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.     

Rheology and extrusion foaming of chain‐branched poly(lactic acid)

In this study, the effect of macromolecular chain‐branching on poly(lactic acid) (PLA) rheology, crystallization, and extrusion foaming was investigated. Two PLA grades, an amorphous and a semi‐crystalline one, were branched using a multifunctional styrene‐acrylic‐epoxy copolymer. The branching of PLA and its foaming were achieved in one‐step extrusion process. Carbon dioxide (CO₂), in concentration up to 9%, was used as expansion agent to obtain foams from the two PLA branched using chain‐extender contents up to 2%. The foams were investigated with respect to their shear and elongational behavior, crystallinity, morphology, and density. The addition of the chain‐extender led to an increase in complex viscosity, elasticity, elongational viscosity, and in the manifestation of the strain‐hardening phenomena. Low‐density foams were obtained at 5–9% CO₂ for semi‐crystalline PLA and only at 9% CO₂ in the case of the amorphous PLA. Differences in foaming behavior were attributed to crystallites formation during the foaming process. The rheological and structural changes associated with PLA chain‐extension lowered the achieved crystallinity but slightly improved the foamability at low CO₂ content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Isothermal melt crystallization and performance evaluation of polylactide/thermoplastic polyester blends with multi‐functional epoxy

A multi‐functional epoxy (ADR) was used to improve compatibilization of poly(lactic acid) (PLA)/ thermoplastic polyester elastomer (TPEE) blends. Influence of ADR on isothermal melt crystallization of the blends was investigated. The results show that isothermal melt crystallization rate of the samples increases with ADR loading. It can be attributed to a nucleation enhancement resulted from an increase of molecular weight and melt viscosity created by the chain extension/branched process of PLA in the presence of ADR. In addition, the maximum crystallinity of the samples shows a decrease with increasing ADR loading because of the chain extended and branched reaction. Quenched and crystallized samples were fabricated using compression molding under different cooling conditions in‐mold. Effects of crystallinity and ADR on mechanical performances of the PLA/TPEE sample were investigated. With increasing the crystallinity, the PLA/TPEE sample shows a marked enhancement in heat resistance. However, the tensile ductility of the crystallized PLA/TPEE sample drastically decreases due to the formation of firm crystal crosslinking and the incompatibility between PLA and TPEE. It is notable that the tensile ductility of the crystallized samples is improved with the introduction of ADR owing to its reactive compatibilization effect. Finally, the crystallized PLA/TPEE/ADR samples with improved heat resistance and relative higher ductility are obtained. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46343.     

Effect of Two‐Step Chain Extension using Joncryl and PMDA on the Rheological Properties of Poly (lactic acid)

This research considers a two‐step chain extension reaction in the presence of two chain extenders, Joncryl and Pyromellitic dianhydride (PMDA), as a solution for poor melt properties of poly (lactic acid) (PLA). The aim of adding PMDA is to increase the carboxyl groups via the anhydride ring‐opening reaction so that the reaction between PLA and Joncryl could be facilitated since the reactivity between the epoxy and carboxyl group is more than epoxy and hydroxyl group. The reactions are confirmed by measuring the acid value, and a two‐step reaction mechanism is suggested. Shear and elongational rheological properties of the samples are investigated; furthermore, gel permeation chromatography analyses and tensile tests are exploited for studying the molecular weight and tensile properties, respectively. The results show that the chain extension reactions lead to an increase in the storage modulus, complex viscosity, and molecular weight. Also, the PLA chains which are extended utilizing both chain extenders simultaneously evince a synergistic improvement in the shear and elongational rheological properties due to longer segments between branching points on the structure.     

Foamability and viscosity behavior of extrusion foamed PLA–pulp fiber biocomposites

This study addresses the effect of fiber reinforcement, chain extension, and physical foaming agent type on foam morphology and viscosity behavior of pulp fiber reinforced poly(lactic acid) (PLA) biocomposites. PLA reinforced with 0, 10, and 20 wt % of bleached kraft pulp fibers with and without chain extender were foamed using two different physical foaming agents (carbon dioxide and isobutane) by extrusion foaming. Densities, foam morphologies, and viscosities were systematically analyzed and compared from the produced foams. As a conclusion, low-density foams are produced with both foaming agents and fiber levels, fiber addition limiting cell growth. Isobutane provides better dimensional stability with narrower cell size distribution, whereas carbon dioxide enables lower foaming temperature. Chain extension is essential to achieve foam with low density and good cell structure. Contrary to nonchain extended PLA, addition of fibers reduced the viscosity of chain extended PLA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48202.     

