PLA Chains Research Articles

Physical ageing and molecular mobility in PLA blends and composites

Poly(lactic acid) (PLA) blends and composites were prepared from thermoplastic starch, poly(butylene-adipate-co-terephtalate), polycarbonate, wood flour and CaSO4 in a wide range of compositions. The thermal transitions of PLA were studied by differential scanning calorimetry. The detailed analysis of the transitions of PLA/thermoplastic starch blends indicated that they all are determined by the molecular mobility of PLA chains. Blending changes molecular mobility, and thus it often decreases glass transition temperature and modifies the extent of enthalpy relaxation. All other transitions and characteristics, i.e. cold crystallization, melting and the corresponding enthalpies, change accordingly. Increased molecular mobility accelerates also the physical ageing of the polymer. The interaction between PLA and the various components used for modification changed in a wide range, but no direct correlation was found between the strength of interaction and molecular mobility.

Thermo-responsive drug release from self-assembled micelles of brush-like PLA/PEG analogues block copolymers

Thermo-responsive brush-like amphiphilic poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate]-b-poly(l-lactide)-b-poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate] [P(MEO2MA-co-OEGMA)-b-PLLA-b-P(MEO2MA-co-OEGMA)] triblock copolymers were synthesized by atom transfer radical polymerization of MEO2MA and OEGMA co-monomers using a α,ω-Bromopropionyl poly(l-lactide) (Br-PLLA-Br) macroinitiator. The resulting copolymers with MEO2MA/OEGMA molar ratio ranging from 79/21 to 42/58 were characterized by 1H nuclear magnetic resonance and size exclusion chromatography. Thermo-responsive micelles were obtained by self-assembly of copolymers in aqueous medium. The micelles are spherical in shape with sizes varying from 20.7 to 102.5nm. A hydrophobic anticancer drug, curcumin, was encapsulated in micelles by using membrane hydration method. The properties of drug loaded micelles were determined by dynamic light scattering, transmission electron microscopy and lower critical solution temperature (LCST) measurements. The micelles size decreases from 102.5nm for blank micelles to 37.6nm with 10.8% drug loading, suggesting that the drug plays an important role in the micellization procedure. The LCST decreases from 45.1°C for blank micelles to 40.6 and 38.3°C with 5.9 and 10.8% drug loading, respectively. In vitro drug release was performed in pH 7.4 PBS at different temperatures. Data show that the release rate was significantly enhanced above the LCST comparing with that below the LCST. The amount of released drug at 41°C was ca. 20% higher than that at 37°C. Burst-like release was depressed due to enhanced interaction between drug with hydrophobic PLA and PMA chains.

Improving the impact property and heat‐resistance of PLA/PC blends through coupling molecular chains at the interface

The influences of both the molecular structure and the melt viscosity differences between Poly(lactic acid) (PLA) and polycarbonate (PC) on the interpenetration of molecular chains at the interface were investigated by comparing the dynamic mechanical properties and morphologies of the as‐prepared PLA/PC solution‐casting blends with those of their corresponding annealed (180°C, 8 h) samples or PLA/PC melt blends. Additionally, two chain extenders containing epoxy groups (ADR and TGDDM) were used to improve the interfacial strength. Subsequently, the interpenetration of PLA and PC molecular chains at the interface was also surveyed. Finally, the effects of the morphology formed by after adding ADR or TGDDM on the impact property, and heat resistance were discussed. The results showed that there was no interpenetration of molecular chains at the interface in PLA/PC melt blends because of the serious hindrance of the molecular structure and the melt viscosity differences. Although the interfacial strength achieved significant increase after adding ADR or TGDDM, the increase of the interfacial strength should be caused by the connection of ADR or TGDDM molecules with PLA and PC molecules at the interface through chemical bonds rather than the entanglements of PLA and PC molecular chains because of no interpenetration of PLA and PC molecular chains at the interface. Thus, the morphology formed after adding ADR or TGDDM is still the type of complete phase separation, which may be the most suitable morphology for achieving high impact and heat resistance PLA/PC blends because these two properties strongly depend on the crystallinity of PLA phase. Copyright © 2015 John Wiley & Sons, Ltd.

