Sizing down and functionalizing polylactide (PLA) resin for synthesis of PLA-based polyurethanes for use in biomedical applications.

Alcoholysis is a promising approach for upcycling postconsumer polylactide (PLA) products into valuable constituents. In addition, an alcohol-acidolysis of PLA by multifunctional 2,2-bis(hydroxymethyl)propionic acid (DMPA) produces lactate oligomers with hydroxyl and carboxylic acid terminals. In this work, a process for sizing down commercial PLA resin to optimum medium-sized lactate oligomers is developed at a lower cost than a bottom-up synthesis from its monomer. The microwave-assisted reaction is conveniently conducted at 220-240 °C and pressure lower than 100 psi. The PLA resin was completely converted via alcohol-acidolysis reaction, with a product purification yield as high as 93%. The resulting products are characterized by FTIR, 2D-NMR, 1H-NMR, GPC, DSC, and XRD spectroscopy. The effects of PLA: DMPA feed ratios and the incorporation of 1,4-butanediol (BDO) on the structures, properties, and particle formability of the alcohol-acidolyzed products are examined. The products from a ratio of 12:1, which possessed optimum size and structures, are used to synthesize PLA-based polyurethane (PUD) by reacting with 1,6-diisocyanatohexane (HDI). The resulting PUD is employed in encapsulating lavender essential oil (LO). Without using any surfactant, stable LO-loaded nanoparticles are prepared due to the copolymer's self-stabilizability from its carboxylate groups. The effect of the polymer: LO feed ratio (1.25-3.75: 1) on the physicochemical properties of the resulting nanoparticles, e.g., colloidal stability (zeta potential > -60 mV), hydrodynamic size (300-500 nm), encapsulation efficiency (80-88%), and in vitro release, are investigated. The LO-loaded nanoparticles show non-toxicity to fibroblast cells, with an IC50 value higher than 2000 µg/mL. The products from this process have high potential as drug encapsulation templates in biomedical applications.

Polyester-based polyurethanes derived from alcoholysis of polylactide as toughening agents for blends with shape-memory properties.

A process for sizing down and functionalizing commercial polylactide (PLA) resin is developed by alcoholysis with 1,4-butanediol (BDO) and propylene glycol (PG) to medium-sized PLA-based diols, with lower cost than a bottom-up synthesis process. These are subsequently used as polyols in preparing polyurethanes (PU) by reacting with 1,6-diisocyanatohexane (HDI). The PLA-based PU has an excellent elongation at break of 487%. The products are suitable as toughening agents for brittle PLA resin due to their highly elastic properties and high compatibility with PLA. The PU products are blended with PLA resin at various compositions, and their physical and mechanical properties and shape recovery are examined. The tensile tests showed enhancements in elongation at break up to 160% with low modulus. The fracture morphology and FTIR results confirm that the blends show strong interfacial interaction and adhesion between the PLA-based PU disperse phase and the PLA matrix. The PLA/PU blends exhibit a high shape recovery efficiency, and their recovery mechanisms are identified. These flexible PLA/PU blends are promising for various applications where bio-compatibility/degradability and high ductility are required, especially as filaments for 3D bio-printing.

Synthesis and quantitative analyses of acrylamide-grafted poly(lactide-co-glycidyl methacrylate) amphiphilic copolymers for environmental and biomedical applications.

Bio-degradable/bio-compatible poly(lactide-co-glycidyl methacrylate), P(LA-co-GMA), a copolymer has been synthesized. The material contains curable CC groups, which enable its self-curing and grafting reactions with other vinyl monomers. The copolymer was grafted with a pH-responsive polyacrylamide (PAAm), by UV-assisted reactions using acrylamide (AAm) and N,N'-methylene bisacrylamide monomers, and various photoinitiator systems. The original copolymer and its partially-cured counterpart were employed in the grafting reaction. Chemical structures and properties of the resulting materials were characterized. Standard quantitative analysis techniques for measurement of the grafted AAm content and the degree of CC conversion have been developed by 1H NMR and FTIR spectroscopy. FTIR offers more advantages, in terms of non-destructive analysis, ease of operation, and lower cost of analysis. The results show that the grafted products from pre-cured P(LA-co-GMA) copolymers contain higher grafted AAm contents than their uncured counterparts. The highest grafted AAm content was obtained by using benzophenone (BP) as an initiator, while camphorquinone (CQ) led to the lowest content. In contrast, the degree of CC conversion of the copolymer from the two initiator systems shows a reverse trend. These amphiphilic and pH-responsive grafted copolymers with tunable AAm contents have a high potential for use in various applications, especially in biomedical and environmental fields.

Properties of poly(lactic acid)/hydroxyapatite composite through the use of epoxy functional compatibilizers for biomedical application.

A composite of 70/30 poly(lactic acid)/hydroxyapatite was systematically prepared using various amounts of glycidyl methacrylate as reactive compatibilizer or Joncryl ADR®-4368 containing nine glycidyl methacrylate functions as a chain extension/branching agent to improve the mechanical and biological properties for suitable usage as internal bone fixation devices. The effect of glycidyl methacrylate/Joncryl on mechanical properties of poly(lactic acid)/hydroxyapatite was investigated through flexural strength. Cell proliferation and differentiation of osteoblast-like MC3T3-E1 cells cultured on the composite samples were determined by Alamar Blue assay and alkaline phosphatase expression, respectively. Result shows that flexural strength tends to decrease, as glycidyl methacrylate content increases except for 1 wt.% glycidyl methacrylate. With an addition of dicumyl peroxide, the flexural strength shows an improvement than that of without dicumyl peroxide probably due to the chemical bonding of the hydroxyapatite and poly(lactic acid) as revealed by FTIR and NMR, whereas the composite with 5 wt.% Joncryl shows the best result, as the flexural strength increases getting close to pure poly(lactic acid). The significant morphology change could be seen in composite with Joncryl where the uniform agglomeration of hydroxyapatite particles oriented in poly(lactic acid) matrix. Addition of the epoxy functional compatibilizers at suitable percentages could also have benefits to cellular attachment, proliferation, differentiation and mineralization. So that, this poly(lactic acid)/hydroxyapatite composite could be a promising material to be used as internal bone fixation devices such as screws, pins and plates.