Microcellular foaming of poly(lactic acid) branched with food-grade chain extenders

This study evaluated the effectiveness and efficiency of two food-grade multifunctional epoxies chain extenders (CE) in branching PLA and improving its foamability. Both CE grades were effective in branching PLA causing increased end mixing torque, shear, elongational viscosities, molecular weight but decreased crystallinity of poly(lactic acid) (PLA) with CE content, due to chain entanglements. CE with low epoxy equivalent weight (EEW) was more efficient than the counterpart with high EEW due to its high reactivity. Neat PLA foams showed poor cell morphology with areas without nucleated cells and had a low expansion, owing to its low elongational viscosity. By contrast, there was a considerable change in the morphology of the PLA foam structure caused by its branching. Chain-extended PLA foams had uniform cell morphology with a high void fraction (up to ~85%) and expansion ratio (an eightfold expansion over unfoamed PLA) due to their high elongational viscosities, suggesting that melt properties of branched PLA were appropriate for optimum cell growth and stabilization during foaming. Overall, CE with low EEW was the most effective grade and 0.25% the optimum content that provided appropriate melt viscosity to produce PLA foams with a homogeneous structure, fine cells, high void fraction, high volume expansion ratio, and cell-population density.     

连续挤出发泡聚乳酸泡孔结构的影响因素

介绍了采用超临界CO2作为发泡剂,连续挤出聚乳酸泡沫塑料的方法。在不同的实验条件下,对聚乳酸进行挤出发泡,得到聚乳酸发泡样品。通过对样品的ESM照片的分析研究,得出了不同的发泡条件对挤出聚乳酸泡沫泡孔结构的影响。结果表明螺杆转速的增加使得泡孔数量增加,泡孔形态更加规整均匀。模头温度影响了泡孔形态,较高的温度会使得样品的泡孔形态受到不利的影响。水分的存在不利于聚乳酸发泡成为均匀发泡倍率高的泡沫制品。成核剂促进异相成核,使发泡样品的泡孔结构更加均匀,大大提高了聚乳酸泡沫塑料的泡孔密度。     

Extrusion blown films of poly(lactic acid) chain‐extended with food grade multifunctional epoxies

The effectiveness and efficiency of two food grade multifunctional epoxies with low and high epoxy equivalent weights in chain extending/branching poly(lactic acid) (PLA) were studied in a torque rheometer. Processing PLA and chain extender (CE) at 200°C for 300 s not only chain‐extended PLA effectively as indicated by a significant increase in the mixing torque as well as PLA's melt viscosity and molecular weight, but also branched it leading to its reduced crystallinity. Chain extension occurred through the ring opening reaction of epoxy groups in the CE with PLA's hydroxyl and/or carboxyl groups. CE with lower epoxy equivalent weight was more efficient due to its higher reactivity. Secondly, the processabilities of PLA films chain‐extended and branched with various amounts of the most efficient CE were assessed. Like in torque rheometer, chain extension and branching also occurred during film production as indicated by PLA's increased molecular weight and decreased crystallinity when blended with CE. However, film manufacture was feasible only for blends with up to 0.5% CE, becoming unprocessable above this content due to chain entanglement leading to increased viscosity. Chain extension/branching of PLA was beneficial in overcoming film's brittleness since its impact strength increased almost linearly with the CE content. POLYM. ENG. SCI., 59:2211–2219, 2019. © 2019 Society of Plastics Engineers     

Blending and foaming thermoplastic starch with poly (lactic acid) by CO2-aided hot melt extrusion