Effect of chain extrender on the compatibility,mechanical and gas barrier properties of poly(butylene adipate-co-terephthalate)/poly(propylene carbonate) bio-composites

Bio-composites consisting of poly(butylene adipate-co-terephthalate) (PBAT), poly(propylene carbonate) (PPC) and epoxy chain extender ADR 4468 were fabricated via melt blending using a torque rheometer. The relationship of the torque, melt viscosity, and molecular weight of the bio-composites was established via polymeric liquid theory to estimate the real-time chain extension reaction rate under different ADR contents. At the meantime, rheological behavior, thermal and mechanical properties, morphologies, gas barrier properties of the PBAT/PPC/ADR bio-composites were systematically characterized. The corresponding results revealed that the water vapor transmission rate (WVTR) reduced by 50% under 30 phr (parts per hundreds of resin) PPC content. The addition of ADR is beneficial to improve the mechanical properties, thermal stability and phase dispersion of PBAT/PPC without affecting the water barrier property. With 3 phr ADR, the tensile stress and elongation at break were increased from 19.5 MPa and 1184% to 26.9 MPa and 1443%, respectively. In addition, the data of the torque rheometer revealed that the chain extension reaction rate and the melt viscosity was increased with the increasing ADR content, but the reaction rate was reduced with the excessive viscosity.     

Preparation and characterization of chain extended Poly(butylene succinate) foams

In order to improve the viscoelasticity and foamability, poly (butylene succinate) (PBS) was modified through reactive melt mixing with chain extender (CE) having multi epoxy‐groups. Subsequently, the prepared chain extended PBS (CEPBS) was foamed in a high pressure stainless steel autoclave using CO₂ as physical blowing agent. The molecular weight, thermal properties, rheological properties, and foam properties of various PBS samples were characterized using gel permeation chromatography, differential scanning calorimetry, rotational rheometer, and scanning electron microscope, respectively. With the introduction of CE, the molecular weight, the crystallization temperature, the complex viscosity and storage modulus of PBS were increased and the crystallization degree of PBS was decreased. At the CE content of 0.75 phr, the cross‐linking structure was formed and the expansion volume ratio increased to nearly 15 times, which meant the chain extension played an important role in the foaming process of PBS. POLYM. ENG. SCI., 55:988–994, 2015. © 2014 Society of Plastics Engineers     

Microcellular extrusion‐foaming of polylactide with chain‐extender

The effects of adding epoxy‐functionalized chain‐extender (CE) and processing conditions such as die temperature on the cell morphology, volume expansion ratio (VER), open cell content (OCC), and crystallization of microcellular extruded polylactide (PLA) were investigated. When compared with pure PLA, the addition of talc decreased the average cell size and increased the cell density. Moreover, the simultaneous addition of talc and CE led to denser and more uniform cell structure up until 1.0% CE content. In general, the volume expansion ratio and open cell content of all the formulations decreased with the die temperature. The addition of talc decreased both VER and OCC, whereas the addition of CE increased both. The die temperature did not affect the degree of crystallinity significantly. The addition of talc increased the crystallinity, but the addition of CE decreased it. Finally, the molecular weight of PLA increased significantly with the addition of CE. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Crystallization kinetics of chain extended poly(lactic acid)/clay nanocomposites

The poly(lactic acid)/clay nanocomposites (PLACNs) were prepared by melt mixing method, then multiepoxide chain extender (CE) was added into PLACNs to induce the branched structure of poly(lactic acid) (PLA) chains. The nonisothermal cold crystallization and isothermal melting crystallization of PLA, PLACNs, and chain extended PLACNs (CEPLACNs) were characterized by DSC and studied by Avrami analysis. The results showed that the inducing of clay and CE affected the crystallization behavior of PLA in different way. Adding CE increased the overall crystallinity of PLA at cooling process, but clay had an opposite effect. Besides that, the addition of CE and clay increased the crystal nuclei number due to the heterogeneous nucleation mechanism. According to the crystallization kinetics study, the inducing of clay almost no effect on the crystal growth rate of PLA, but the branched structure had a pronounced effect for improving crystal growth rate of PLA. POLYM. COMPOS., 36:2123–2134, 2015. © 2014 Society of Plastics Engineer     

