A.A. Deschamps

Poly(ethylene oxide)/poly(butylene terephthalate) segmented block copolymers: the effect of copolymer composition on physical properties and degradation behavior

In this study, the influence of copolymer composition on the physical properties and the degradation behavior of thermoplastic elastomers based on poly(ethylene oxide) (PEO) and poly(butylene terephthalate) (PBT) segments is investigated. These materials are intended to be used in medical applications where degradability of the implant is desired. PEOT/PBT copolymers are microphase separated and up to four thermal transitions are measured by differential scanning calorimetry. Phase separation in the system is enhanced by increasing the molecular weight of starting poly(ethylene glycol) (PEG) or by increasing the PBT content. The mechanical properties, swelling characteristics and degradation rates of the copolymers are influenced by the phase separation. By changing the PEOT/PBT composition, tensile strengths vary from 8 to 23 MPa and elongations at break from 500 to 1300%. Water uptake ranges from 4 to 210%. The in vitro degradation of PEOT/PBT copolymers occurs via hydrolysis and oxidation. In both cases, degradation is more rapid for copolymers with high contents of PEO. Deterioration of copolymer films takes place when the films are exposed to light in the absence of antioxidant. In preventing oxidation under daylight conditions, Irganox 1330 turned out to be a more efficient antioxidant for the copolymers than vitamin E.

Design of segmented poly(ether ester) materials and structures for the tissue engineering of bone.

In this study, PEOT/PBT segmented copolymers of different compositions have been evaluated as possible scaffold materials for the tissue engineering of bone. By changing the composition of PEOT/PBT copolymers, very different mechanical and swelling behaviors are observed. Tensile strengths vary from 8 to 23 MPa and elongations at break from 500 to 1300%. Water-uptake ranges from 4 up to as high as 210%. The in vitro degradation of PEOT/PBT copolymers occurs both by hydrolysis and oxidation. In both cases degradation is more rapid for copolymers with high PEO content. PEOT/PBT scaffolds with varying porosities and pore sizes have been prepared by molding and freeze-drying techniques in combination with particulate-leaching. The most hydrophilic PEOT/PBT copolymers did not sustain goat bone marrow cell adhesion and growth. However, surface modification by gas plasma treatment showed a very much improved polymer-cell interaction for all PEOT/PBT copolymer compositions. Their mechanical properties, degradability and ability to sustain bone marrow cell growth make PEOT/PBT copolymers excellent materials for bone tissue engineering.

In vivo and in vitro degradation of poly(ether ester) block copolymers based on poly(ethylene glycol) and poly(butylene terephthalate).

Two in vivo degradation studies were performed on segmented poly(ether ester)s based on polyethylene glycol (PEG) and poly(butylene terephthalate) (PBT) (PEOT/PBT). In a first series of experiments, the in vivo degradation of melt-pressed discs of different copolymer compositions were followed up for 24 weeks after subcutaneous implantation in rats. The second series of experiments aimed to simulate long-term in vivo degradation. For this, PEOT/PBT samples were pre-degraded in phosphate buffer saline (PBS) at 100 degrees C and subsequently implanted. In both series, explanted materials were characterized by intrinsic viscosity measurements, mass loss, proton nuclear magnetic resonance spectroscopy (1H-NMR) and differential scanning calorimetry (DSC). In both studies the copolymer with the higher PEO content degraded the fastest, although all materials degraded relatively slowly. To determine the nature of the degradation products formed during hydrolysis of the copolymers, 1000 PEOT71PBT29 (a copolymer based on PEG with a molecular weight of 1000 g/mol and 71 wt% of PEO-containing soft segments) was degraded in vitro at 100 degrees C in phosphate buffer saline (PBS) during 14 days. The degradation products present in PBS were analyzed by 1H-NMR and high performance liquid chromatography/mass spectroscopy (HPLC/MS). These degradation products consisted of a fraction with high contents of PEO that was soluble in PBS and a PEOT/PBT fraction that was insoluble at room temperature. From the different in vitro and in vivo degradation experiments performed, it can be concluded that PEOT/PBT degradation is a slow process and generates insoluble polymeric residues with high PBT contents.

Poly(ether ester amide)s for tissue engineering

Poly(ether ester amide) (PEEA) copolymers based on poly(ethylene glycol) (PEG), 1,4-butanediol and dimethyl-7,12-diaza-6,13-dione-1,18-octadecanedioate were evaluated as scaffold materials for tissue engineering. A PEEA copolymer based on PEG with a molecular weight of 300 g/mol and 25wt% of soft segments (300 PEEA 25/75) and the parent PEA polymer (0/100) sustain the adhesion and growth of endothelial cells. The in vivo degradation of melt-pressed PEEA and PEA discs subcutaneously implanted in the back of male Wistar rats was followed up to 14 weeks. Depending on the copolymer composition, a decrease in intrinsic viscosity of about 20-30% and mass loss up to 12% were measured. During the degradation process, erosion of the surface was observed by scanning electron microscopy and light microscopy. The thermal properties of the polymers during degradation were measured by differential scanning calorimetry. During the first 2 weeks, a broadening of the melting endotherm was observed, as well as an increase in the heat of fusion. Porous matrices of PEEAs and PEA could be prepared by molding mixtures of polymer and salt particles followed by leaching of the salt.

Phase separation and physical properties of PEO-containing poly(ether ester amide)s

Poly(ether ester amide) (PEEA) copolymers based on poly(ethylene glycol) (PEG), 1,4- butanediol, and dimethyl-7,12-diaza-6,13-dione-1,18-octadecanedioate (a diester-diamide monomer) were synthesized by a two-step polycondensation reaction. The obtained segmented copolymers are hydrophilic, with a water uptake of 24–340%. PEEA copolymers showed microphase separation, as observed by differential scanning calorimetry (DSC). The long spacing determined by small-angle X-ray scattering shows an increase in the hydrophilic domain size with increasing PEO content. By varying the copolymer composition, the E-modulus of PEEA could be varied between 61 and 427 MPa, with tensile strengths ranging from 12 to 39 MPa. The elongation at break can reach values up to 850%. The mechanical properties decrease with the uptake of water. However, PEEAs with a relatively low content of PEO still retain good tensile properties and are, in principle, suitable for biomedical applications.