Prof. Jon M. Matxain

@article{Irigoyen2026,

title = {Quantum-Chemical Study for Understanding the Low Incorporationof 2-Methylen-1,3-Dioxepane (MDO) in Radical Ring-Opening Copolymerizationwith Vinyl Monomers},

author = {Mikel Irigoyen and Alice Marchand and Xabier Lopez de Pariza and Timo Melchin and Aitor Barquero and Jon M. Matxain and Haritz Sardón and Jose R. Leiza and Fernando Ruipérez},

doi = {10.1021/acs.macromol.6c00681},

issn = {1520-5835},

year  = {2026},

date = {2026-07-28},

urldate = {2026-07-28},

journal = {Macromolecules},

volume = {59},

number = {14},

pages = {8509--8521},

publisher = {American Chemical Society (ACS)},

abstract = {<jats:title>Abstract</jats:title>

                  <jats:p>Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs), particularly 2-methylene-1,3-dioxepane (MDO), offers a robust pathway to introduce degradable ester linkages into nondegradable vinyl backbones. However, the rational design of these materials is currently hindered by highly comonomer-dependent open-to-closed (ester vs acetal) incorporation ratios. In this study, a rigorous density functional theory (DFT) framework integrating systematic conformational sampling and implicit solvation is employed to establish a unified structure–reactivity map for MDO copolymerization across a diverse set of vinyl monomers. The computational results reveal that while MDO homopolymerization is thermodynamically driven toward quantitative ring opening due to the irreversibility of the open-chain radical, copolymerization is governed by a fine-tuned competition between the kinetic accessibility of vinyl addition and the stability of the resulting cyclic adduct. The closed-propagation barrier is primarily dictated by a SOMO–LUMO interaction, where the electronic nature and α-substitution of the comonomer modulate orbital overlap and energy. Three distinct reactivity regimes are identified: (1) high open incorporation (e.g., MDO, crotonates), where high vinyl barriers and adduct reversibility favor β-scission; (2) intermediate competition (e.g., vinyl acetate); and (3) ring-retention dominance (e.g., acrylates), where rapid vinyl addition and deep thermodynamic stabilization suppress the degradable pathway. This work provides a qualitative molecular basis for the rational selection of comonomers to maximize CKA incorporation in the open form for next-generation sustainable vinyl polymers.</jats:p>},

keywords = {IT2067, POL-KT},

pubstate = {published},

tppubtype = {article}

}

@article{Gastearena2026,

title = {An insight into the monomeric isomerism in the polymerization of glycidol with B(C6F5)3: A DFT study of the initiation, propagation and cyclization steps},

author = {Xuban Gastearena and Fernando Ruipérez and Fabienne Barroso-Bujans and Anabel Lam and Jon M. Matxain},

doi = {10.1016/j.polymer.2026.129792},

issn = {0032-3861},

year  = {2026},

date = {2026-04-02},

urldate = {2026-04-02},

journal = {Polymer},

volume = {350},

number = {129792},

publisher = {Elsevier BV},

keywords = {IT2067, POL-KT},

pubstate = {published},

tppubtype = {article}

}

@article{Calvo2026,

title = {Polymer-metal oxide interfaces in XHNBR/PA6 blends: computational insights toward sustainable crosslinking},

author = {Unai Calvo and Jon M. Matxain and Jose Javier Egurrola and Aizeti Burgoa and Fernando Ruipérez},

doi = {10.1039/d5ra09279e},

issn = {2046-2069},

year  = {2026},

date = {2026-02-11},

journal = {RSC Adv.},

volume = {16},

number = {10},

pages = {9167--9179},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {Polyamide 6 (PA6) is a high-performance thermoplastic widely used in engineering applications, while carboxylated hydrogenated nitrile rubber (XHNBR) provides viscoelastic damping and reactive carboxyl groups for crosslinking with metal oxides.},

keywords = {IT2067, POL-KT},

pubstate = {published},

tppubtype = {article}

}