Eliminating the thermal degradation of polylactic acid by the modification of a macromolecular epoxy-type chain extender

A novel macromolecular epoxy chain extender was synthesized and used to modify the PLA resin for developing conventional melt extrusion technology. Fourier-transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and ¹H nuclear magnetic resonance (¹H NMR) characterized the successful synthesis. For the first time, the molecular weight $\left({\overline{M}}_w\right)$ plays a key role in preventing thermal degradation and chain extension were discussed experimentally. Macromolecular chain extender showed superior advantages in that the chain extender with higher molecular weight was easier to get the long chain branched (LCB) structure in the modification of PLA. The characterization by rotational rheometer, GPC, melt index, chemical titration, and differential scanning calorimeter (DSC), results demonstrate that the macromolecular epoxy chain extender could decrease the concentration of terminal carboxyl groups and increase ${\overline{M}}_w$ with only 0.5% dosage. At a concentration ≥2%, there were a large number of long chain branched structures in the chain extension system for modified PLA. It showed better melt strength and would influence the crystallinity of PLA which would significantly improve the processability of PLA, especially in high-temperature extrusion, blow molding, spinning, and other processing technologies and applications.     

亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究

将聚氨基环氧基硅氧烷（PSQ）以及亚磷酸酯功能化的聚氨基环氧基硅氧烷（PPSQ）与聚乳酸（PLA）通过熔融共混制备了扩链PLA。研究了亚磷酸酯基团的引入对PSQ在PLA中的扩链和阻燃性能的影响,探究PPSQ在PLA中的阻燃机理。结果表明,相比于PSQ,PPSQ可以明显提高PLA的分子量和复合黏度,具有更好的扩链作用;PPSQ的引入可以明显改善PLA的阻燃性能,使得PLA?PPSQ的极限氧指数提高至25.4 %,比纯PLA提升了31.6 %,且使得PLA的热释放速率峰值和总热释放量分别下降了18.1 %和16.6 %。分析可知,由于亚磷酸酯基团的引入,促使PLA?PPSQ中的硅元素在燃烧过程中向炭层表面迁移形成更多富含碳化硅和氧化硅的致密炭层,起到隔热隔氧的作用,进而发挥优异的阻燃性能。     

Poly (vinyl alcohol)/polylactic acid blend film with enhanced processability,compatibility, and mechanical property fabricated via melt processing

Poly (vinyl alcohol)/polylactic acid (PVA/PLA) blend film, which is environment friendly and has potential applications in food and electronic packaging fields, was fabricated by melt extrusion casting. Fourier transform infrared spectroscopy analysis confirmed the formation of the hydrogen bonding between PLA and PVA, which improved the compatibility of PLA with PVA, making PLA uniformly dispersed in PVA matrix as small spheres, even when PLA content increase to 15 wt%. In this way, the original hydrogen bond network among PVA was disturbed and the chain mobility of PVA was activated, endowing PVA/PLA blends with lower melt viscosity than bot modified PVA and PLA, and the blend films with the increased crystallinity, mechanical property, and water resistance. Compared with PVA film, the crystallinity, tensile strength and Young's modulus of the blend film with 15 wt% PLA, respectively, increased by 15.1%, 9 and 51 MPa, and the water contact angle enlarged from 23° to 60°.     

