Flexible and Tough Poly(lactic acid) Films for Packaging Applications: Property and Processability Improvement by Effective Reactive Blending

This study demonstrates a practical means to overcome inherent brittleness problem of poly(lactic acid) (PLA) and make PLA feasible as packaging material. PLA with suitable processability is utterly required for package manufacturers, where flexible, tough PLA film is essential for packers and end users. Highly flexible PLA films with 60‐fold increase in elongation at break (Eb) over that of the neat PLA were successfully produced by integrating effective reactive blending and economical film blowing process. The ‘two‐step’ blending was used to prepare PLA compound; poly(butylene adipate‐co‐terephthalate) (PBAT – another biodegradable polymer) was first blended with 0.5–1% chain extender (epoxy‐functionalized styrene acrylic copolymer) (ESA), followed by subsequent blending with PLA in twin‐screw extruder. Blown films of reactive blend of PLA/PBAT/ESA (80/20/1) showed impressively high Eb of 250% versus a very low Eb of 4% for the neat PLA. Resulting blown films still possessed high modulus of 2 GPa, yield stress of 50–60 MPa and good toughness of ~100 MPa. Significant enhancement in the film's ductility was attributed to homogeneous blend with developed fine strand‐like structure as a result of effective in situ compatibilization and good interfacial adhesion between the PLA and PBAT. PLA/PBAT/ESA blend also offered improved processability. Resulting films had acceptable haze of ~10% for common packaging, and clearer film close to PLA (≤2%) could be obtained by designing PLA skin layers in multilayer structure. Films of PLA/PBAT/1%ESA exhibit potential as packaging material; their mechanical and optical properties are comparable with or even exceed some existing films used in the market. Copyright © 2015 John Wiley & Sons, Ltd.     

PBAT/PCL共混薄膜在草莓保鲜包装中的应用

目的通过聚己内酯(PCL)来改善聚己二酸-对苯二甲酸丁二酯(PBAT)的自粘性、成膜性及气体透过性,探究不同厚度和不同气体透过性的PBAT/PCL共混薄膜包装对新鲜草莓的保鲜效果。方法利用双螺杆挤出流延机组制备不同厚度和不同气体透过性的PBAT/PCL共混薄膜,并用于草莓的密闭包装。结果纯PBAT的自粘性由于PCL的添加得到改善,且不同厚度及共混比例的PBAT/PCL共混薄膜气体透过量不同,但CO_2/O_2选择透过比几乎不变。当薄膜用于草莓包装时,PBAT/PCL20薄膜草莓包装内部的CO_2浓度从第2天开始迅速进入平衡状态,维持在体积分数为2%~3%的范围,而O_2的体积分数随着贮藏时间逐渐降低后达到6%~7%。结论少量PCL的添加可改善PBAT的自粘性,一定厚度和透过性的PBAT/PCL共混膜可以使包装内部建立起低氧高二氧化碳的气氛环境,抑制草莓的呼吸作用,延长其保鲜期。     

Development of multilayer films with improved aroma barrier properties for durian packaging application

The symmetrical A/B/A structure of multilayer blown films was fabricated in this study. The immiscible low‐density polyethylene/polylactic acid (LDPE/PLA) blend was set as a core (B) layer and LDPE was used as skin (A) layers. The compositions of PLA in the core layer were varied from 20 to 50 wt%. The thickness of each layer was 10 μm (total film thickness of ~ 30 μm). In a blown film co‐extrusion process, the morphology of the fiber/ribbon‐like structures of LDPE/PLA blend was developed. Such structures had interesting effects on gas permeability and aroma barrier properties of the films. For instance, multilayer LDPE films containing 40 and 50 wt% PLA (P40 and P50) showed the reduction of oxygen permeability (PO₂) approximately 20% and 43%, respectively, compared with the neat LDPE film. A long tortuous path for gas and aroma transportation through film thickness was created from the developed ribbon‐like structures of the PLA minor phase. For durian packaging application, fresh‐cut durian of 300 g was packed in the developed multilayer films, LDPE, and HDPE (Control), stored at 4°C for 7 days. Results demonstrated that the steady‐state condition of 10% to 13% O₂ and 8% to 10% CO₂ was achieved in all packages except in the HDPE. Moreover, the P40 and P50 films exhibited an outstanding aroma barrier property for three major durian volatiles : diethyl sulfide, ethyl propanoate, and 2‐ethyl‐1‐hexanol. Overall results clearly indicated that the multilayer LDPE films containing PLA exhibited a significantly improved aroma barrier performance with optimum gas permeability desirable for modified atmosphere packaging to retain quality of fresh‐cut durian throughout the storage period.     