Biomaterials are materials that can be biodegradable or obtained from renewable resources. Among them, poly (lactic acid) (PLA) and thermoplastic starch (TPS) represent an interesting alternative to replace petro-sourced thermoplastics. In this study, blends made by TPS addition to PLA were subjected to a foaming process using supercritical CO₂-aided extrusion. Extruder die temperature and CO₂ content were the most prominent parameters explaining the structure of the foams obtained. Both parameters were intimately linked since the CO₂ flow depends on the melt temperature, the lower the temperature, the higher the CO₂ solubility. Therefore, the die temperature was chosen to pilot the process. Whatever the experimental conditions, a 50/50 (in wt%) blend was poorly foamed due to the strong incompatibility between both biopolymers. However, the blend made of 80 wt% PLA and 20 wt% TPS gave evenly foamed samples. In terms of expansion and type of porosity this blend behaved like pure PLA with high porosity, up to 96%, and the presence of a threshold die temperature separating a close cell porosity at lowest temperatures and an open cell structure above the threshold. This temperature threshold was however significantly lower to that obtained with pure PLA.     

Preparation and characterization of high‐molecular‐weight poly(l‐lactic acid) by chain‐extending reaction with phosphites

Poly(l ‐lactic acid) (PLLA) of high molecular weight was prepared by a chain‐extending reaction in a microcompounder. Phosphites were used as chain extenders to increase the molecular weight of the PLLA prepolymer, which was prepared by the bulk polycondensation of l‐lactic acid. The effects of the amount of phosphite, the temperature, and the screw speed on the torque of the PLLA melt were studied. Under the optimal conditions, the molecular weight of PLLA increased from 62,100 to 126,000 g/mol. The chemical structure and crystallinity of PLLA were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR and ¹³C‐NMR, differential scanning calorimetry, and X‐ray diffraction. The mechanical properties of PLLA were measured. The results indicate that triphenyl phosphite (TPPi) was an effective chain extender for PLLA. The role of the TPPi in chain extending is suggested to be an esterification‐promotion agent. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly (lactic acid) foaming

Poly (lactic acid) or polylactide (PLA) is an aliphatic thermoplastic polyester produced from renewable resources and is compostable in the environment. Because of the massive use of foamed products of petroleum-based polymers, PLA foams have been considered as substitutes for some of these products. Specifically, because of PLA's competitive material and processing costs, and its comparable mechanical properties, PLA foams could potentially replace polystyrene (PS) foam products in a wide array of applications such as packaging, cushioning, construction, thermal and sound insulation, and plastic utensils. Due to their biocompatibility, PLA foams can also be used in such biomedical applications as scaffolding and tissue engineering. But PLA has several inherent drawbacks, which inhibit the production of low-density foams with uniform cell morphology. These drawbacks are mainly the PLA's low melt strength and its slow crystallization kinetics. During the last two decades, researchers have investigated the fundamentals of PLA/gas mixtures, PLA foaming mechanisms, and the effects of material modification on PLA's foaming behavior through various manufacturing technologies. This article reviews these investigations and compares the developments made thus far in PLA foaming.     

Physical extruder foaming of poly(lactic acid)—processing and foam properties

The article describes extrusion foaming of poly(lactic acid) (PLA) using carbon dioxide in the supercritical state as foaming agent emphasizing the steps required to establish a stable extrusion process. Low melt strength of PLA plays a role in optimizing processing conditions. The tests included PLA grades of different viscosity in addition to a chain extender. Processing at low temperature is possible due to the plasticizing effect of the CO₂ on the PLA melt and a sufficiently low melt temperature is also a prerequisite in production of stable foams due to improved melt strength. Foams were characterized by density, cell structure, crystallinity, and mechanical properties in compression. Low density, microcellular foams with density down to 20–30 kg/m³ were obtained for three different PLA grades. Varying die temperature and pressure drop rate we can explain observed abrupt drops in density with increasing CO₂ content by the interplay between cell nucleation and gas diffusivity at given temperatures. An effect on melt strength similar to using a chain extender is achieved by lowering the melt temperature at the die. Observed variations in sample crystallinity do not correlate with foam density. The PLA foams have good energy absorption capability. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