Comparison of melting and crystallization behaviors of polylactide under high-pressure CO2, N2, and He

This study investigated the melting and crystallization behaviors of polylactide (PLA) under high-pressure CO₂, N₂, and helium (He) using a high-pressure differential scanning calorimeter and a wide-angle X-ray diffractometer. The results showed that the PLA's melting temperature was depressed only when contacted with pressurized CO₂ where at high CO₂ pressures the lubricating gas molecules induced more imperfect melt and cold crystals during the cooling and heating cycle. PLA's melt crystallization was analyzed during both isothermal and nonisothermal processes. In contrast to the effect of dissolved CO₂ that expedited the PLA's crystallization rate, N₂ showed almost a neutral impact on the PLA's crystallization kinetics. Because of the lower solubility, N₂ gas dissolved in the PLA had a diminutive plasticization effect, and thereby it could only counterbalance its negative hydraulic pressure effect. Moreover, as the helium pressure increased, the PLA's final crystallinity was reduced due to the dominant effect of helium's hydraulic pressure.     

TDI/BPO改性PBS的力学性能研究

本文采用扩链手段和交联手段对PBS进行改性研究。分别选用甲苯2,4-二异氰酸酯(TDI)为扩链剂,过氧化苯甲酰(BPO)为交联剂。使用乌氏黏度计、索氏抽提器对改性体系的特性黏数和交联度进行测定;使用哈克转矩流变仪、毛细管流变仪、差示扫描量热仪、万能拉力测试机等手段测试了改性体系的加工性能,流变性能,结晶与热性能,以及力学性能等。研究了扩链剂和交联剂用量对改性体系性能的影响。结果表明,随着TDI用量的增加,PBS改性体系的特性黏数逐渐增大,加工体系的平衡扭矩提高,熔体黏度呈现出增大的趋势,从而熔体强度增大。通过扩链反应,结晶温度提高,结晶度降低,熔点升高,拉伸强度变化不大,当TDI用量为1.0%时,拉伸强度最大。随着BPO用量的增加,PBS改性体系的交联度逐渐增大,加工性能得到改善,熔体黏度大幅提高,从而熔体强度增大。交联度的增大使得改性体系的结晶温度提高,结晶度和熔点均降低,拉伸强度呈现出先增大后减小的趋势。     

Molecular,rheological, and crystalline properties of low‐density polyethylene in blown film extrusion

The molecular weight and its distribution, degree of long chain branching and cooling rate strongly influence crystallinity during processing, which in turn determines the processability and the ultimate properties of the blown film. Generally a decrease in the number of branches and molecular weight of the polymer and the cooling rate results in an increase of the crystallinity. Length of the main chain and extent of branching in low‐density polyethylene (LDPE) are also factors that affect melt rheology and film crystallinity. Long chain branched polyethylene is suitable in the blown film process due to its better melt strength for bubble stability. The objective of this article is to describe the effect of molecular properties (e.g. molecular weight and its distribution, degree of long chain branching etc) of LDPE on film crystallinity at different cooling rates of blown film extrusion. Two different grades of LDPE were selected to investigate molecular characteristics, crystallinity, and rheology. The resins were processed in a blown film extrusion pilot plant using four different cooling rates. Molecular, rheological, and crystalline properties of the resins were key parameters considered in this study. POLYM. ENG. SCI., 47:1983–1991, 2007. © 2007 Society of Plastics Engineers     

Synthesis of branched poly(lactide) using polyglycidol and thermal, mechanical properties of its solution-cast film

Branched poly(lactide)(PLA)s with various lengths of graft chain were synthesized by ring-opening polymerization of l- or d-lactide (l- or d-LA) in bulk using polyglycidol as a macroinitiator. The properties of polymer films of branched PLLA or PDLA obtained and their stereocomplex were investigated through thermal analysis and tensile testing. The branched PLLA or PDLA film exhibited a lower glass transition temperature (T_g), melting temperature (T_m), crystallinity, Young's modulus and a higher strain at break than the corresponding linear PLLA or PDLA film. The branched PLLA/branched PDLA stereocomplex film showed a high maximum stress and a high Young's modulus keeping its high strain at break. Moreover, the usefulness of branched PLLA or PDLA as a plasticizer of linear PLLA was investigated with 1:9 blend or stereocomplex film prepared from the branched PLLA or branched PDLA and linear PLLA. The blend or linear PLLA/branched PDLA stereocomplex film showed a higher strain at break compared with linear PLLA film. The mechanical properties of the blend or linear PLLA/branched PDLA stereocomplex film could easily be controlled by changing the molecular weight of branched PLA.     

