Partially bio‐based tri‐ and hexaallyl monomers: Synthesis from naturally occurring myo‐inositol and polyaddition with dithiols

myo‐Inositol, a naturally occurring cyclic hexaol, was converted to 2,4,6‐tri‐O‐allyl‐myo‐inositol and 1,2,3,4,5,6‐hexa‐O‐allyl‐myo‐inositol. Polyaddition of the former product, a tri(allyl ether) bearing three hydroxyl groups, with dithiols yielded the corresponding networked polymers. Their glass transition temperatures (T_gs) were higher than those of networked polymers formed by the polyaddition of 1,3,5‐tri‐O‐methyl‐2,4,6‐tri‐O‐allyl‐myo‐inositol. This implied the reinforcement of the networks by hydrogen bonding between the hydroxyl groups. Polyaddition of the latter product, a hexa(allyl ether), with dithiols yielded the corresponding networked polymers with much higher T_gs than those of all of the aforementioned networked polymers. This implied that efficient use of the hexafunctional monomer leads to the formation of more densely crosslinked polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1524–1529     

Cross‐metathesis of biorenewable dioxalates and diols to film‐forming degradable polyoxalates

Starting from commonly available sugar derivatives, a single step protocol to access a small family of isohexide‐dioxalates ( 2a–c ) has been established. The synthetic competence of 2a–c has been demonstrated by subjecting them to condensation polymerization. Quite surprisingly, the proton NMR of poly(isomannide‐co‐hexane)oxalate revealed a 1:2 ratio between isomannide‐dioxalate ( 2a ) and 1,6‐hexanediol ( 3a ) in the polymer backbone. This intriguing reactivity was found to be an outcome of a cross metathesis reaction between 2a and 3a . The cross metathesis products 3a ”[2‐(2‐methoxyacetoxy)ethyl 2‐(2‐hydroxyethoxy)‐2‐(λ3‐oxydanylidene)acetate] and 2a ‘(3R,6R)‐6‐hydroxyhexahydrofuro[3,2‐b]‐furan‐3‐yl methyl oxalate were isolated in a control experiment. Based on direct and indirect evidence, and control experiments, an alternative polymerization mechanism is proposed. Polymerization conditions were optimized to obtain polyoxalates P1(2a‐3a)‐P9(2c‐3c) with molecular weights in the range of 14,000–68,000 g/mol, and narrow polydispersities. The identity of the polyoxalates was unambiguously established using 1‐2D NMR spectroscopy, MALDI‐ToF‐MS, and GPC measurements. The practical implication of these polymers is demonstrated by preparing transparent, mechanically robust films. The environmental footprint of the selected polyoxalates was investigated by subjecting them to solution and solid‐state degradation. The polyoxalates were found to be amenable to degradation. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1584–1592     

Synthesis of poly(ω‐pentadecalactone)‐b‐poly(acrylate) diblock copolymers via a combination of enzymatic ring‐opening and RAFT polymerization techniques

Herein the first reported preparation of diblock copolymers of the polyethylene‐like polyester poly(ω‐pentadecalactone) (PPDL) via a combination of enzymatic ring‐opening polymerization (eROP) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization techniques is described. PPDL was synthesized via eROP using Novozyme 435 as a catalyst and a bifunctional initiator/chain transfer agent (CTA) appropriate for the eROP of ω‐pentadecalactone (PDL) and RAFT polymerization of acrylic and styrenic monomers. Chain growth of the PPDL macro‐CTA was performed to prepare acrylic and styrenic diblock copolymers of PPDL, and demonstrates a facile, metal‐free, and “greener” alternative to preparing acrylic diblock copolymers of polyethylene (PE). Diblock copolymer architecture was substantiated via analysis of ¹H NMR spectroscopic, UV‐GPC chromatographic, DSC onset crystallization (T_c), and MALDI‐ToF mass spectrometric data. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3326–3335     

Green chemistry for the synthesis of methacrylate-based hydrogels crosslinked through Diels–Alder reaction

This study describes an environmentally friendly and green synthetic approach for the preparation of poly(aminoethylmethacrylate)-based hydrogels crosslinked through Diels–Alder (DA) reaction in water. This “click” reaction offers the possibility of preparing chemically crosslinked hydrogels in the absence of any catalyst, initiator or coupling agent, thus preserving the biocompatibility of the material. The suitable furan diene was obtained by modifying a methacrylate polymer by its reaction with furfural, a first generation compound derived from renewable resources. Methacrylate-based complementary polymeric dienophiles were also prepared by introducing maleimide groups into the structure. The products obtained at different steps were characterized by FTIR, NMR and TGA techniques. The study of the rheological properties of the hydrogels proved the success of this green “click” synthetic strategy confirming the formation of chemically crosslinked networks by the use of the Diels–Alder reaction. Furthermore, SEM studies revealed promising morphological properties of the ensuing hydrogels in terms of biomedical applications.     

Monomers and polymers from plant oils via click chemistry reactions

As a consequence of the depleting of fossil reserves and environmental issues, today, plant oils and fatty acids derived therefrom have a respectable status within the polymer chemistry community. However, maximizing the benefits of these renewable feedstocks requires the utilization of sustainable and efficient chemical transformations. The emergence of click chemistry concept and especially the renaissance of thiol‐ene addition reaction have had an impact on the way to make plant oil‐derived polymers. This highlight discusses the applicability and success of thiol‐ene addition and other click reactions in the transformation of oleochemicals into monomers and polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Enzymatic syntheses of unsaturated polyesters based on isosorbide and isomannide

The search for materials produced from renewable sources aiming at the substitution of petroleum‐based derivates is an area of intense investigation. In this work, the enzymatic copolymerization of isosorbide or isomannide with diethyl adipate and fractions of different unsaturated diesters (diethyl itaconate, diethyl fumarate, diethyl glutaconate, and diethyl hydromuconate) were examined using CAL‐B as catalyst. The polyesters prepared using one‐step syntheses were characterized by SEC, NMR, and MALDI‐TOF MS. In addition, syntheses with linear diols were carried out in bulk to evaluate the reactivity of cyclic diols in producing unsaturated polyesters using enzymatic catalysis, as well as to evaluate the occurrence of addition side reactions on the double bonds. Isosorbide and isomannide yielded unsaturated polymers with values in the order of 4,000‐16,000 when fumarate or glutaconate esters were added in 5 mol % ratio against adipate. In all cases MALDI‐TOF confirmed the presence of unsaturated units. Although these polyesters have unreacted double bonds they are prone to crosslinking and ready to further functionalization, like anchoring bioactive molecules. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3881–3891