Metallic phytates as efficient bio-based phosphorous flame retardant additives for poly(lactic acid)

In this study, we evaluated the potential flame retardant effect of different metallic phytates as biosourced phosphorous additives for poly(lactic acid) (PLA). Starting from sodium phytate, the sodium cations were replaced by aluminum, iron or lanthanum cations as attested by elemental analysis. PLA-metallic phytate composites containing 20 or 30 wt% of additives were produced by melt blending in an internal mixer and their fire properties, thermogravimetric resistance have been characterized as well as the PLA chain degradation occurring during melt processing. The most significant flame retardant effect, observed by cone calorimeter test, was obtained when aluminum phytate was used. Cone calorimeter testing combined with pyrolysis combustion flow calorimetry (PCFC) analysis indicated that the barrier effect was more significant in the case of PLA filled with aluminum phytate. However, aluminum phytate proved to be responsible for PLA chain degradation during melt processing. Combinations of metallic phytate and native sodium phytate overcame this negative effect and allowed for limiting the thermal degradation of PLA during melt processing while preserving good fire performances, i.e. significant pHRR reduction and V-2 classification in UL-94 test.

Recycling PLA to multifunctional oligomeric compatibilizers for PLA/starch composites

Simple one-pot valorization of poly(lactic acid) (PLA) to green additives was demonstrated. PLA was thermally recycled in the presence of polyols, which accelerated the degradation process by reacting with PLA chains. As a result low molecular weight oligomers with polyols end-groups were formed. The reaction between PLA and multifunctional alcohols i.e. glycerol, sorbitol, glucose and starch were confirmed by FTIR, 1H NMR, SEC and MALDI-MS. The resulting amphiphilic products were evaluated as compatibilizer candidates for PLA/starch blends. Multiple techniques demonstrated that the obtained oligomers strengthened the interfacial adhesion and improved the compatibility and flexibility of extruded and melt-blended PLA/starch composites. The developed one-pot procedure required no solvent or catalyst offering good possibilities for up-scaling. It was, thus, demonstrated that PLA can be recycled to low molecular weight compatibilizers by simple process of thermal heating in the presence of polyols. This provides profound promise for retaining the material value of old PLA products at the same time as biobased additives are produced.

Peculiar crystallization kinetics of biodegradable poly(lactic acid)/poly(propylene carbonate) blends

Binary blends of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) were found to display a peculiar crystallization kinetics. The two biodegradable polymers were blended by melt mixing, to obtain binary blends at various compositions. Temperature‐modulated calorimetry and dynamic‐mechanical analysis indicated that the blend components are partially miscible, and display two separate glass transitions, at temperatures intermediate to those of the plain polymers. Electron microscopy analysis disclosed the morphology of PLA/PPC blends, made of PPC‐rich particles finely dispersed within the PLA‐rich matrix. The possible establishment of interactions between the functional groups of the two polymers upon melt mixing has been hypothesized as the reason for partial miscibility and compatibility of the two biodegradable polymers. The PLA/PPC blends display good mechanical properties, with enhanced performance at rupture compared with plain PLA. Most importantly, the addition of PPC affects also the crystallization kinetics of PLA, since the more mobile PPC chains favor diffusion of the stiffer PLA chain segments towards the growing crystals, which fastens the spherulite growth rate of PLA. Such positive influence of an amorphous polymer on crystal growth rate has been demonstrated here for the first time in blends that display phase‐separation in the melt. POLYM. ENG. SCI., 55:2698–2705, 2015. © 2015 Society of Plastics Engineers

Macromolecular chain structure design, synthesis and analysis of poly(l-lactide) linking ultraviolet absorbing groups

Poly(L-lactide) (PLA) with different chain structures was designed, and successfully synthesized by ring opening polymerization using 2-hydroxy-4-(3-methacryloxy-2-hydroxylpropoxy) benzophenone (BPMA), 2,2′-dihydroxy-4,4′-(2-hydroxylpropoxy) dibenzophenone (DHDBP) and 2-hydroxy-4-(2,3-dihydroxylpropoxy) benzophenone (HPBP) as initiators, respectively, to produce corresponding PLA-B (end-capped with BPMA), PLA-DB (end-capped with DHDBP) and PLA-HB-PLA (blocked with HPBP in the middle). High-molecular-weight PLA-DB400 with good visible light transparency and UV opacity was prepared. The chemical structures of the samples were characterized, the crystallization behavior, thermal stability, UV absorption properties and transmittance of PLA were investigated and analyzed. Results of GPC and DSC reveal that when the number average molecular weights (Mn) of PLA are around 4000, termination of a UV absorbing group like DHDBP greatly restricts the crystallization of PLA due to the larger volume and rigidity of the end-capping group, but increasing Mn to about 12 000 or higher weakens the hindering effect, resulting in a similar degree of crystallization (Xc). TG results show that PLA-DB400 has the best thermal stability due to the highest molar mass. When the UV absorber is blocked in the PLA chain, the restriction and steric hindrance of the absorber are much stronger than that in the end-capped material, making Xc significantly reduced. UV absorbance of the PLA solutions reveals that the introduction of UV absorbing groups gives an absorption to UV light below 350 nm and the position of the introduced groups has no influence on the UV absorption properties although the content of the UV group does enhance the UV absorbance, of which PLA-DB has the highest since DHDBP bears two 2-dihydroxybenzophenone groups. The transparency of PLA films is neither affected by position nor content of the introduced UV absorbing groups, which is very beneficial for the application of PLA in packaging materials that require high transparency.