Introducing four different branch structures in PET by reactive processing––A rheological investigation

Chain extension/branching by reactive processing is a well-known method to enhance the rheological properties of polymers. In this study, pyromellitic dianhydride, poly(glycolic acid), triglycidyl isocyanurate, and bisphenol A diglycidyl ether were used as chain extender/branching agents to produce branched Polyethylene terephthalate (PETs) with four different molecular structures. According to the linear rheological characterizations, the storage modulus and complex viscosity of modified PET samples enhanced significantly after branching. The shear viscosities of modified PET show a pronounced shear-thinning behavior and a remarkable increase at low frequencies, which can be an indication of the existence of long-chain branches (LCBs) in the molecular structure of polymer and broadening the molecular weight distribution. Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) analysis were used to investigate the effect of branching agents on the chemical structure and thermal properties of PET, respectively. DSC results show that higher amounts of LCBs lead to lower melting and crystallization temperatures.     

Improvement of mechanical properties of polylactide by equal channel multiple angular extrusion

The combination of high strength and toughness is always the goal of high-performance polymer materials for industrial use. This study addresses the potentialities of a solid state equal-channel multiple-angular extrusion (ECMAE) in production of polylactide (PLA) with simultaneous improvement in toughness, strength, and thermal stability. Chain extender Joncryl was used to form PLA with different chain length and morphology (linear or branched PLA). It is demonstrated that simple shear deformation implemented in ECMAE results in formation of an orientation order, an increase in the degree of crystallinity, and the creation of α crystals with an increased degree of perfection. The value of the effects achieved depends on the type of PLA morphology. The best result is observed in the case of linear PLA. ECMAE-modified linear PLA possess the better combination of strength, modulus, and ductility than the branched one. Compared with neat linear PLA, ECMAE-modified linear PLA shows 12%, 26%, 217%, and 40% increase in tensile strength, Young's modulus, strain at break and impact strength, respectively. Additionally, the storage modulus shows an improved thermal stability of ECMAE-modified PLA.     

Determination of modified polyamide 6's foaming windows by bubble growth simulations based on rheological measurements

Reactive extrusion was used to modify virgin polyamides 6 (v-PA6) and to prepare chain extended PA6 (CE-PA6) and long-chain branched PA6 (LCB-PA6) for the melt foaming process. This was done using a twin-screw extruder and the following modifiers: a chain extender ADR-4368 and a branching agent maleic anhydride grafted polypropylene. A reaction mechanism was proposed to explain the chain extension and long-chain branching reactions and was verified by the Fourier transform infrared spectroscopy data. The analysis of the gel permeation chromatography data showed that LCB-PA6 presented a strong increase in the molecular weight and in the dispersity index. Moreover, the rheological properties of the v-PA6 and modified PA6 resins were characterized by a dynamic shear test. The LCB-PA6 compared with CE-PA6 showed much higher shear viscosity and longer characteristic relaxation times, indicating the presence of an LCB structure. A uniaxial elongation test showed that the LCB-PA6 had the highest melt viscosity and melt strength as well as most obvious strain-hardening behavior. A high-pressure differential scanning calorimeter under compressed CO₂ was used to investigate the PA6's crystallization properties so as to analyze its minimum temperature of foaming windows. The melt foamability of the CE-PA6 and the LCB-PA6 was verified by batch melt foaming experiments with CO₂ as the blowing agent and maximum temperature of foaming windows was also quantitatively determined by numerical simulation of bubble growth based on the rheological measurements. The results showed that the LCB-PA6 foams had a smaller cell diameter, a larger cell density, a greater expansion ratio, and wider foaming temperature window than the CE-PA6. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48138.     

长链支化聚丙烯的流变性能研究

利用反应挤出法制备了长链支化聚丙烯,采用旋转流变仪和毛细管流变仪对纯聚丙烯及其改性聚丙烯进行测试,用流变学理论进行表征。结果表明,聚丙烯加入支化剂后,产生了长支链,分子量增大,分子量分布变宽;在一定范围内,随着支化剂量的增大,其支化程度增加;在低频处,能模量G'比损耗模量G″对长支链的出现及量变更敏感;加入支化剂后熔体强度明显增大,且支化的程度越高熔体强度越大,可拉伸性变小,能有效地改善材料的加工性能。