Structure-property relationships in renewable composites of poly(lactic acid) reinforced by low amounts of micro- and nano-kraft-lignin.

We investigate the direct and indirect effects of micro- and nano-kraft lignin, kL and NkL, respectively, at a quite low amount of 0.5 wt%, in poly(lactic acid) (PLA)-based composites. These renewable composites were prepared via two routes, either simple melt compounding or in situ reactive extrusion. The materials are selected and prepared using targeted methods in order to vary two variables, i.e., the size of kL and the synthetic method, while maintaining constant polymer chain lengths, L-/D-lactide isomer ratio and filler amounts. The direct/indirect effects were respectively investigated in the amorphous/semicrystalline state, as crystallinity plays in general a dominant role in polymers. The investigation involves structural, thermal and molecular mobility aspects. Non-extensive polymer-lignin interactions were recorded here, whereas the presence of the fillers led to both enhancements and suppressions of properties, e.g., glass transition, crystallization, melting temperatures, etc. The local and segmental molecular dynamics map of the said systems was constructed and is shown here for the first time, demonstrating both expected and unexpected trends. An interesting discrepancy between the trends in the calorimetric measurement against the dielectric Tg is revealed, providing indications for 'dynamical heterogeneities' in the composites as compared to neat PLA. The reactive extrusion as compared to compounding-based systems was found to exhibit stronger effects on crystallizability and mobility, most, probably due to the severe enhancement of the chains' diffusion. In general, the effects are more pronounced when employing nano-lignin compared to micro-lignin, which is the expected beneficial behaviour of nanocomposites vs. conventional composites. Interestingly, the variety of these effects can be easily manipulated by the proper selection of the preparation method and/or the thermal treatment under relatively mild conditions. The latter capability is actually desirable for processing and targeted applications and is proved here, once again, as an advantage of biobased polyesters such as PLA.

Segmental mobility in sustainable copolymers based on poly(lactic acid) blocks built onto poly(butylene succinate) in situ.

Two series of newly synthesized sustainable block copolymers based on poly(butylene succinate) (PBSu) and polylactide (PLA) were studied. The copolymers were synthesized by a ring-opening polymerization of PLA in the presence of two initial PBSu of low molar mass. We focused on the effects of the PBSu/PLA ratio (1/99 up to 15/85), chain length and initial PBSu length on the final thermal transitions in the copolymers with an emphasis on molecular mobility/dynamics and subsequently on crystallization. Both aspects are considered relevant to the final materials performance, as well as facilitation of polymer renewability. Calorimetry and dielectric spectroscopy were the main investigation tools. In the amorphous state (i.e., in which the direct effects of copolymer structure are assessable), the segmental mobility of neat PLA was significantly faster in the copolymers. Segmental mobility was monitored via the decrease in the calorimetric and dielectric (α relaxation) glass-transition temperatures, Tg and Tg,diel, respectively. The effect was systematic with an increase in the PBSu/PLA ratio, and was rationalized through the plasticizing role of PBSu (low-Tg component) and facilitated also by the simultaneous lowering of the chain length in the copolymers. Dielectric spectroscopy allowed evaluation of the dynamical fragility (cooperativity) of chains, which was strongly suppressed in the copolymers. This finding suggested an increase in free volume or a gradual increase of interchain distances. This phenomenon could favor the natural enzymatic degradation of the systems (compostability), which is limited in neat PLA. We recorded enhancement of nucleation and the crystalline fraction in the copolymers that was likely connected with faster chain diffusion. Further lowering of the Tg with the implementation of crystallization was noted (which seemed a controversial effect) but which indicated crystallization-induced phase separation.

Direct and indirect effects on molecular mobility in renewable polylactide-poly(propylene adipate) block copolymers as studied via dielectric spectroscopy and calorimetry.

In this work, we study a series of sustainable block copolymers based on polylactide, PLA, and poly(propylene adipate), PPAd, both polymers being prepared from renewable resources. Envisaging a wide range of future applications in the frame of a green and circular economy, e.g., packaging materials replacing conventional petrochemicals, the employment of PPAd aims at lowering the glass transition and melting temperatures of PLA and, finally, facilitation of the enzymatic degradation and compostability. The copolymers have been synthesized via ring opening polymerization of lactides in the presence of propylene adipate oligomers (5, 15 and 25%). The direct effects on the molecular mobility by the structure/composition are assessed in the amorphous state employing broadband dielectric spectroscopy (BDS) and calorimetry. BDS allowed the recording of local PLA and PPAd dynamics in all cases. The effects on local relaxations suggest favoring of interchain interactions, both PLA-PPAd and PPAd-PPAd. Regarding the more important segmental dynamics, the presence of PPAd leads to faster polymer chain diffusion, as monitored by the significant lowering of the dielectric and calorimetric glass transition temperature, Tg. This suggests the plasticizing role of PPAd on PLA (majority) in combination with the lowering of the average molar mass, Mn, in the copolymers from ∼75 to ∼30 kg mol-1, which is the actual scope for the synthesis of these materials. Interestingly, a strong suppression in fragility (chain cooperativity) is additionally recorded. In contrast to calorimetry and due to the high resolving power of BDS, for the higher PPAd fraction, the weak segmental relaxation of PPAd was additionally recorded. Overall, the recordings suggest a strong increase in free volume and two individual dynamic states, one for 0 and 5% PPAd and another for 15 and 25% PPAd. Within the latter, we gained indications for partial phase nano-separation of PPAd. Regarding indirect effects, these were followed via crystallization. Independent of the method of crystallization, namely, melt or cold, the presence of PPAd led to the systematic lowering of crystallization and melting temperatures and enthalpies. The effects reflect the decrease of crystalline nuclei, which is confirmed by optical microscopy as in the copolymers fewer although larger crystals are formed.