Physicochemical and emulsifying properties of “extended” triblock copolymers

Two series of poly(ethylene glycol)-b-polylactide-b-poly(e-caprolactone) (MPEG-PLA-PCL) triblock copolymers with similar end-blocks (MPEG and PCL) lengths but varying mid-block (PLA) lengths were prepared by ring-opening polymerization (ROP) method and characterized by 1H NMR and GPC. The influence of mid-block length of these obtained copolymers on their surface activity, aggregation behavior, and emulsifying properties was investigated. When short PLA chain was inserted into the MPEG-PCL diblock copolymers, the formed triblock copolymers offer the advantage over the corresponding diblock copolymers. They allow higher solubility, faster interfacial adsorption, tighter micelle molecular packing, slightly larger micelle size, and higher emulsifying volume. When PLA chain was long, however, the triblock copolymers exhibited different properties due to the hydrophobicity of the chain. PLA chain length does not significantly affect the equilibrium surface tension. The findings based on this study not only demonstrate the important role of an inserted block with intermediate hydrophobicity on the physicochemical and emulsifying properties of block copolymers but also emphasize the impact of the chain length on these properties.

Crystallization Kinetics of Poly(1,4-butylene adipate) with Stereocomplexed Poly(lactic acid) Serving as a Nucleation Agent

Poly(1,4-butylene adipate) (PBA), poly(l-lactic acid) (PLLA), and poly(d-lactic acid) (PDLA) are biodegradable and environmentally friendly polymers. PLLA- and PDLA-formed stereocomplex crystallites (SCs) by solvent-casting served as nucleating agents of PBA. The isothermal crystallization kinetics and morphology of PBA and 0.2–3 wt % PBA/SC composites were studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The crystallization rate of neat PBA and PBA/SC composites increased as the crystallization temperature increased. With the addition of 3 wt % SC, the half-time for crystallization of the PBA/SC composite decreased by 25–47% for isothermal crystallization at 38–44 °C compared with that of neat PBA. In the presence of SC, the number of PBA nuclei increased, and the spherulite size decreased substantially. Therefore, the addition of SC to PBA induces heterogeneous nucleation. The product of the surface free energies of the PBA/SC composites is considerably higher than that of PBA because of the presence of amorphous PLA chains that limit the PBA chain flexibility, thereby leading to an increase in the surface free energy.

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO2 nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO2 and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO2 are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO2 are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO2 nanocomposites.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing.

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high-χ lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 °C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

The crystallization behavior of porous poly(lactic acid) prepared by modified solvent casting/particulate leaching technique for potential use of tissue engineering scaffold

The porous poly(lactic acid) (PLA) foams potential for tissue engineering usage are prepared by a modified solvent casting/particulate leaching method with different crystallinity. Since in typical method the porogens are dispersed in the solution and flow with the polymers during the casting and the crystallinity behavior of PLA chains in the limited space cannot be tracked, in this work the processing is modified by diffusing the PLA solution into a steady salt stack. With a thermal treatment before leaching while maintaining the stable structure of the porogens stack, the crystallinity of porous foams is made possible to control. The characterizations indicate that the porous PLA foams have a lower crystallizability than the bulk materials. Pores and caves of around 250μm size are obtained in samples with different crystallinity. The macro-structures are not much impaired by the crystallization nevertheless the morphological effect of the heating process is still obvious.