The difference of equilibrium melting point between poly(l‐lactic acid) and poly(l‐lactic acid)/poly(d‐lactic acid) blends: cases with three molecular weights

In order to explore the origin of the higher melting point of poly(lactic acid) (PLA) stereocomplex crystal (SC) than that of homo‐crystal (HC), the equilibrium melting point () differential between SC and HC was determined using the Hoffman–Weeks method. The results showed that, for PLA samples with M_n around 16, 20 and 65 kg mol^?1, the differential between SC and HC is around 36, 42 and 55 °C, respectively. Thus, the higher melting point of SC compared to HC does not stem from differential only. For PLA samples with lower M_n, the supercooling differential between poly(l ‐lactic acid) (PLLA)/poly(d ‐lactic acid) (PDLA) blends and PLLA is smaller than that with higher M_n, which means chain diffusion behavior is crucial for SC formation in PLLA/PDLA blends. The fact that the SC adopts the intermolecular parallel arrangement rather than the adjacent chain folding is verified by the greater slope of the melting point of SC versus crystallization temperature fitting curve when M_n is relative higher. © 2018 Society of Chemical Industry     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties,crystallization characteristics,and foaming behavior of polytetrafluoroethylene‐reinforced poly(lactic acid) composites

In this study, poly(lactic acid) (PLA)/polytetrafluoroethylene (PTFE) composites containing different amounts of PTFE were prepared by melt blending. The mechanical, crystallization, and foaming properties of the prepared composites were investigated. Tensile test results indicated that the mechanical properties of the composite with PTFE showed significant reinforcement and toughening effects. The average elongation‐at‐break of the composite increased by 72% compared with pure PLA. Scanning electron microscopy (SEM) showed that the PTFE elongated into fibrils during blending and formed a physical network of entanglements in the melt. Differential scanning calorimetry (DSC) also showed that PTFE had a significant nucleation effect on polymer crystals and greatly increased the crystallinity of the PLA matrix. Moreover, PTFE dramatically enhanced the melt viscosity of PLA, which was investigated by rheological tests. The injection molding foaming experiments revealed that adding 1 wt% PTFE had the most notable heterogeneous nucleation effect on foamed cells, with the cell size decreasing from 81.5 μm for neat PLA to 25.2 μm, and the cell density increasing from 1.34 × 10⁸ cells/cm³ to 2.53 × 10⁹ cells/cm³. POLYM. ENG. SCI., 57:570–580, 2017. © 2016 Society of Plastics Engineers     

Factors affecting the degradation and drug‐release mechanism of poly(lactic acid) and poly[(lactic acid)‐co‐(glycolic acid)]

This paper reviews the most important factors affecting the degradation and drug‐release rate of bio‐erodible polymers for better control in biomedical applications. There are several factors that influence the overall rate of degradation, in addition to pH and copolymer composition. In general, polymer degradation is accelerated by greater hydrophilicity in the backbone or end groups, lesser crystallinity, lower average molecular weight, and smaller size of the finished device. At the moment, literature reflects contradictions about the role played by chemically reactive additives, crystallinity and degradation path. Factors affecting degradation and drug‐release rate are discussed in their decreasing order of importance, including intrinsic properties of polymers and processing parameters. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

Blends of poly(ε‐caprolactone‐b‐lactic acid) and poly(lactic acid) for hot‐melt applications