可全生物降解PLA/PBAT/PHBV共混材料的结构与性能

为了得到刚性与韧性平衡的聚乳酸（PLA）基可生物降解共混材料,通过熔融共混挤出法制备了不同质量比的PLA/己二酸-对苯二甲酸-丁二酯共聚物（PBAT）/聚（3-羟基丁酸-co-羟基戊酸共聚酯（PHBV）可全生物降解共混材料,采用SEM、TG、DSC、毛细管流变仪和万能材料试验机对PLA/PBAT/PHBV共混材料的形态结构、热性能、流变性能和力学性能进行了研究。结果表明:PLA/PBAT/PHBV共混材料的热失重起始分解温度相对纯PHBV提高了45 ℃,热稳定性提高;共混体系中各组分的玻璃化转变温度与单一体系相比几乎无变化,PLA/PBAT/PHBV共混体系为完全不相容体系,同时PBAT和PHBV的加入阻碍了PLA的冷结晶;PLA/PBAT/PHBV 共混体系的共混形态呈“海-岛”分布,PBAT和PHBV均匀地分散于PLA基体中,相界面分明;随着PBAT含量增加,PLA/PBAT/PHBV共混材料熔体的流动性增加,温度变化对黏度的影响变大;PLA/PBAT/PHBV质量比为70/20/10的共混材料可在保留纯PLA 60%拉伸应力的同时,拉伸应变提高到纯PLA的2.6倍,韧性得到改善。所得结论表明PLA/PBAT/PHBV质量比为70/20/10的共混材料的综合力学性能较纯PLA好。      

Using Graphene Oxide to Enhance the Barrier Properties of Poly(lactic acid) Film

The ultra‐thin (polyethyleneimine/graphene oxide)_n [(PEI/GO)_n]multilayer films on poly(lactic acid) (PLA) were constructed via the layer‐by‐layer assembly. Here, the electrostatic interactions between PEI and GO were used to obtain the nanoscale composite membrane of (PEI/GO)_n on the surface of PLA film. With the number of assembling layers increased, the oxygen permeability (PO₂) of PLA film decreased substantially. As a 0.06 wt% GO solution was used with only four layers, the PO₂ decreased from 53.8 to 0.377 × 10^?4 cm³/m²/d/Pa, only 0.7% of the original PLA film. At the same time, the coated PLA film also presented a good transparency and better mechanical properties. It is a novel way to use GO on biodegradable packaging materials. Copyright © 2014 John Wiley & Sons, Ltd.     

In situ lamination of starch‐based baked foam packaging with degradable films

A technique for making biodegradable food service packaging comprising a starch–fibre core and a biodegradable film laminate is described. The biodegradable films were made of polylactic acid (PLA), polybutylene succinate/terephthalate (PBST), rubber latex and polybutylene adipate/terephthalate (PBAT). The technique involved an in situ process for laminating a baked foam product in a single step. A critical element of the in situ technique involved using a heat insulating fibre sheet to stabilize heat‐sensitive laminate films during the baking/lamination process. The PLA‐, PBST‐ and PBAT‐laminated samples were baked for 6min at 120°C. The latex‐laminated sample, which was much more heat‐stable, did not need the insulating sheet and was baked for 3min at 160°C. Starch‐based foam laminated with PLA, PBST or PBAT generally had higher density and greater tensile and flexural strength than the non‐laminated control. Starch foam laminated with a rubber latex film had tensile and flexural properties similar to the non‐laminated control, due to the low modulus and elasticity of the latex film. The in situ lamination process improved the adhesion of the starch foam core with the fibre sheet, PLA and latex films compared to a post‐lamination process. All of the laminate materials provided a low water vapour permeance. The films degraded in a compost mixture but at a much slower rate compared to starch. Copyright © 2006 John Wiley & Sons, Ltd.     

