987 research outputs found
Stereo block copolymers of L- and D-lactides
Sequential diblock copolymers composed of L- and D-lactic acid residues were synthesized through a living ring-opening polymerization of L- and D-lactide initiated by aluminium tris(2-propanolate). The composition of the block copolymers was varied by changing the reaction conditions and monomer over initiator ratio and confirmed by 1H NMR analysis, molecular weight determination and optical rotation measurements. Molecular weights ranged from 1,3 to 2,0 · 104 with 1,2 < Mw/Mn < 1,4. Stereocomplex formation in all block copolymers was determined using differential scanning calorimetry showing melting temperatures of about 205°C
Synthesis of biodegradable polyesteramides with pendant functional groups
Morpholine-2,5-dione derivatives having substituents with benzyl-protected carboxylic acid, benzyloxycarbonyl-protected amine and p-methoxy-protected thiol groups, respectively, were prepared in 29-58% yield by cyclization of the corresponding N-[(2RS)-bromopropionyl]-L-amino acids. Polyesteramides with protected pendant functional groups were obtained by ring-opening copolymerization of either ε-caprolactone or DL-lactide with morpholine-2,5-dione derivatives having protected functional substituents. The copolymerizations were carried out in the bulk at 130°C using stannous octoate as an initiator and using low mole fractions (0,05, 0,10 and 0,20) of morpholine-2,5-dione derivatives in the feed. The molecular weight of the resulting copolymers ranged from 1,4 to 8,3 · 104. The ring-opening homopolymerization of morpho-line-2,5-dione derivatives with protected functional substituents was not successful. Polyesteramides with either pendant carboxylic acid groups or pendant amine groups were prepared by catalytic hydrogenation of the corresponding protected copolymers. Treatment of copolymers having pendant p-methoxybenzyl-protected thiol groups with trifluoromethanesulfonic acid resulted not only in the removal of the p-methoxybenzyl group but also in severe degradation of the copolymers, due to acidolysis of main-chain ester bonds
Stereocomplex formation in ABA triblock copolymers of poly(lactide) (A) and poly(ethylene glycol) (B)
Two series of triblock copolymers of poly(ethylene glycol) (PEG, number-average molecular weight [bar M ]n = 6000) and poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) were prepared by ring-opening polymerization of lactide initiated by PEG end groups using stannous octoate as a catalyst, either in refluxing toluene or in the melt at 175°C. The weight percentage of PLA in the polymers varied between 15 and 75 wt.-%. Blends of polymers containing blocks of opposite chirality were prepared by co-precipitation from homogeneous solutions. The melting temperatures of the crystalline PEG and PLA phases strongly depended on the composition of the polymers. The melting temperature of the PLA phase in the blends was approximately 40°C higher than that of the single block copolymers. Stereocomplex formation between blocks of enantiomeric poly(lactides) in PEG/PLA block copolymers was established for the first time. Water uptake of polymeric films prepared by solution casting was solely determined by the PEG content of the film
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