Maurizio Penco

Degradation behaviour of block copolymers containing poly(lactic-glycolic acid) and poly(ethylene glycol) segments

The degradation behaviour of a new class of multi-block copolymers containing poly(D,L-lactic-glycolic acid) (PLGA) and poly(ethylene glycol) (PEG) segments was studied under conditions mimicking those found in biological fluids. The dissolution times of the new PLGA-PEG multi-block copolymers mainly depend on the length of the PEG segments present in their structure, i.e., on their PEG content on a weight/weight basis. At higher PEG contents, partially degraded PLGA segments are brought in solution by attached PEG segments. In all cases, the dissolution rates decrease by increasing the total surface area of the specimens tested.

Thermal properties of a new class of block copolymers based on segments of poly(d,l-lactic-glycolic acid) and poly(ε-caprolactone)

Abstract The results of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic-mechanical thermal analysis (DMTA) investigations performed on a new class of multi-block copolymers based on poly( d , l -lactic-glycolic acid) (PLGA) and diol-terminated poly(e-caprolactone) (PCDT) segments are reported. The synthesis and molecular weight characterisation of these materials, having a structure of poly(ester-carbonate)s, were described in a recent paper. In the present work the influence of the length of PCDT segments and of the molar ratio between the d , l -lactic acid (LA) and glycolic acid (GA) residues on thermal stability, degree of crystallinity and glass transition temperature (Tg) has been investigated. Materials completely amorphous or having variable degrees of crystallinity have been obtained modulating the above parameters. The TGA traces run under nitrogen atmosphere exhibit two degradation processes that can be ascribed to the PLGA and PCDT segments, respectively. In addition, the thermal-stability increases with the LA content in the PLGA blocks.

Synthesis and properties of novel block copolymers containing poly(lactic-glycolic acid) and poly(ethyleneglycol) segments.

A synthetic process for obtaining high-molecular-weight block copolymers containing poly(lactic-glycolic acid) and poly(ethylene glycol) segments has been established. This process involves the reaction of poly(ethylene glycols) with phosgene, followed by polycondensation of the resulting alpha, omega-bis(chloroformates) with poly(lactic-glycolic acid) oligomers. The copolymers have been characterized for their molecular weight, solubility properties, water absorption and preliminarily thermal behaviour. All evidence points to the conclusion that the process described is a general one, enabling biodegradable polymers to be obtained tailor-made according to specific requirements.

New poly(ester-carbonate) multi-block copolymers based on poly(lactic-glycolic acid) and poly(ε-caprolactone) segments

A new family of multi-block copolymers having the structure of poly(ester-carbonate)s was obtained by a chain-extension reaction involving poly(lactic-glycolic acid) oligomers (PLGA) and oligomeric α,ω-bishydroxy-terminated poly(e-caprolactone)s (PCDT). The latter were first transformed into α,ω-bis(chloroformate)s, which were subsequently condensed in the presence of amines with both the hydroxylic and the carboxylic end-groups of PLGA oligomers. Several samples differing in the length of the PCDT segments and in the composition of the PLGA segments were prepared and characterized for their physico-chemical properties. All of them had high molecular weight. good solubility in organic solvents, and modest swellability in aqueous media. As regards their thermal behaviour, some samples showed evidence of the presence of a a crystalline phase. Since these products are potentially useful as bioerodible materials in drug delivery systems, some preliminary results on their degradation behaviour under conditions mimicking those found in biological fluids are reported.

Thermogravimetric investigation of two classes of block copolymers based on poly(lactic-glycolic acid) and poly(ε-caprolactone) or poly(ethylene glycol)

Abstract The thermogravimetric analysis (TGA) of two classes of multi-block copolymers based on poly( d , l -lactic-glycolic acid) (PLGA) and diol-terminated poly(e-caprolactone) (PCDT) or poly(ethylene glycol) (PEG) segments is reported. These materials, having the structure of poly(ester-carbonate)s, were synthesized by a chain extension reaction. The influence of the length of PCDT or PEG segments and of the molar ratio of d , l -lactic acid (LA) and glycolic acid (GA) residues on thermal stability in air and nitrogen atmosphere has been investigated. For comparison purposes the degradation behaviour of starting oligomers was also studied. TGA under nitrogen shows two degradation processes that can be ascribed to the PLGA and PCDT or PEG segments, respectively. In addition, the thermal stability increases with the LA content in the PLGA blocks. In the tests run under air two degradation steps have also been observed, though the former occurs in general at higher temperatures.

Self-repairing systems based on ionomers and epoxidized natural rubber blends.