Revisiting Non-Conventional Crystallinity-Induced Effects on Molecular Mobility in Sustainable Diblock Copolymers of Poly(propylene adipate) and Polylactide.

This work deals with molecular mobility in renewable block copolymers based on polylactide (PLA) and poly(propylene adipate) (PPAd). In particular, we assess non-trivial effects on the mobility arising from the implementation of crystallization. Differential scanning calorimetry, polarized light microscopy and broadband dielectric spectroscopy were employed in combination for this study. The materials were subjected to various thermal treatments aiming at the manipulation of crystallization, namely, fast and slow cooling, isothermal melt- and cold-crystallization. Subsequently, we evaluated the changes recorded in the overall thermal behavior, semicrystalline morphology and molecular mobility (segmental and local). The molecular dynamics map for neat PPAd is presented here for the first time. Unexpectedly, the glass transition temperature, Tg, in the amorphous state drops upon crystallization by 8-50 K. The drop becomes stronger with the increase in the PPAd fraction. Compared to the amorphous state, crystallization leads to significantly faster segmental dynamics with severely suppressed cooperativity. For the PLA/PPAd copolymers, the effects are systematically stronger in the cold- as compared to the melt-crystallization, whereas the opposite happens for neat PLA. The local ßPLA relaxation of PLA was, interestingly, recorded to almost vanish upon crystallization. This suggests that the corresponding molecular groups (carbonyl) are strongly involved and immobilized within the semicrystalline regions. The overall results suggest the involvement of either spatial nanoconfinement imposed on the mobile chains within the inter-crystal amorphous areas and/or a crystallization-driven effect of nanophase separation. The latter phase separation seems to be at the origins of the significant discrepancy recorded between the calorimetric and dielectric recordings on Tg in the copolymers. Once again, compared to more conventional techniques such as calorimetry, dielectric spectroscopy was proved a powerful and quite sensitive tool in recording such effects as well as in providing indirect indications for the polymer chains' topology.

Poly(Lactic Acid) Composites with Lignin and Nanolignin Synthesized by In Situ Reactive Processing.

Poly(lactic acid) (PLA) composites with 0.5 wt% lignin or nanolignin were prepared with two different techniques: (a) conventional melt-mixing and (b) in situ Ring Opening Polymerization (ROP) by reactive processing. The ROP process was monitored by measuring the torque. The composites were synthesized rapidly using reactive processing that took under 20 min. When the catalyst amount was doubled, the reaction time was reduced to under 15 min. The dispersion, thermal transitions, mechanical properties, antioxidant activity, and optical properties of the resulting PLA-based composites were evaluated with SEM, DSC, nanoindentation, DPPH assay, and DRS spectroscopy. All reactive processing-prepared composites were characterized by means of SEM, GPC, and NMR to assess their morphology, molecular weight, and free lactide content. The benefits of the size reduction of lignin and the use of in situ ROP by reactive processing were demonstrated, as the reactive processing-produced nanolignin-containing composites had superior crystallization, mechanical, and antioxidant properties. These improvements were attributed to the participation of nanolignin in the ROP of lactide as a macroinitiator, resulting in PLA-grafted nanolignin particles that improved its dispersion.

Synthesis, Properties, and Enzymatic Hydrolysis of Poly(lactic acid)-co-Poly(propylene adipate) Block Copolymers Prepared by Reactive Extrusion.

Poly(lactic acid) (PLA) is a biobased polyester with ever-growing applications in the fields of packaging and medicine. Despite its popularity, it suffers from inherent brittleness, a very slow degradation rate and a high production cost. To tune the properties of PLA, block copolymers with poly(propylene adipate) (PPAd) prepolymer were prepared by polymerizing L-lactide and PPAd oligomers via reactive extrusion (REX) in a torque rheometer. The effect of reaction temperature and composition on the molecular weight, chemical structure, and physicochemical properties of the copolymers was studied. The introduction of PPAd successfully increased the elongation and the biodegradation rate of PLA. REX is an efficient and economical alternative method for the fast and continuous synthesis of PLA-based copolymers with tunable properties.