The paper describes a new method of copolymerization of glycolide with l-lactide with the use of a low toxic compoundZr(acac)4as initiator at a temperature of 100 up to 150 °C. Copolymerization at 150 °C is very fast and reached nearly 100% yield. The values of the copolymerization coefficients were estimated as r G = 3.3 and r L = 0.5. The process of chain propagation was also examined, and a significant influence of transesterification on the final structure of copolymer was observed. The microstructure of the chain was determined by NMR spectroscopy. It was found that more segmental structure had been formed as compared with the structure of the copolymer obtained in copolymerization initiated by tin compounds. This structure influences thermomechanical properties of the copolymers. The crystallinity of copolymers obtained is higher than that of the formed in the presence of Sn(oct)2. One of their most characteristic features concerned their good mechanical properties, in many cases better than those of adequate copolymers obtained with the use of tin compounds as initiators.

A series of copolymers with various compositions were synthesized by bulk ring-opening polymerization of glycolide and epsilon-caprolactone, using stannous (II) octoate or zirconium (IV) acetylacetonate as initiator. Reaction time and temperature were varied so as to induce different chain microstructures. The resulting copolymers were characterized by (1)H NMR, SEC, DSC, and X-ray diffraction. The average lengths of glycolyl (L(G)) and caproyl sequences (L(C)) and the degree of randomness (R) were calculated and compared to the values of completely random chains. The concentration of CGC sequences was also obtained which resulted from transesterification reactions. Data showed that stannous (II) octoate leads to less transesterification than zirconium (IV) acetylacetonate, and lower temperatures lead to less transesterification than higher ones. The copolymers exhibited a more or less blocky chain structure because of the reactivity difference between glycolide and epsilon-caprolactone. The crystalline structure and thermal properties depend on both the composition and the chain microstructure. PGA- and PCL-type crystallites were obtained for copolymers with intermediate compositions.

Bioresorbable new terpolymers of l-lactide, glycolide, and trimethylene carbonate with different compositions were synthesized via ring-opening polymerization reaction of the cyclic monomers using low-toxicity zirconium(IV) acetylacetonate as initiator. The thermal and mechanical properties were investigated by means of thermogravimetry, differential scanning calorimetry, stress−strain measurements, and dynamical mechanical analysis. The glass transition temperature of the terpolymers changes with composition from 12 to 42 °C in a predictable manner. All terpolymers display shape memory properties and, after undergoing 100% deformation, they recover the permanent shape in a time frame of seconds. Terpolymers with high l-lactide content show a glass transition in the range of 38−42 °C, recovery temperature close to body temperature, and good recovery ratio (>0.89). Low-toxicity bioresorbable terpolymers with shape memory properties are promising new materials for biomedical applications.

Zirconium(IV) acetylacetonate [Zr(acac)4] is a very good initiator for the terpolymerization of glycolide with L‐lactide and ϵ‐caprolactone. The microstructure of the obtained terpolymer was determined by NMR spectroscopy and then compared with terpolymers obtained in the presence of stanous(II) octoate [Sn(oct)2]. Samples obtained with Zr(acac)4 were characterized by a segmental‐chain microstructure. Apart from relatively long lactidyl microblocks, there were also segments made of random copolymer of glycolide with lactide. Such a structure is formed as a result of strong transesterification caused by active caproyl chain endings attacking the glycolidyl groups. Domination of this type of transestrification is shown. The growth of terpolymer chains and the influence of transesterification on gradual changes of the microstructure of the forming terpolymer chain were examined. Significant differences among glycolide, lactide, and the least reactive caprolactone were observed. The results of differential scanning calorimetric examinations of the obtained terpolymers are presented. Differences between the structures of random terpolymers obtained during terpolymerization initiated by Sn(oct)2 and those obtained by Zr(acac)4 influence their thermal properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3129–3143, 2002

A series of glycolide/epsilon-caprolactone copolymers were compression molded and allowed to degrade in a pH 7.4 phosphate buffer at 37 degrees C. Degradation was monitored by various analytical techniques such as (1)H NMR, X-ray diffraction, DSC, CZE, ESI-MS, and inherent viscosity measurements. The results show that the degradation rate depends not only on the copolymer composition but also on its chain microstructure. Generally, copolymers with a higher C-G bond content or a higher degree of randomness exhibit higher degradation rates. Sequences with odd numbers of glycolyl units such as -CGC- and -CGGGC-, which result from the second mode transesterification, appear more resistant to hydrolysis. As a consequence, degradation residues obtained at the later stages of degradation are mainly composed of long glycolyl and caproyl sequences linked by -CGC- and -CGGGC- ones. The degradation rate of the copolymers depends also on the degree of crystallinity of each component which is related to the block length. The caproyl component can be preferentially degraded if it is in the amorphous state and the glycolyl component is semicrystalline.

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Poly(l-lactide-co-glycolide) (PLLAGA) copolymers and poly(dl-lactide) (PDLLA) were synthesized using the low toxicity compound zirconium(IV) acetylacetonate. Blends with synthetic atactic poly(3-hydroxybutyrate) (a-PHB) were prepared in film form by solvent casting. The solid-state properties of the plain polymers and of the blends were investigated by thermogravimetric analysis coupled with mass spectrometry (TGA−MS), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and stress−strain measurements. The a-PHB/PDLLA blends are miscible over the whole composition range. On the other hand, blends of a-PHB with PLLAGA copolymers containing 5 and 16 mol % of GA units show partial miscibility. The solubility limit of a-PHB in PLLAGA is around 20 wt % in both cases. In the blends, the a-PHB in excess to this value segregates as a pure phase. The mechanical properties of blend films of either PDLLA or PLLAGA containing up to 50 wt % of a-PHB can be modulated by changing blend composition. The tenacity progressively increases by the addition of a-PHB not only in the miscible amorphous a-PHB/PDLLA system but also in the partially miscible a-PHB/PLLAGA blends.

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the 13C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006