Microcellular extrusion foaming of poly(lactide)/poly(butylene adipate-co-terephthalate) blends

Foamed poly(lactide) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends were processed via the microcellular extrusion process using CO₂ as a blowing agent. Talc has been added to promote heterogeneous nucleation. Two types of PLA/PBAT blend systems were investigated: Ecovio, which is a commercially available compatibilized PLA/PBAT blend; and a non-compatibilized PLA/PBAT blend at the same PLA/PBAT ratio (i.e., 45:55 by weight percent). Six different formulations were investigated: pure PLA, PLA-talc, Ecovio, Ecovio-talc, non-compatibilized PLA/PBAT blend, and non-compatibilized PLA/PBAT-talc. The effects of various processing parameters such as die temperature, talc and compatibilization on various foaming properties such as cell morphology, volume expansion ratio (VER), open cell content (OCC) and crystallinity were investigated. As per the DSC thermograms, it was observed that compatibilization has merged the two distinctive melting peaks of PLA and PBAT into a single peak while lowering the peak temperature. In general, the addition of talc has decreased the average cell size and VER and increased the cell density and crystallinity; however, it has varying effects on the open cell content. Compatibilization has reduced the average cell size and volume expansion but increased the cell density and had varying and no effects on the OCC and crystallinity, respectively. Similar to compatibilization, the die temperature was found to have varying and no effects on the OCC and crystallinity, respectively. Except for PLA and non-compatibilized PLA/PBAT blend, the cell size and VER of all other formulations did not vary much throughout the entire temperature range (130–150 °C). The cell density was found to be insensitive to die temperatures except for Ecovio and Ecovio-talc.     

PLA/PBAT/PLA-g-MAH可生物降解复合材料的形态结构与性能分析

通过熔融共混法制备马来酸酐接枝聚乳酸(PLA-g-MAH)用于改善聚乳酸/聚己二酸-对苯二甲酸丁二酯共混物(PLA/PBAT)的相容性,并对复合材料的形态结构、力学性能和生物降解性能进行研究。SEM结果显示,添加增容剂PLA-g-MAH后,PLA/PBAT共混物两相间的界面明显变得模糊,说明PLA-g-MAH对共混物有一定的增容作用;增容剂PLA-g-MAH的加入,使复合材料的拉伸强度和弯曲强度相比于纯PLA略有下降,但其冲击强度有一定程度的提高,断裂伸长率有显著提高,比纯PLA的断裂伸长率提高了约17倍,表现出良好的力学性能;另外,PLA-g-MAH的加入提高了共混物的生物降解性能。     

苯乙烯-丙烯酸甲酯共聚物对聚苯乙烯/聚乳酸共混物力学性能和流变性能的影响

采用无皂乳液聚合法合成了苯乙烯-丙烯酸甲酯共聚物(PSMA)(n(St)∶n(MA)=75∶25),将PSMA与聚苯乙烯(PS)和聚乳酸(PLA)熔融共混制备了PSMA含量不同的PS/PLA共混物(m(PS)∶m(PLA)=1∶4),利用扫描电子显微镜、电子拉力机和转矩流变仪对共混物的相结构、力学性能以及流变行为进行了表征。结果表明,加入少量PSMA即能有效提高PLA与PS的相容性,减小PS/PLA共混物中分散相的相尺寸,提高PLA与PS两相间粘接作用;加入质量分数为0.5%的PSMA时,PS/PLA共混物的力学性能达到最佳;未加PSMA时,PS/PLA共混物在高剪切速率下剪切变稀显著,甚至低于纯PS,加入PSMA后,在高剪切速率下的剪切变稀程度与纯PLA相当。     

纳米纤维素/聚乳酸复合材料的降解性能

目的研究纳米纤维素/聚乳酸(NCC/PLA)复合薄膜在不同降解条件下的降解情况。方法在p H值为3,7,11的溶液及紫外光照射条件下,降解自制的复合薄膜,通过测失重率、扫描电子显微镜观察、X射线光电子能谱分析等手段,分析p H值、光照和NCC的添加与复合材料降解能力间的关系,研究其降解机理,并与纯PLA薄膜对比。结果 NCC/PLA复合薄膜在碱性条件下质量损失最快,酸性稍慢,中性更慢,紫外光照射下最慢,复合薄膜质量损失均比纯PLA薄膜多。在p H值为3和7的溶液及紫外光照射降解后,NCC/PLA复合薄膜氧碳原子数量的比值均比未降解时增大,分别提高了35.16%,36.66%,38.65%。结论 NCC的添加提高了NCC/PLA复合薄膜的降解性能,在不同降解过程中,薄膜表面C原子所占比例减少,相对地O原子所占比例增加,氧碳原子数量的比值增大。     

Morphology,interfacial and mechanical properties of polylactide/poly(ethylene terephthalate glycol) blends compatibilized by polylactide-g-maleic anhydride

