A simple and convenient method for the preparation of degradable poly(ethylene oxide) (PEO) is presented in this work. Through metal-free copolymerization of ethylene oxide with L-Lactide (LLA), very low content of LLA could be randomly incorporated into the backbone of PEO in the presence of triethylborane. In the presence of the latter Lewis acid, the reactivity of LLA could be curtailed, and transesterification reactions suppressed. The copolymerization of EO with LLA resulted in P(EO-co-LLA) samples of low to moderate content in ester units, and of controlled molar mass and low dispersity value. Reactivity ratios were determined using the non-terminal model (Beckingham-Sanoja-Lynd BSL equation) and the terminal model (Meyer–Lowry ML equation), respectively. The NMR characterization of the copolymer samples conbined with the kinetic treatment shows that non-terminal model describes adequately the copolymerization of EO with LLA. The resulting copolymers were further studied by differential scanning calorimetry (DSC); hydrolysis experiments were carried out to show the degradability of the prepared PEO samples containing a few percentage of ester units.

A one-pot, two-step protocol for the direct synthesis of polyurethanes containing few carbonate linkages through polycondensation of diamines, dihalides, and CO2 in the presence of Cs2CO3 and tetrabutylammonium bromide is described. The conditions were optimized by studying the polycondensation of CO2 with 1,6-hexanediamine and 1,4-dibromobutane as model monomers. Then, various diamines and dihalides were tested under optimal conditions. Miscellaneous samples of such carbonate-containing polyurethanes exhibiting molar masses from 6000 to 22 000 g/mol (GPC) and yields higher than 85% were obtained. The thermal properties of such polyurethanes were unveiled by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA): they were found very similar to those of traditional polyurethanes obtained by diisocyanates + diols polycondensation.

Tetrabutylammonium carbonate (TBAC) which is obtained by treating CO2 with tetrabutylammonium hydroxide is shown to perform as an ideal difunctional initiator for the copolymerization of carbon dioxide (CO2) and propylene oxide (PO) in the presence of triethylborane (TEB). In this system, CO2 thus serves as the initiating moiety of its own copolymerization with epoxides when used in the form of a carbonate salt. Based on this remarkable result, mono-, tri-, and tetrafunctional ammonium carboxylate initiators and also other difunctional carboxylate initiators were synthesized and used for the synthesis of well-defined ω-hydroxyl-polycarbonates with linear and star structures. Well-defined telechelics, three- and four-armed star samples of molar mass varying from 1 kg/mol to 10 kg/mol, with around 95% carbonate content, were successfully synthesized. The structure of the obtained polycarbonate ω-polyols were characterized by 1H NMR, MALDI-TOF, and GPC. The terminal hydroxyl functionality of polycarbonate diol was further used for polycondensation with diisocyanates to afford polyurethanes. Finally, taking TBAC as an example, the recyclability of this ammonium-based initiator is demonstrated for the preparation of polycarbonate diols.

A rapid and efficient method to remove thiocarbonylthio end groups from polymers prepared by reversible addition–fragmentation chain transfer (RAFT) is described. The elimination process is obtained in less than 1 min by treating the solution of RAFT-synthesized polymers with 5 equiv of trialkylborane (TAB) in the presence of oxygen under an ambient temperature. The versatility of this method was checked on the most relevant families of thiocarbonylthio chain transfer agents (CTA), including dithioesters, trithiocarbonates, dithiocarbamates, and xanthates, carried by the corresponding RAFT-synthesized polymers. UV, NMR, and MALDI-TOF MS characterization results all confirm the complete removal of their terminal CTA groups.

Glycidyl azide polymer or poly(glycidyl azide) which is considered as an excellent energetic binder or plasticizer in advanced solid propellants is generally obtained by post-modification or azidation of poly(epichlorohydrin). Here we report that glycidyl azide can be directly homopolymerized through anionic ring-opening polymerization to access poly(glycidyl azide) using onium salts as initiator and triethyl borane as activator. Molar masses of poly(glycidyl azide) up to 11.0 Kg/mol are achieved in a controlled manner with a narrow polydispersity index (PDI ≤ 1.2). Similarly, alternating poly(glycidyl azide carbonate) are also prepared through alternating copolymerization of glycidyl azide with carbon dioxide. Lastly, the copolymerization of glycidyl azide with other epoxide monomers is carried out; the azido functions carried by glycidyl azide which are successfully incorporated into the backbones of polyethers and polycarbonates based on cyclohexene oxide and propylene oxide subsequently served to introduce other functions by click chemistry.

This study demonstrates the successful use of CO as versatile carbonation agent for the synthesis of 5-membered and 6-membered bicyclic glycocarbonates from methyl α-d-mannopyranoside (MDM) and methyl α-d-galactopyranoside (MDG). On the one hand, these two sugars were cyclized into 5-membered glycocarbonates by mere reaction of CO with their hydroxyls either at cis-2,3 or cis-3,4 positions and without resorting to phosgene or its derivatives. The reactivity of the obtained 5-membered cyclic glycocarbonates were further tested with hexyl- and dodecyl amine. The self-assembling behavior of the formed alkyl glycosides in water was investigated and characterized by transmission electron microscope (TEM). On the other hand, secondary hydroxyls at 2- and 3- positions in MDM and MDG were first protected by a ketal group and by two ether, respectively before subjecting their respective 6-position hydroxyl to bromination. Their respective 6-bromo and 4-hydroxyl functions were subsequently reacted in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and CO. The resulting 6-membered cyclic glycocarbonates were then polymerized using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) or DBU as organocatalyst. All the synthesized 5- and 6-membered cyclic glycocarbonates and polyglycocarbonates were thoroughly characterized by FT-IR, H, C NMR and MALDI-ToF and Gel Permeation Chromatography (GPC).

Whatever the chemistry used for the synthesis of aliphatic polycarbonates, in particular, those of high molar mass, the adventitious presence of water leads to bimodal GPC traces and affords polycarbonate samples of uncontrolled and unpredictable molar masses. It appears that among all reagents used in the copolymerization of CO2 and epoxides, CO2 is the most difficult one to dry. To address this issue, triisobutylaluminum (TiBA) was employed in this work to dry CO2 through a bubbling method; its drying capability was investigated in the context of the copolymerization of CO2 with epoxides initiated by onium chloride in the presence of triethylborane (TEB). It was then compared to the efficiency of other already reported drying agents such as phosphorus pentoxide, molecular sieves and commercially available CO2 purifiers. With TiBA-dried CO2, its copolymerizations respectively with propylene oxide (PO) and cyclohexene oxide (CHO) could be successfully achieved in a wide range of degrees of polymerization (DP), with the value of DP as high as 16000. Diblock copolymers poly(propylene carbonate-b-cyclohexene carbonate) (PPC-b-PCHC) could also be prepared through sequential addition of epoxide monomers. The polycarbonates obtained under the conditions were all well-defined as characterized by NMR, GPC, triple detector-GPC, and differential scanning calorimetry (DSC).