The condensation reaction product of poly(lactic acid) (PLA) and a hydroxyl‐terminated four‐armed poly(ε‐caprolactone) (PCL) was studied by size‐exclusion chromatography, DSC, and NMR. The use of both L ‐lactic acid (LLA) and rac‐lactic acid (rac‐LA) was studied and the use of two different catalysts, stannous 2‐ethylhexanoate [Sn(Oct)₂] and ferrous acetate [Fe(OAc)₂], was also investigated. The thermal stability and adhesive properties were also measured for the different formulations. The characterization results suggested the formation of a blend of PLA and a block‐copolyester of PLA and PCL. The results further indicated partial miscibility in the amorphous phase of the blend showing only one glass‐transition temperature in most cases, although no randomized structures could be detected in the block‐copolymers. The polymerization in the Fe(OAc)₂‐catalyzed experiments proceeded slower than in the Sn(Oct)₂‐catalyzed experiments. The discoloring of the polymer was minor when Fe(OAc)₂ was used as catalyst, but significant when Sn(Oct)₂ was used. The ferrous catalyst also caused a slower thermal degradation. Differences in the morphology and in the adhesive properties could be related to the stereochemistry of the poly(lactic acid). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 196–204, 2004     

Melt flow behavior in capillary extrusion of nanosized calcium carbonate‐filled poly(L‐lactic acid) biocomposites

Nanosized calcium carbonate (nano‐CaCO₃)‐filled poly‐L ‐lactide (PLLA) biocomposites were compounded by using a twin‐screw extruder. The melt flow behavior of the composites, including their entry pressure drop, melt shear flow curves, and melt shear viscosity were measured through a capillary rheometer operated at a temperature range of 170–200°C and shear rates of 50–10³ s^?1. The entry pressure drop showed a nonlinear increase with increasing shear stress and reached a minimum for the filler weight fraction of 2% owing to the “bearing effect” of the nanometer particles in the polymer matrix melt. The melt shear flow roughly followed the power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Hence, adding a small amount of nano‐CaCO₃ into the PLLA could improve the melt flow behavior of the composite. POLYM. ENG. SCI., 52:1839–1844, 2012. © 2012 Society of Plastics Engineers     

UV‐excitable fluorescent poly(lactic acid) fibers

The UV‐excitable fluorescent poly(lactic acid) (PLA) fibers were spun by the traditional melt spinning process, and the effects of the fluorescent powder content (w(FP)) and draw ratio (DR) on the structure and properties of the fluorescent PLA fibers were investigated, respectively. The results showed that the emission spectra of fluorescent PLA fibers were peaked at 530 nm after UV excitation, indicating the PLA fibers would emit green light under UV light. With the increasing of w(FP), the relative fluorescence intensity of PLA fibers increased gradually, whereas more and larger protrusions were formed on the fiber surface due to the agglomeration of fluorescent powder, both the crystallinity and mechanical properties of fluorescent PLA fiber showed the decreasing trend with the increase of w(FP). With the increase of DR, the tensile strength of fluorescent PLA fibers increased gradually, whereas the relative fluorescence intensity of PLA fibers increased firstly and then decreased, and the highest fluorescence intensity was obtained when the DR was 3.6. In addition, the confocal laser scanning microscope can be used well to simulate the 3D distribution of fluorescent powder among the PLA fibers. POLYM. ENG. SCI., 56:373–379, 2016. © 2016 Society of Plastics Engineers     

Compatibilization of the poly(lactic acid)/poly(propylene carbonate) blends through in situ formation of poly(lactic acid)‐b‐poly(propylene carbonate) copolymer

The in situ formation of poly(lactic acid)‐b‐poly(propylene carbonate) (PLA‐b‐PPC) block copolymers were carried out by the reaction between PLA and PPC in the presence of tetrabutyl titanate via transesterification. Molecular weight measurements and ¹³C nuclear magnetic resonance spectroscopy revealed that PLA‐b‐PPC block copolymers with higher molecular weight were obtained by controlling the reactivity point ratio between PLA chains and PPC chains in PLA/PPC reaction system. The sample with a composition of PLA:PPC = 40:60 (wt %) and a catalyst amount of 0.5 wt % had a more proportionable reactivity point ratio between PLA chains and PPC chains compared with other samples, resulting in a most conspicuous transesterification and inconspicuous chain scission reaction. Therefore, its high molecular weight fraction (M_w > 40.0 × 10⁴) increased 80%. The formation of macromolecular PLA‐b‐PPC copolymer could strengthen the entanglement between PLA and PPC molecular chains, which resulted in an increased viscosity of blends at low shear rate. In addition, the elongation at break of sample with a composition of PLA:PPC = 40:60 (wt %) and a catalyst amount of 0.5 wt % was nearly as twice as which without catalyst because of the improving miscibility of PLA domains and PPC matrix by the compatibilization of PLA‐b‐PPC copolymer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46009.     