Morphology development, melt linear viscoelastic properties and crystallinity of polylactide/polyethylene/organoclay blend nanocomposites

ABSTRACTPolylactide/polyethylene blends (PLA/PE) and their nanocomposites were prepared via the melt blending process. The effects of organoclay, compatibilizer (PE‐g‐MA), and PE content on morphology, linear viscoelastic properties of the melt and cold crystallization of the samples have been studied. The Palierne model is applied to predict the rheological behavior of unfilled blends. It implies that there is a quantitative agreement between model and experimental data for low PE content blend. From WAXD and the rheological behavior, it is shown that organoclay exhibits a higher extent of intercalation and dispersion in PLA/PE/organoclay nanocomposite than in PLA/organoclay nanocomposite. The DSC results present that the addition of compatibilizer into blend nanocomposite increases cold crystallization temperature of PLA by about 3°C. This can be explained by the role of compatibilizer in transfer of a part of organoclay from PLA matrix to droplets resulting in increase of PLA chain mobility and, therefore, slightly greater cold crystallization temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41300.

Dramatic Improvements in Strain Hardening and Crystallization Kinetics of PLA by Simple Reactive Modification in the Melt State

Poly(lactic acid) (PLA) is chemically modified by radical mediated solvent-free, peroxide-initiated grafting of triallyl trimesate (TAM) coagent in the melt state. When compared with the parent material and with PLA samples treated with peroxide alone, coagent-modified materials demonstrate higher molar mass and improved melt rheological properties, including substantial improvements in melt elasticity and strain hardening under uniaxial extension. Although similar rheological modifications are obtained by PLA chain extension using a multi-functional epoxide oligomeric chain extender, the coagent-modified material demonstrates significantly enhanced crystallinity and crystallization rates. The appearance of a distinct crystallization exothermic peak and the disappearance of the cold crystallization temperature point to a nucleation effect in the coagent modified PLA, which together with the rheological enhancements can promote the processability of this material in conventional thermoplastics operations.

Adipate and Citrate Esters as Plasticizers for Poly(Lactic Acid)/Thermoplastic Starch Sheets

Poly(lactic acid) (PLA) and thermoplastic starch (TPS) sheets plasticized with different adipate and citrate esters were produced by a calendering-extrusion process. The incorporation of plasticizers significantly reduced the glass transition temperature and increased the PLA chain mobility thus improving the mechanical properties. Among the plasticizers employed, diethyl adipate significantly increased the elongation of the sheets and slightly increased the water vapor permeability. Micrographs revealed the incompatibility between starch and PLA, and there was no plasticizer phase separation, suggesting that the plasticizer concentration was adequate. The incorporation of adipate or citrate esters improves the mechanical properties and processability of PLA/TPS sheets produced by calendering extrusion at a pilot scale.

Studies on Melt Processable Biocomposites of Polylactic Acid

Melt processable microcrystalline cellulose (MCC)/poly(lactic acid) (PLA) composites were successfully prepared by twin-screw extrusion. Several characterization techniques were used to investigate the effect of MCC on rheological behavior, morphology, crystallization and melting behavior of the PLA and structure–property correlation of the MCC/PLA composites has been established. Rheological measurements showed that the addition of MCC has a dramatic influence on the low frequency relaxations of PLA chains and above 5 % of MCC, it forms percolated network structure. Differential scanning calorimeter analysis showed that MCC acted as nucleating agent enhancing crystallization below the percolation concentration. Properties of MCC/PLA composites have been compared with that of talc and CaCO3 filled composites. Talc is found to be more effective in crystallizing PLA than MCC and CaCO3. MCC/PLA composites are found be melt processable like that of talc and CaCO3 filled PLA composites.

Melt Free-Radical Grafting of Maleic Anhydride onto Biodegradable Poly(lactic acid) by Using Styrene as A Comonomer

Maleic anhydride (MA) was grafted onto poly(lactic acid) (PLA) in the presence of styrene (St) by using a free-radical grafting methodology. The grafting degree (Dg) of MA was increased from 0.65 wt % to 1.1 wt % with the St/MA ratio up to 2/1, where the grafting efficiency (Eg) of MA was 27%. However, both Dg and Eg were decreased with further increasing of the St/MA ratio to 4/1. The Dg of MA increased with MA concentration and showed a maximum at 180 °C in the temperature range of 165 °C–190 °C. The grafting mechanisms of MA in the presence of St are analyzed based on titration, thermogravimetric analysis and infrared results, i.e., MA is grafted onto PLA chains via single monomers and a charge-transfer-complex (CTC) at St/MA ratios of ≤ 1/1, while dominantly via St-co-MA oligomers at St/MA ratios of around 2/1. Copolymerization rather than grafting of St and MA occurs at St/MA ratios of around 4/1. The thermal stability of PLA was compromised to a certain extent by the grafting of MA, resulting in reductions in the decomposition temperature (Td-5%) and molecular weight of the PLA. In addition, the crystallization and melting temperatures of the PLA were slightly reduced after the grafting.

