Polyurethanes based on poly(epsilon-caprolactone) (PCL) (750-2800 g/mol) and 1,4-butane diisocyanate (BDI) with different soft segment lengths and constant uniform hard segment length were synthesized in absence of catalysts for the production of a degradable meniscus scaffold. First the polyesterdiols were endcapped with BDI yielding a macrodiisocyanate with a minimal amount of side reactions and a functionality of 2.0. Subsequently, the macrodiisocyanates were extended with 1,4-butanediol in order to obtain the corresponding polyurethane. The polyurethanes had molecular weights between 78 and 160 kg/mol. Above molar masses of 1900 g/mol of the polyesterdiol crystalline PCL was found while the hard segment showed an increase in melting point from 78 to 122 degrees C with increasing hard segment content. It was estimated that the percentage crystallinity of the hard segment varied between 92 and 26%. The Young's modulus varied between 30 and 264 MPa, the strain at break varied between 870 and 1200% and tear strengths varied between 97 and 237 kJ/m2.
Porous scaffolds have been made from two polyurethanes based on thermally induced phase separation of polymer dissolved in a DMSO/water mixture in combination with salt leaching. It is possible to obtain very porous foams with a very high interconnectivity. A major advantage of this method is that variables like porosity, pore size, and interconnectivity can be independently adjusted with the absence of toxic materials in the production process. The obtained compression moduli were between 200 kPa and 1 MPa with a variation in porosity between 76 and 84%. Currently the biological and medical aspects are under evaluation.
In this study it was investigated whether hydrogels could be used for an accommodating lens. The requirements of such a hydrogels are a low modulus, high refractive index, transparency, and strength. Since conventional hydrogels do not possess this combination of properties, a novel preparation method and new polymers are introduced. As starting materials poly(1-hydroxy-1,3-propanediyl), poly(ethylene-co-vinyl alcohol), poly(vinyl alcohol), and poly(allyl alcohol) were used. The first three were cross-linked with a number of diisocyanate compounds. Network formation was performed at low concentrations in a good solvent. Mixing of the polymer solution and cross-linker appeared to be crucial for transparency. Poly(1-hydroxy-1,3-propanediyl), cross-linked with a slow reacting diisocyanate block, shows the most promising properties with respect to refractive index, transparency, tensile strength, and modulus. Poly(allyl alcohol) hydrogel was made by compression molding. The hydrogel was transparent and had a high refractive index and low modulus. It was concluded that hydrogels could be used as accommodating lens material.
Using a micro-extruder a new class of polyurethanes, polyacylurethanes (PAUs), based on poly(3-caprolactone) (PCL) oligomers and terephthaloyl diisocyanate was synthesized. These polymers are anticipated to have potential for biodegradable and/or biomedical applications. Therefore, PAUs were synthesized without the use of any, possibly toxic, catalysts. PCL diols of different molecular mass were used, namely 750, 1000, 1250, 1500, 2000, 3000 and 4000 g/mol. These diols were synthesized by thermal polymerization at 150 8C without the use of any catalyst. The PAUs of terephthaloyl diisocyanate were synthesized by reactive extrusion using a micro-extruder of 5 cm 3 at 130 8C. The PAUs obtained were characterized using DSC, GPC, DMTA, SAXS and tensile testing. Surprisingly, PAUs based on PCL chains of 750, 1000, 1250 and 1500 g/mol were found to show microphase separation/micro crystallization as proven by SAXS data combined with DSC. This microphase separation creates elastomeric properties as is known from polyurethanes. In the PAUs based on PCL chains of 2000, 3000 and 4000 g/mol part of the PCL was found to crystallize and no evidence of any phase separation of the acylurethane block was found.
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