Reactive blending of poly(L‐lactic acid) with poly(ethylene‐co‐vinyl alcohol)

Poly(L ‐lactic acid) (PLLA) was blended with poly(ethylene‐co‐vinyl alcohol) (EVOH) in the presence of an esterification catalyst to induce reaction between the hydroxyl groups of EVOH and the terminal carboxylic group of PLLA. Nascent low‐molecular‐weight PLLA, obtained from a direct condensation polymerization of L ‐lactic acid in bulk state, was used for the blending. Domain size of the PLLA phase in the graft copolymer was much smaller than that corresponding to a PLLA/EVOH simple blend. The mechanical properties of the graft copolymer were far superior to those of the simple blend, and the graft copolymer exhibited excellent mechanical properties even though the biodegradable fraction substantially exceeded the percolation level. The grafted PLLA reduced the crystallization rate of the EVOH moiety. Melting peak temperature (T_m) of the PLLA phase was not observed until the content of PLLA in the graft reaction medium went over 60 wt %. The modified Sturm test results demonstrated that biodegradation of EVOH‐g‐PLLA took place more slowly than that of an EVOH/PLLA simple blend, indicating that the chemically bound PLLA moiety was less susceptible to microbial attack than PLLA in the simple blend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 886–890, 2005     

Effects of the chain‐extender content on the structure and performance of poly(lactic acid)–poly(butylene succinate)–microcrystalline cellulose composites

Composites of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) and microcrystalline cellulose (MCC) as reinforcements of the polymer matrix were prepared by melt blending to improve the brittleness of PLA. As a reactive compatibilizer, a chain extender was used in an attempt to solve the composites’ interfacial problems and to improve their mechanical properties; Fourier transform infrared spectroscopy indicated that the chain extender functionally reacted with PLA, PBS, and MCC mainly through end carboxyls or end hydroxyls. Scanning electron microscopy indicated that the chain extender significantly improved the cohesive interfacial forces. Differential scanning calorimetry and X‐ray diffraction showed that the chain extender inhibited crystallization, and these effects were greater when its percentage was increased. The addition of chain extender improved the tensile and impact strength of the composites, and this improvement was proportional to the chain‐extender percentage. However, the elongation at break decreased when the chain‐extender percentage was over 0.5% because of mild crosslinking within the resin matrix. Rheology indicated that the complex viscosity and storage and loss moduli of the composites increased with increasing amount of chain extender; this indicated that the addition of chain extender improved the melt strength and processability of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44895.     

Blown film extrusion of poly(lactic acid) without melt strength enhancers

Processing strategies were developed to manufacture poly(lactic acid) (PLA) blown films without melt strength enhancers (MSEs). The effects of processing temperature on PLA's melt properties (shear and elongational viscosities), PLA grades, and other processing conditions [ratio of take‐up roller to extruder's rotational screw speeds or processing speed ratio (PSR) and internal air pressures] on film's blow‐up ratio were examined. Experimental results indicate that extrusion‐blown amorphous and semicrystalline PLA films can be successfully manufactured without MSEs by controlling melt rheology through processing temperature and other extrusion processing conditions. PLA processed at lower extrusion temperature had higher melt viscosities, which favored the formation of stable films depending on the PSR and internal air pressure used. Inappropriate control of PSR and internal air pressure led to unstable films with various processing defects such as melt sag, bubble dancing, or draw resonance, irrespective of the lower extrusion processing temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45212.