recently, our group proposed the postpolymerization modification reactions based on the aminolysis of α,αdifluoroacetate esters. [20][21][22] In those studies, we rationalized the experimental conditions for the aminolysis postpolymerization modifications on the basis of mechanistic information obtained by means of density functional theory (DFT) calculations. Specifically, we estimated the transition states (TSs) for the aminolysis of α,α-difluoroacetates using nudged elastic band (NEB) calculations 23 at DFT level and subsequent transit-guided quasi-Newton 24 calculations for methylamine and methyl α,α-difluoro-α-phenylacetate as simplified prototype reactants.…”

Building Machine Learning Models for Reactivity Prediction in Radiation-Induced Graft Polymerization Using Interpretable Parameters

“…[1][2][3][4] Synthetic pathways into functional polymers include direct polymerization of tailor-made functionalized monomers, polymer analogous reactions of reactive pre-polymers with functional units, polymer blends, etc. [5][6][7] Although various synthetic strategies would be feasible, the surface modification method, which enables the introduction of substrates with specific functions on the surface of polymeric materials, is a crucial method for improving the properties of polymeric materials. [8][9][10][11][12][13][14] Generally, the functionality of a polymeric material is governed by the properties of the material surface that is solely in contact with the external environment.…”