The development of materials with the ability of intrinsic self-repairing after damage in a fashion resembling that of living tissues has important scientific and technological implications, particularly in relation to cost-effective approaches toward damage management of materials. Natural rubbers with epoxy functional groups in the macromolecular chain (ENR) and ethylene-methacrylic acid ionomers having acid groups partially neutralized with metal ions possess self-repairing behavior following high energy impacts. This research investigates the self-repairing behavior of both ENR and ionomers during ballistic puncture test on the basis of their thermal and mechanical properties. Heterogeneous blending of ionomers and ENR have also been used here as a strategy to tune the thermal and mechanical properties of the materials. Interestingly, blends of sodium ion containing ionomer exhibit complete self-repairing behavior, whereas blends of zinc ion containing ionomer show limited mending. The chemical structure studied by FTIR and thermal analysis shows that both ion content of ionomer and functionality of ENR have significant influence on the self-repairing behavior of blends. The mobility of rubbery phases along with its interaction to ionomer phase in the blends significantly changes the mending capability of materials. The healing behavior of the materials has been discussed on the basis of their thermal, mechanical, and rheological tests for each materials.

Multiblock copolymers based on segments of poly (D, L-lactic-glycolic acid) and poly(ethylene glycol) or poly(∈-caprolactone): A comparison of their thermal properties and degradation behavior

A comparison of the thermal properties of two classes of poly(D,L-lactic-glycolic acid) multiblock copolymers is reported. In particular, the results of differential scanning calorimetry, and thermogravimetric analysis of copolymers containing poly(ethylene glycol) (PEG) or diol-terminated poly(∈-caprolactone) (PCDT) segments are described. The influence of the chemical structure and the length of PEG and PCDT on thermal stability, degree of crystallinity and glass transition temperature (T g ) is discussed. Finally, an evaluation of the hydrolytic behavior in conditions mimicking the physiological environment is reported.

Thermal degradation of two classes of block copolymers based on poly(lactic-glycolic acid) and poly(e-caprolactone) or poly(ethylene glycol)

Thermodegradative investigations of two classes of multi-block copolymers containing poly(D,L-lactic-glycolic acid) (PLGA) and either poly(ethylene glycol) (PEG) or poly(e-caprolactone) diol-terminated (PCDT) segments were performed. In particular, the influence of the type and length of the segments as well as of the molar ratio between the D,L-lactic acid (LA) and glycolic acid (GA) residues was investigated at 180°C in air by viscometry, FT-IR analysis and isothermal thermogravimetry. The thermal oxidative degradation of these materials is largely affected by the LA/GA ratio, a higher LA content generally imparting higher stability. The FT-IR analysis suggests that, depending on the composition of the PLGA segments, degradative processes are triggered which can lead to a preferential degradation of the blocks.

Autonomous healing materials based on epoxidized natural rubber and ethylene methacrylic acid ionomers

The development of autonomous healing material has an enormous scientific and technological interest. In this context, this research work deals with the investigation of autonomous healing behavior of epoxidized natural rubber (ENR) and its blends with ethylene methacrylic acid ionomers. The autonomous healing behavior of ENR and its blends containing two different ionomers [poly(ethylene-co-methacrylic acid sodium salt) (EMNa) and poly(ethylene-co-methacrylic acid zinc salt) (EMZn)] has been studied by ballistic puncture tests. Interestingly, EMNa/ENR blends exhibit complete healing just after the ballistic test but EMZn/ENR blends do not show full self-repairing. The healing efficiency has been evaluated by optical microscopy and a depressurized air-flow test. The healing mechanism has been investigated by characterizing thermal and mechanical properties of the blends. The chemical structure studied by FTIR and thermal analysis show that the ion content of ionomers and functionality of ENR has a significant influence on the self-healing behavior.

Binary blends based on poly(vinyl chloride) and multi-block copolymers containing poly(ε-caprolactone) and poly(ethylene glycol) segments

Binary blends based on poly(vinyl chloride) (PVC) were prepared both by casting from tetrahydrofuran (THF) and by mixing in the melt form, in a discontinuous mixer, PVC and multi-block copolymers containing poly(e-caprolactone) (PCDT) and poly(ethylene glycol) (PEG) segments. PCDT-PEG copolymers were synthesized using a polycondensation reaction where the α,ω-bis-chloroformate of an oligomeric poly(e-caprolactone) diol terminated (PCDT) and oligomeric PEG were employed as macromonomers. For comparison purposes, blends PVC with starting oligomers as well as with mixtures containing a typical low molecular plasticizer, dioctylphthalate (DOP), were also prepared. The copolymer miscibility was studied by differential scanning calorimetry (DSC) and FT-IR spectroscopy. The blend morphology was investigated by polarized light microscopy (PLM). A higher miscibility with PVC was observed for copolymers compared to PEG.