Structural Basis for Unique Hierarchical Cylindrites Induced by Ultrahigh Shear Gradient in Single Natural Fiber Reinforced Poly(lactic acid) Green Composites

A local shear flow field was feasibly generated by pulling the ramie fiber in single fiber reinforced poly(lactic acid) (PLA) composites. This was featured by an ultrahigh shear gradient with a maximum shear rate up to 1500 s(-1), a level comparable to that frequently occurring during the practical polymer processing. To distinguish shear-induced self-nucleation and ramie fiber-induced heterogeneous nucleation, the shear history was classified by pulling the fiber for 5 s (pulled sample) and pulling out the fiber during 10 s (pulled-out sample), while the static fiber-induced crystallization was carried out as the counterpart. As a result of the ultrahigh shear gradient, the combination of primary shear-induced nucleation in the central region and secondary nucleation in the outer layer assembled the unique hierarchical superstructures. By comparing the architectural configurations of interphases formed in the static, pulled, and pulled-out samples, it was shown that the hierarchical cylindrites underwent the process of self-nucleation driven by the applied shear flow, very different from the formation of fiber-induced transcrystallinity (TC) triggered by the heterogeneous nucleating sites at the static fiber surface. The twisting of transcrystallized lamellae may take place due to the spatial hindrance induced by the incredibly dense nuclei under the intense shearing flow, as observed in the synchrotron X-ray diffraction patterns. The influence of chain characteristics on the crystalline morphology was further explored by adding a small amount of poly(ethylene glycol) (PEG) to enhance the molecular mobility of PLA. It was of interest to find that the existence of PEG not only facilitated the growth rates of TC and cylindrites but also improved the preferential orientation of PLA chains and thus expanded the ordered regions. We unearthed lamellar units that were composed of rich fibrillar extended chain crystals (diameter of 50-80 nm). These results are of importance to shed light on tailoring crystalline morphology for natural fibers reinforced green composite materials. Of immense practical significance, too, is the crystalline evolution that has been tracked in the simple model penetrated with an ultrahigh shear gradient, which researchers have so far been unable to replicate during the practical melt processing, such as extrusion and injection molding.

Maintaining Structural Stability of Poly(lactic acid): Effects of Multifunctional Epoxy based Reactive Oligomers

In order to reduce the effects of hydrolytic degradation and to maintain sufficient viscosity during processing of biomass based poly(l-lactic acid) (PLLA), various epoxy functional reactive oligomers have been characterized and incorporated into the degraded fragments as chain extenders. The molecular weight of PLLA increased with the increase in functionality of the reactive oligomers. No further increase in molecular weight was observed for oligomers with functionality of greater than five. Under our experimental conditions, no gelation was found even when the highest functionality reactive oligomers were used. This is attributed to the preferential reaction of the carboxylic acid versus the negligible reactivity of the hydroxyl groups, present at the two ends of the degraded PLLA chains, with the epoxy groups. The study provides a clear understanding of the degradation and chain extension reaction of poly(lactic acid) (PLA) with epoxy functional reactive oligomers. It is also shown that a higher functionality and concentration of the reactive oligomers is needed, to bring about a sufficient increase in the molecular weight and hence the hydrolytic stability in circumstances when PLA chains suffer significant degradation during processing.

Synthesis and characterization of star polylactide by ring-opening polymerization of l-lactic acid O-carboxyanhydride

Ring-opening polymerization of l-lactic acid O-carboxyanhydride was catalyzed by 4-dimethylaminopyridine in the presence of polyols pentaerythritol (PER) or dipentaerythritol (DPE). A high yield and relatively high molecular weight of 4- or 6-arm star PLA were obtained. The reaction was observed to be conducted easily and controllably. NMR analysis revealed that the end of the star PLA chain is a hydroxyl group and the central core is a PER or DPE group. The crystallinity of star PLA is lower than that of linear PLA. The crystallinity of 4-arm star PLA is lower than that of 6-arm PLA. Compared with that of 4-arm star PLA, the molecular arrangement of 6-arm star PLA may be relatively more regular.