Synthesis, Characterization, and Cyclic Stress Influenced Degradation of a Poly(Ethylene) Glycol Based Poly(Beta-Amino Ester)

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Keim, Terra Ann
Gall, Ken
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Poly(beta-amino esters) are photopolymerizable and biodegradable polymers prepared by the combination of amines with diacrylates. This study aims to fundamentally understand the polymer network formed by poly(ethylene)glycol diacrylate (PEGDA) MW 700 and 3-methoxypropylamine (3MOPA) as well as to characterize the degradation response of this material with and without cyclic loading. The networks were formed by a two-step process; (1) the synthesis of amine-co-peg diacrylate macromers through a step growth reaction, followed by (2) UV initiated chain growth network formation of the diacrylated macromers. Macromer reaction chemistry was confirmed by 1H NMR measurements. UV calorimetric analysis revealed that network formation was dependent on molecular weight of the PEGDA monomer and light intensity, but not temperature in the range of 20 °C to 40 °C. The glass transition temperature of all networks was measured to be in the range of -40 °C to -30°C with a rubbery moduli ranging from 4 to 10 MPa, depending on the molecular weight of the PEGDA monomer. Partial crystallization was discovered to occur in the networks containing higher molecular weight PEGDA only in the presence of humidity and high frequency cyclic loading. Degradation studies were performed with and without applied cyclical stress, and in both cases elastic modulus decrease and mass loss occurred steadily over a 24-hour period. Increasing frequency of applied compressive stress during degradation served to slightly lower degradation rates, especially in samples cycled at high frequency, which crystallized. In all materials, applied cyclic load resulted in catastrophic fracture of the material prior to an appreciable decrease in modulus. The experiments reveal that degradation rate and failure mode can be influenced by the addition of cyclic loading and this should be considered when screening biodegradable polymers for applications that include mechanical loading.
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