Author, as appears in the article.: Bensabeh N., Ronda J., Galià M., Cádiz V., Lligadas G., Percec V.

Department: Química Analítica i Química Orgànica

URV's Author/s: Cádiz Deleito, Maria Virginia / Galià Clua, Marina Teresa / Lligadas Puig, Gerard / Ronda Bargalló, Juan Carlos

Keywords: Hashtag Etiqueta «#» @uroweb @residentesaeu @infoAeu

Abstract: Cu(0) wire-catalyzed single electron transfer¿living radical polymerization (SET-LRP) of (−)-menthyl acrylate, a biobased hydrophobic monomer, was investigated at 25 °C in ethanol, isopropanol, ethyl lactate, 2,2,2-trifluoroethanol (TFE), and 2,2,3,3-tetrafluoropropanol (TFP). All solvents are known to promote, in the presence of N ligands, the mechanistically required self-regulated disproportionation of Cu(I)Br into Cu(0) and Cu(II)Br2. Both fluorinated alcohols brought out their characteristics of universal SET-LRP solvents and showed the proper polarity balance to mediate an efficient polymerization of this bulky and hydrophobic monomer. Together with the secondary alkyl halide initiator, methyl 2-bromopropionate (MBP), and the tris(2-dimethylaminoethyl)amine (Me6-TREN) ligand, TFE and TPF mediated an efficient SET-LRP of MnA at room temperature that proceeds through a self-generated biphasic system. The results presented here demonstrate that Cu(0) wire-catalyzed SET-LRP can be used to target polyMnA with different block lengths and narrow molecular weight distribution at room temperature. Indeed, the use of a combination of techniques that include GPC, 1H NMR, MALDI-TOF MS performed before and after thioetherification of bromine terminus via ¿thio¿bromo¿ click chemistry, and in situ reinitiation copolymerization experiments supports the near perfect chain end functionality of the synthesized biobased hydrophobic polymers. These results expand the possibilities of SET-LRP into the area of renewable resources where hydrophobic compounds are widespread.

Thematic Areas: Química Polymers and plastics Polymer science Medicina ii Materials chemistry Materiais Interdisciplinar Farmacia Engenharias iv Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, organic Biotecnología Biomaterials Bioengineering Biochemistry & molecular biology Astronomia / física

ISSN: 15257797

Author's mail: gerard.lligadas@urv.cat virginia.cadiz@urv.cat juancarlos.ronda@urv.cat marina.galia@urv.cat

Author identifier: 0000-0002-8519-1840 0000-0003-2689-5407 0000-0002-0668-6600 0000-0002-4359-4510

Last page: 1268

Record's date: 2023-02-22

Journal volume: 19

Papper version: info:eu-repo/semantics/submittedVersion

Link to the original source: https://pubs.acs.org/doi/abs/10.1021/acs.biomac.8b00090

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Biomacromolecules. 19 (4): 1256-1268

APA: Bensabeh N., Ronda J., Galià M., Cádiz V., Lligadas G., Percec V. (2018). SET-LRP of the Hydrophobic Biobased Menthyl Acrylate. Biomacromolecules, 19(4), 1256-1268. DOI: 10.1021/acs.biomac.8b00090

Article's DOI: 10.1021/acs.biomac.8b00090

Entity: Universitat Rovira i Virgili

Journal publication year: 2018

First page: 1256

Publication Type: Journal Publications