Stereo block copolymers of L- and D-lactides

Sequential diblock copolymers composed of L- and D-lactic acid residues were synthesized through a living ring-opening polymerization of L- and D-lactide initiated by aluminium tris(2-propanolate). The composition of the block copolymers was varied by changing the reaction conditions and monomer over initiator ratio and confirmed by 1H NMR analysis, molecular weight determination and optical rotation measurements. Molecular weights ranged from 1,3 to 2,0 · 104 with 1,2 < Mw/Mn < 1,4. Stereocomplex formation in all block copolymers was determined using differential scanning calorimetry showing melting temperatures of about 205°C

Synthesis of biodegradable polyesteramides with pendant functional groups

Morpholine-2,5-dione derivatives having substituents with benzyl-protected carboxylic acid, benzyloxycarbonyl-protected amine and p-methoxy-protected thiol groups, respectively, were prepared in 29-58% yield by cyclization of the corresponding N-[(2RS)-bromopropionyl]-L-amino acids. Polyesteramides with protected pendant functional groups were obtained by ring-opening copolymerization of either ε-caprolactone or DL-lactide with morpholine-2,5-dione derivatives having protected functional substituents. The copolymerizations were carried out in the bulk at 130°C using stannous octoate as an initiator and using low mole fractions (0,05, 0,10 and 0,20) of morpholine-2,5-dione derivatives in the feed. The molecular weight of the resulting copolymers ranged from 1,4 to 8,3 · 104. The ring-opening homopolymerization of morpho-line-2,5-dione derivatives with protected functional substituents was not successful. Polyesteramides with either pendant carboxylic acid groups or pendant amine groups were prepared by catalytic hydrogenation of the corresponding protected copolymers. Treatment of copolymers having pendant p-methoxybenzyl-protected thiol groups with trifluoromethanesulfonic acid resulted not only in the removal of the p-methoxybenzyl group but also in severe degradation of the copolymers, due to acidolysis of main-chain ester bonds

Stereocomplex formation in ABA triblock copolymers of poly(lactide) (A) and poly(ethylene glycol) (B)

Two series of triblock copolymers of poly(ethylene glycol) (PEG, number-average molecular weight [bar M ]n = 6000) and poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) were prepared by ring-opening polymerization of lactide initiated by PEG end groups using stannous octoate as a catalyst, either in refluxing toluene or in the melt at 175°C. The weight percentage of PLA in the polymers varied between 15 and 75 wt.-%. Blends of polymers containing blocks of opposite chirality were prepared by co-precipitation from homogeneous solutions. The melting temperatures of the crystalline PEG and PLA phases strongly depended on the composition of the polymers. The melting temperature of the PLA phase in the blends was approximately 40°C higher than that of the single block copolymers. Stereocomplex formation between blocks of enantiomeric poly(lactides) in PEG/PLA block copolymers was established for the first time. Water uptake of polymeric films prepared by solution casting was solely determined by the PEG content of the film

In situ forming stereocomplexed and post-photocrosslinked acrylated star poly(ethylene glycol)-poly(lactide) hydrogels

Biodegradable acrylate end-group functionalized poly(ethylene glycol)-poly(lactide) (PEG-PLA) star block copolymer hydrogels were formed by the consecutive physical gelation through stereocomplexation of star shaped PEG-(PLLA)8 and PEG-(PDLA)8 enantiomers and UV photopolymerization. The 8-armed PEG-PLA star block copolymers were prepared by ring opening polymerization of lactide onto an amine end-group functionalized PEG with a molecular weight of 20 kg/mol using stannous octoate as a catalyst. The degree of polymerization of the PLA blocks was 12 lactyl units and the end hydroxyl groups were reacted with acryloyl chloride to give the required acrylate end groups. Aqueous solutions of enantiomeric mixtures of the PEG-(PLA)8 macromonomers formed physically crosslinked hydrogels above a critical gel concentration of 4 w/v%. Subsequent photopolymerization at 365 nm in the presence of Irgacure 2959 resulted in gels with improved mechanical properties and hydrolytic stability. With 40% polymer mass loss after 45 d in vitro, these hydrogels show excellent resistance against hydrolytic degradation and dissolution, which is believed to result from the combination of stable amide linkages between the PEG and PLA blocks and the high physical and chemical crosslink density owing to the star architecture

Controlled synthesis of biodegradable lactide polymers and copolymers using novel in situ generated or single-site stereoselective polymerisation initiators

Polylactides and their copolymers are key biodegradable polymers used widely in biomedical, pharmaceutical and ecological applications. The development of synthetic pathways and catalyst/initiator systems to produce pre-designed polylactides, as well as the fundamental understanding of the polymerization reactions, has continuously been an important topic. Here, we will address the recent advances in the ring-opening polymerization of lactides, with an emphasis on the highly versatile in situ generated initiator systems and single-site stereoselective initiators. The in situ generated initiators including in situ formed yttrium, calcium and zinc alkoxides all have been shown to bring about a rapid and living polymerization of lactides under mild conditions, which facilitated the preparation of a variety of advanced lactide-based biomaterials. For example, well-defined di- and tri-block copolymers consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic polyester blocks, which form novel biodegradable polymersomes or biodegradable thermosensitive hydrogels, have been prepared. In the past few years, significant progress has also been made in the area of stereoselective polymerization of lactides. This new generation of initiators has enabled the production of polylactide materials with novel microstructures and/or properties, such as heterotactic (–RRSSRRSSRRSS–) polylactide, crystalline syndiotactic (–RSRSRSRSRSRS–) polylactide and isotactic stereoblock (–RnSnRnSn–) polylactide, exhibiting a high melting temperature. The recently developed polymerizations using in situ generated initiators and stereoselective polymerizations have no doubt opened a brand-new avenue for the design and exploration of polylactides and their copolymers