Polylactide/poly(ethylene terephthalate glycol) (PLA/PETG 80/20 wt) blends compatibilized with polylactide-g-maleic anhydride (PLA-g-MAH) were prepared by melt blending and the rheological, morphological and mechanical properties of the blends were studied. PLA/PETG (80/20 wt) blend formed a typical sea-island morphology, while upon compatibilization, the size and size distribution of the dispersed phase decreased significantly and the 3 wt% PLA-g-MAH compatibilized blend exhibited the smallest phase size and the narrowest distribution of the dispersed particles. The interfacial tension between PLA and PETG was determined from the morphological characteristics and the viscoelastic response of PLA/PETG blends via using two emulsion models. A minimum for PLA/PETG blend containing 3 wt% PLA-g-MAH was observed from both Palierne model and G–M model. The elongation-at-break increased by ∼320%, from 6.9% for PLA to 28.7% for the blend containing 3 wt% PLA-g-MAH without significant loss in the tensile modulus and tensile strength.     

生物降解聚酯PLA/PBSA共混体系的制备与结构性能

采用熔融共混法制备了PLA/PBSA共混材料;采用DSC,TG,DMA和拉伸力学试验研究了该共混体系的热性能和力学行为;采用土壤悬浊拟环境降解实验法研究了共混材料的生物降解性;同时对该体系的生物降解机理及影响因素进行了初步探讨。结果表明,PLA/PBSA为非均相结晶/结晶高分子共混体系;PLA含量增加,有利于提高材料的模量和拉伸强度;增加PBSA的含量,可以提高PLA/PBSA共混体系的环境生物降解性。PLA/PBSA是力学性能和降解性能互补的生物降解材料。     

Effect of biaxial‐simultaneous stretching conditions on OTR and CO2 permeation of CO2 laser perforated poly(lactic acid) film

The biaxially oriented poly(lactic acid) films prepared using simultaneous biaxial stretching were perforated by CO₂ laser with the power of 60 W. The focal spot diameter was fixed at 103 μm. Pulse durations were varied from 1 to 30 μs, which corresponds to the fluence from 1.4 to 42.6 J/cm². The perforated microhole size increased with increasing laser energy. The shape of microholes was circular for the films of equi‐biaxial stretching, whereas elliptical microholes were formed with its long and short axes corresponding to the directions of higher and lower stretch ratios, respectively. Comparing the laser perforation behavior of the as‐drawn films and annealed films, the opening of a microhole in the annealed films started at higher laser fluence, and at the same fluence the size of microhole was smaller. Gas transmission rates of the biaxially oriented poly(lactic acid) films with different thicknesses were examined. The oxygen transmission rates (OTR) of film improved with increased microhole diameter. The OTR of films containing 1 microhole/103 cm² (hole diameter of ~110 μm) was 184, 150, and 98 cm³/d in comparison with the OTR for the original films without microhole of only 16, 10, and 8 cm³/d, respectively. Packaging films with OTR higher than 100 cm³/d (equivalent to the 9700 cm³/m²/d) are required to create a modified atmosphere inside the package of fresh produce for shelf‐life extension. Measured OTR and CO₂TR values of the 3 different shapes of microhole were compared and discussed.     

Development of an active polylactic acid (PLA) packaging film by adding bleached bagasse carboxymethyl cellulose (CMCB) for mango storage life extension

This study aimed to determine the properties of a new active packaging film in order to extend the storage life of fresh mangoes by packing “Nam Dok Mai” mangoes (Mangifera indica Linn) with an active packaging film composed of biodegradable polymer and cellulose derivatives. A new packaging bag was produced primarily by blending polylactic acid (PLA) with spray‐dried carboxymethyl cellulose (CMC) from bleached bagasse (CMC_B) at various concentrations (0%, 1%, 2%, and 4% w/w). The film thickness of the PLA and PLA/CMC_B bags was 75 μm. Unpacked mangoes were used as control before the packaged ones were stored at export conditions (13 ± 1°C and 90 ± 5% relative humidity [RH]) to evaluate the efficiency of the PLA/CMC_B film. Mango respiration and ethylene production rate were measured periodically in a packaging atmosphere as an indicator of ripeness. Changing fruit physio‐chemistry parameters were also studied, including weight loss, peel and flesh colour, firmness, total soluble solid (TSS), and total acidity (TA). The capacity of PLA/CMC_B packaging to absorb water vapour and prolong mango shelf life was demonstrated, and active packaging function by control of RH was also demonstrated. The absorption of PLA/CMC_B packaging was increased dramatically at 4% (w/w) CMC_B mixed with PLA. At this CMC_B concentration, the packaging film could extend the shelf life of mangoes for 42 days in export condition as well as decrease the physio‐chemistry parameters and respiratory rate, which were significantly enhanced when compared with those of control mangoes or unpacked mangoes (P ≤ 0.05), which had a shelf life of approximately 3 weeks.     

