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The quality of the monomers lactic acid and lactide as well as the chemical changes induced during polymerization and processing are crucial parameters for controlling the properties of the resulting poly(lactic acid) (PLA) products. This review presents the most important analysis and characterization methods for quality assessment of PLA and its precursors. The impurities typically present in lactic acid or lactide monomers and their possible origins and effects on resulting PLA products are discussed. The significance of the analyses for the different polymer production stages is considered, and special applications of the methods for studying features specific for PLA-based materials are highlighted.

Poly-l-lactide/poly-d-lactide (PLLA/PDLA) stereocomplex had much higher hydrolytic stability compared to plain PLLA, but at the same time shorter and more acidic degradation products were formed. Both materials were subjected to hydrolytic degradation in water and in phosphate buffer at 37 and 60 degrees C, and the degradation processes were monitored by following mass loss, water uptake, thermal properties, surface changes, and pH of the aging medium. The degradation product patterns were determined by electrospray ionization-mass spectrometry (ESI-MS). The high crystallinity and strong secondary interactions in the stereocomplex prevented water uptake and resulted in lower mass loss and degradation rate. However, somewhat surprisingly, the pH of the aging medium decreased much faster in the case of PLLA/PDLA stereocomplex. In accordance, the ESI-MS results showed that hydrolysis of PLLA/PDLA resulted in shorter and more acidic degradation products. This could be explained by the increased intermolecular crystallization due to stereocomplexation, which results in an increased number of tie chains. Because mainly these short tie chains are susceptible to hydrolysis this leads to formation of shorter oligomers compared to hydrolysis of regular PLLA.

l-Lactide was ring-opening polymerized in the melt by using different organic monocarboxylic iron complexes. The complexes were those of iron and acetic acid, butyric acid, isobutyric acid, dichloroacetic acid, and trifluoroacetic acid. The polymerization temperature was in the range 170−210 °C, polymerization time between 0.5 and 25 h, and amount of catalyst added varied between 0.12 and 1.20 wt %. Iron butyrate and iron dichloroacetate complexes were low efficient catalysts in the ring-opening polymerization due to hydrolysis during the preparation. Iron acetate, iron trifluoroacetate, and iron isobutyrate complexes were efficient catalysts yielding a high molar mass poly(l-lactide) with a high monomer conversion. Under optimum conditions a poly(l-lactide) with a molar mass (M w) of ca. 150 000 g/mol could be prepared. Monomer conversions over 85% were obtained in many experiments. High polymerization temperatures are required though with these kinds of iron catalysts, and some racemization of the polymerization products is evident. The polymerization experiments indicate that the oxidation state of the iron has an influence on the efficiency of the catalysts and that the iron is chemically bound to the polymer.

Impact-modified and unmodified L-polylactide and L-polylactide-polycaprolactone co-polymer films were evaluated for their suitability as materials for cheese packaging. The polymers were in some cases compounded with nanoclays as a possible route to enhanced barrier properties and/or with cyclodextrin complexes designed to provide slow release of encapsulated antimicrobials for control of mould growth on packaged cheeses. The materials demonstrated complete biodegradation under controlled composting conditions and the extruded films had acceptable transparency. Moisture uptake by films and a decrease in polymer molecular weight with time of exposure to high humidity were identified as areas of concern, although the polymer stability experiments were undertaken at 25°C and stability at normal cheese storage temperatures (~4°C) is expected to be better. Nanoclay addition enhanced the thermal stability of the polymer but reduction of oxygen and water vapour permeability to target levels through incorporation of 5% w/w nanoclay was not achieved, possibly in part due to inadequate dispersion of the nanoclays in the chosen polymer matrices. On the positive side, a novel impact-modified polylactide was developed that overcame problems with brittleness in unmodified L-polylactide and L-polylactide-polycaprolactone copolymer films, and tests indicated that a cyclodextrin-encapsulated antimicrobial (allyl isothiocyanate) incorporated in L-polylactide-polycaprolactone co-polymer films would be effective in controlling fungi on packaged cheeses. Migration of substances from the L-polylactide or L-polylactide-polycaprolactone films into cheese is not expected to be a problem.

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Poly(lactic acid) (PLA) stereocomplexes have high potential as renewable materials for advanced polymer applications, mainly due to their high melting temperature (Tm, typically 230–240°C). The properties of PLA stereocomplexes consisting of linear high molar mass homopolymers have been studied extensively in the past, but the available information about the possibilities to affect the thermal properties of the stereocomplex by varying the structure of the blend components has not been sufficient. Novel stereocomplexes containing linear or star‐shaped D‐lactic acid (D‐LA) oligomers and high molar mass poly(L‐lactide) (L‐PLA) were thus prepared. The Tm and melting enthalpy (ΔHm) of the racemic crystallites were found to depend strongly on both the blending ratio and the arm‐length of the D‐lactic acid oligomer. The preparation method of the oligomers, i.e. step‐growth polymerization or ring‐opening polymerization (ROP), did not affect the Tm or ΔHm of the blends significantly. Slightly higher ΔHm values were, however, obtained, when linear oligomers were used. The results thus indicated that the Tm and ΔHm of PLA stereocomplexes could be optimized, simply by selecting a D‐LA oligomer having a suitable arm‐length and structure as the other blend component. The possibility to adjust the melting behavior of the stereocomplex blend is a significant advantage and could make PLA suitable for a wider range of products used at elevated temperatures. Copyright © 2010 John Wiley & Sons, Ltd.

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