• Extending the Scope of Benign and Thermally Stable Organocatalysts: Application of Dibenzoylmethane for the Bulk Copolymerization of l-Lactide and ɛ-Caprolactone

    The use of dibenzoylmethane as benign and thermally stable new organocatalyst for the solvent-free ring-opening copolymerization of l-lactide and ɛ-caprolactone is reported here. Such β-diketone molecule allows preparing well-defined P(LA-co-CL) copolyesters exhibiting a gradient to a random structure at 155 C

  • Isotactic degradable polyesters derived from O-carboxyanhydrides of l-lactic and l-malic acid using a single organocatalyst/initiator system

    The preparation of stereoregular isotactic P(l-BnMA) and PLLA by ring-opening polymerization (ROP) of 5-(S)-[(benzyloxycarbonyl)methyl]-1,3-dioxolane-2,4-dione (l-malOCA) and (S)-5-methyl-1,3-dioxolane-2,4-dione (l-lacOCA) is reported. The polymerization process was shown to be well controlled using two easily accessible single organocatalyst/initiator systems, pyridine/l-benzyl(Bn)malate and pyridine/lactic acid (Py·LA) ion pair adducts respectively. The obtained biodegradable polymers displayed narrow dispersity (ĐM) and excellent molar mass control. All ROP reactions were conducted at ambient temperature. The stereoregularity and thermal properties of the materials were thoroughly studied, demonstrating the retention of high levels of isotactic enrichment.

  • Temperature responsive PEG-based polyurethanes “à la carte”

    Temperature responsive polymers able to alter their chemical or physical properties have been extensively investigated. Most of these polymers have an alkane polymer backbone with only carbon-carbon bonds. In this sense, the design of thermoresponsive polymers not only with sharp transition temperatures but also possessing hydrolizable linkages such as esters, carbonates or urethanes in the main backbone are highly desired. Here we show a library of thermoresponsive cationic and anionic polyurethanes synthesized by copolymerization of isophorone diisocyanate with poly(ethylene glycol) and ionic diols. These polyurethanes exhibit lower critical solution temperatures (LCST) that can be easily tuned from 20 °C to 60 °C by altering the polyurethane composition. Our findings show that LCST temperature could be reduced by the using poly(ethylene glycol) of lower molecular weight and/or increasing the hydrophobicity of the employed ionic diol. We also demonstrated that the thermoresponsive behavior could be translated to hydrogels based on those ionic polyurethanes. These “a la carte” thermoresponsive polyurethanes materials present a great potential in the biomedical field due to the presence of hydrolizable linkages in the main polymer backbone.

  • Synthesis and characterization of poly (ε-caprolactam-co-lactide) polyesteramides using Brønsted acid or Brønsted base organocatalyst 2

    Polyesteramides (PEAs) are considered intriguing materials due to the combination of the favorable degradable capacity of aliphatic polyesters given by the hydrolizable ester groups and the desirable thermal and mechanical behavior of polyamides given by the amide groups. Between polyamides and polyester families, poly(ε-caprolactam) and poly(l-lactide) stand out due to their commercial value and outstanding properties. Nevertheless, to date these two monomers have not been co-polymerized due to their different reactivities. In this work, we report for the first time, up to our knowledge, the synthesis of poly(ε-caprolactam-co-l-lactide) copolymers with different compositions. Two different catalysts: (a) Brønsted acid ionic liquid 1-(4-sulfobutyl)-3-methylimidazolium hydrogen sulfate (BAIL) and (b) Brønsted base P4-t-Bu have been explored. In the presence of Brønsted acid the l-lactide reactivity is higher than the ε-caprolactam while in the presence of Brønsted base the opposite behavior is observed. Using Kelen-Tudos method the monomer reactivity ratios are calculated and obtained as rCLa = 0.39 and rLA = 1.6 and rCLa = 2.2 and rLA = 0.1 using BAIL and P4-t-Bu, respectively. These differences in the monomer reactivity ratios give us the possibility to create copolymers with different chain microstructure depending on the employed catalyst between 2 and 9 kDa. Thus, using P4-t-Bu random copolymers can be obtained at high l-lactide concentration and blocky character copolymers at high ε-caprolactam concentration. Meanwhile, using BAIL catalyst random like copolymers are obtained at high ε-caprolactam contents and blocky character at high l-lactide contents.

  • Organocatalytic ring-opening polymerization of l-lactide in bulk: A long standing challenge

    The exponential increase in the use of plastic demands that biosourced and biodegradable polymers such as poly(l-lactide)s (PLLA)s be considered to replace some petroleum based polymers in a range of applications. In order to produce PLLA in the greenest manner, i.e. by ring-opening polymerization (ROP) of l-lactide using an organocatalyst in solvent free conditions at high temperature (in bulk) has proven to be a significant challenge. Indeed, the high required temperature (180 °C) has led to poorly controlled polymerizations as a result of transesterification reactions of the PLLA backbone, racemization of the lactide monomers as well as the degradation and thus deactivation of the organocatalyst. We report herein the efforts made over the past 20 years in order to conduct the ROP of l-lactide in bulk by using organic molecules and the problems encountered by the scientific community in addressing this challenge to date.

  • Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Amino Acids

    Organocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer from a catalyst to a polymer in the organocatalyzed ring-opening polymerization (ROP) of rac-lactide (rac-LA). We have polymerized rac-LA using the diastereomeric densely substituted amino acids (2S,3R,4S,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (endo-6) and (2S,3S,4R,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (exo-6), combined with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a cocatalyst. Both diastereoisomers not only showed the ability to synthesize enriched isotactic polylactide with a Pm higher than 0.90 at room temperature but also were able to preferentially promote the polymerization of one of the isomers (l or d) with respect to the other. Thus, exo-6 preferentially polymerized l-lactide, whereas endo-6 preferred d-lactide as the substrate. Density functional theory calculations were conducted to investigate the origins of this unique stereocontrol in the polymerization, providing mechanistic insight and explaining why the chirality of the catalyst is able to define the stereochemistry of the monomer insertion.

  • Non-Isocyanate Polyurethane Soft Nanoparticles Obtained by Surfactant-Assisted Interfacial Polymerization

    Polyurethanes (PUs) are considered ideal candidates for drug delivery applications due to their easy synthesis, excellent mechanical properties, and biodegradability. Unfortunately, methods for preparing well-defined PU nanoparticles required miniemulsion polymerization techniques with a nontrivial control of the polymerization conditions due to the inherent incompatibility of isocyanate-containing monomers and water. In this work, we report the preparation of soft PU nanoparticles in a one-pot process using interfacial polymerization that employs a non-isocyanate polymerization route that minimizes side reactions with water. Activated pentafluorophenyl dicarbonates were polymerized with diamines and/or triamines by interfacial polymerization in the presence of an anionic emulsifier, which afforded non-isocyanate polyurethane (NIPU) nanoparticles with sizes in the range of 200–300 nm. Notably, 5 wt % of emulsifier was required in combination with a trifunctional amine to achieve stable PU dispersions and avoid particle aggregation. The versatility of this polymerization process allows for incorporation of functional groups into the PU nanoparticles, such as carboxylic acids, which can encapsulate the chemotherapeutic doxorubicin through ionic interactions. Altogether, this waterborne synthetic method for functionalized NIPU soft nanoparticles holds great promise for the preparation of drug delivery nanocarriers.

  • The organocatalytic ring-opening polymerization of N-tosyl aziridines by an N-heterocyclic carbene

    The ring-opening polymerization of N-tosyl aziridines, in the presence of 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene as an organocatalyst and an N-tosyl secondary amine as initiator mimicking the growing chain, provides the first metal-free route to well defined poly(aziridine)s (PAz) and related PAz-based block copolymers.

  • Organic-acid mediated bulk polymerization of ε-caprolactam and its copolymerization with ε-caprolactone

    Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step-growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε-caprolactam (ε-CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε-CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε-CLa , being the Brønsted acid ionic liquid: 1-(4-sulfobutyl)−3-methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End-group analysis by 1H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε-CLa and ε-caprolactone is demonstrated. As a result, poly(ε-caprolactam-co-ε-caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties.

  • Room temperature synthesis of non-isocyanate polyurethanes (NIPUs) using highly reactive N-substituted 8-membered cyclic carbonates

    There is a growing interest to develop green synthetic pathways towards industrially relevant polymers such as polyurethanes without the use of toxic and dangerous isocyanate monomers. The most promising route towards non-isocyanate polyurethanes (NIPUs) is the aminolysis of dicyclic carbonates derived from renewable resources. Although, cyclic carbonates of 5- and 6-members have been successfully proposed, aminolysis of these compounds requires the use of high temperatures to obtain high conversions and subsequently high molecular weight NIPUs. Indeed, these cyclic carbonates do not allow the achievement of high molecular weight NIPUs using low reactive diamines analogous to two of the most industrially relevant aliphatic diisocyanates. Herein, we report a (bis) N-substituted 8-membered cyclic carbonate that could be prepared from naturally abundant epoxides, diamines and dimethyl carbonate using sustainable chemical routes. This N-substituted 8 membered cyclic carbonate appeared to be much more reactive than the smaller 5- and 6-membered cyclic carbonates. Due to this increased reactivity, we obtained high molecular weight NIPUs using a variety of diamines, including industrially relevant hindered aliphatic diamines, such as 5-amino-1,3,3-trimethylcyclohexanemethylamine (IPDA) and 4,4′-methylenebis(cyclohexylamine). The synthesis of NIPUs was demonstrated at room temperature without the need for any additional catalyst. Altogether, this paper shows that (bis) N-substituted 8-membered cyclic carbonates are ideal starting materials for the synthesis of sustainable non-isocyanate polyurethanes (NIPUs).

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement 642671