Synthesis Of Biodegradable Copolymers Research Articles

Synthesis of Biodegradable Copolymer of Poly(isobutyl vinyl ether)-co-Poly(ε-Caprolactone) using Half-Sandwich Metallocene Catalyst and their Application as Plasticizer for Poly(Vinyl Chloride)

ABSTRACTIn this work, we studied the synthesis of biodegradable copolymers of the type poly(isobutyl vinyl ether)-co-(ε-caprolactone) (PIBVE-co-PCL) using a homogeneous mono-cyclopentadienyltitanium catalyst and methylaluminoxane (MAO) as co-catalyst. These copolymers can also be used as plasticizers for flexible poly(vinyl chloride) (PVC), improving its thermal properties. The copolymer PIBVE-co-PCL could be synthesized with a high conversion (>90%). The use of 39 wt.% of the copolymer in the formulation of PVC decreases its glass transition temperature (Tg) by -6.51 °C. By varying the copolymer composition it is possible to obtain PVC with different Tg values that could be used for different applications. A particular application where one could use this type of copolymer is in PVC formulations for the fabrication of blood bags. The toxicity of dioctyl phthalate (DOP), which is the more commonly used plasticizer for PVC, limits the use of these formulations for the mentioned purpose. The PVC plasticized with the biodegradable copolymer showed an increase in the degradation temperature, improving the thermal stability of the PVC formulation in comparison with the phthalates usually used as plasticizers.

Synthesis of Biodegradable Copolymers Based on Ethylene Vinyl Acetate and Polylactic Acid

In the present study biodegradable copolymers of ethylene vinyl acetate and polylactic acid were synthesized using transesterification reactions, the structure, morphology, mechanical properties and biodegradability of the produced materials were characterized. Ethylene vinyl acetate was modified with polylactic acid in an internal mixer using titanium propoxide as transesterification catalyst. The graft copolymers were characterized by elemental analysis, infrared spectroscopy, rheology, scanning electron microscopy and thermal analysis. Selective extractions for all copolymers were made, and the results indicate that a maximum of 25 % of EVA-g-PLA copolymer was synthesized by this method. Biodegradation tests were carried out using the standard ISO 14851 (1999), which specifies a method for determining the biochemical oxygen demand in a closed respirometer. This procedure allowed to synthesize biodegradable copolymers with mechanical properties similar to conventional polymers.

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

AbstractUsing 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

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. IV. Copolymerization of glycolide with trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate: Microstructure analysis of copolymer chains by high‐resolution nuclear magnetic resonance spectroscopy

AbstractThe results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate are described. The copolymerization was conducted in the presence of low‐toxicity zirconium(IV) acetylacetonate as an initiator. With this kind of initiator, the composition of the comonomer units in the copolymer chains was assumed to be obtained with high efficiency. Despite significant differences in the comonomer reactivity, in copolymers containing comparable amounts of glycolidyl and carbonate sequences, highly randomized chain structures were observed. This effect resulted from strong intermolecular transesterification that proceeded during the studied copolymerization and caused glycolidyl microblock randomization. The assignment of the spectral NMR lines to appropriate comonomer sequences of polymeric chains was performed in the region of methylene protons of glycolidyl units in 1H NMR spectra of the copolymers and in the carbonyl region of carbon spectra. The equations were formulated for a detailed characterization of the obtained copolymer chains, the average lengths of the blocks, and the transesterification and randomization coefficients. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 98–114, 2006

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. III. Synthesis and chain‐microstructure analysis of terpolymer obtained from L‐lactide, glycolide, and ϵ‐caprolactone initiated by zirconium(IV) acetylacetonate

AbstractZirconium(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

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. II. Copolymerization of glycolide with ϵ‐caprolactone initiated by zirconium(IV) acetylacetonate and zirconium(IV) chloride

AbstractThe aim of this article is to show a new method of copolymerizing glycolide and caprolactone with the low‐toxicity zirconium(IV) acetylacetonate and zirconium(IV) chloride as initiators. Such initiators enabled us to obtain copolymers with very good efficiency and good mechanical properties. The reactivity of the initiators was defined, and the chain‐propagation process was examined. On the basis of an NMR examination and differential scanning calorimetry thermograms, we found that the samples obtained at 100 °C with the initiators were characterized by a segmental chain microstructure, which provided good mechanical properties. When the synthesis was carried out at 150 °C, a more randomized structure was obtained, which caused crucial changes in the properties of the copolymers and decreases in the mechanical properties. Because of their properties, the obtained copolymers could be successfully applied as degradable surgical implants or drug carriers. The results show that the copolymers obtained with zirconium(IV) acetylacetonate and chloride could successfully replace ones obtained in the presence of tin compounds as far as medical applications are concerned. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1379–1394, 2002

Synthesis of Biodegradable Copolymers with the Use of Low Toxic Zirconium Compounds. 1. Copolymerization of Glycolide with l-Lactide Initiated by Zr(Acac)4

The paper describes a new method of copolymerization of glycolide with l-lactide with the use of a low toxic compoundZr(acac)4as 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 rG = 3.3 and rL = 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.