MFC-structured biodegradable poly(l-lactide)/poly(butylene adipate-co-terephatalate) blends with improved mechanical and barrier properties

Both polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable polymers. They are thermoplastics which can be processed using conventional polymer processing methods. In this study, microfibrillar-reinforced composites (MFC) based on PLA/PBAT (PLA/Ecoflex^®) blends in different weight ratios were prepared under industry-relevant conditions by melt extrusion followed by continuous cold drawing of the extrudates. Strip-like specimens (films) and plates (laminates) of the drawn blends were prepared by compression molding (CM) at processing temperature above the melting temperature (T _m) of PBAT, but below T _m of PLA. SEM and WAXS observations show that the extruded blend components are isotropic, but become highly oriented after drawing, and they are converted into MFC-structured polymer–polymer composites after CM. An effect of PLA microfibrils on the non-isothermal crystallization of the Ecoflex during cooling from the melt, associated with the formation of crystalline regions of the matrix around the fibrils, was observed. Depending on the blend composition, the compression-molded samples possess a 3- to 7-time higher tensile strength as well as a 15–30 higher modulus than the neat Ecoflex. In addition, the MFC-structured plates exhibited superior barrier properties compared to the neat Ecoflex, e.g., the oxygen permeability decreased by up to 5 times.     

Square and Rectangular Symmetry Tiles from Bulk and Thin Film 3‐Miktoarm Star Terpolymers

The directed self assembly of a 3‐miktoarm star terpolymer (polyisoprene‐arm‐polystyrene‐arm‐polyferrocenylethylmethylsilane (3μ‐ISF)) into a (4.8²) square symmetry Archimedean tiling pattern is described. Bulk samples of 3μ‐ISF generate equilibrium columnar (4.8²) tile patterns (symmetry p 4 mm) on annealing, which is preceded by a metastable c 2 mm centered rectangular structure. In contrast, in thin films of 3μ‐ISF blended with PS homopolymer, the c 2 mm phase is stable with columns oriented out of plane when the film thickness is below 50 nm. However, the 3μ‐ISF/homopolymer blend rapidly forms a p 4 mm symmetry when the film thickness is ～80 nm, with grain sizes of several μm and excellent order. Defects in the p4mm structure are described.     

HECS-g-PDLLA共聚物的微波合成及与聚乳酸的相容性

在微波作用下,以辛酸亚锡为催化剂,羟乙基壳聚糖（HECS）为大分子引发剂引发D,L-丙交酯（D,L-LA）开环聚合制备羟乙基壳聚糖-g-聚乳酸（HECS-g-PDLLA）,通过红外（IR）、元素分析（EA）、氢核磁共振（1H-NMR）、X射线衍射（XRD）和差示扫描量热分析（DSC）对产物进行了表征。然后采用溶液共混法...     

PBAT/ZSM-5分子筛共混薄膜的制备与性能

目的 以聚己二酸-对苯二甲酸丁二酯(PBAT)为基材,制备PBAT/ZSM-5分子筛共混薄膜,研究分子筛含量对薄膜性能的影响.方法 通过共混熔融挤出流延法制得含不同质量分数ZSM-5分子筛(0％,1％,3％,5％,7％)的PBAT薄膜,测定分析不同分子筛质量分数对薄膜的颜色、透明性、结构、气体阻隔性、力学性能等性能的影响.结果 随着分子筛质量分数的增加,透明性和断裂伸长率显著降低,抗拉强度先增加后降低,质量分数为1％分子筛的薄膜抗拉强度相对较大,较纯PBAT薄膜增加了12.34％;薄膜氧气透过性能整体上呈上升趋势,二氧化碳透过性和CO2/O2透过比均逐渐增加,水蒸气透过性显著降低,与纯PBAT薄膜相比,质量分数为7％分子筛PBAT薄膜的氧气和二氧化碳透过系数分别增加了18.48％,33.51％,水蒸气透过系数下降了43.28％,CO2/O2透过比由原来的8.84增加到9.96;薄膜表面和横截断面均变得粗糙,局部区域有团聚现象,且随分子筛含量的增加而变得明显.结论 ZSM-5分子筛的少量加入,可以影响PBAT薄膜力学性能,降低其水蒸气透过性,调节薄膜的气体选择透过性,为其应用于生鲜果蔬包装提供基础.     

不同相对分子质量聚乙二醇增塑聚乳酸共混物的制备与性能

文中探究不同相对分子质量聚乙二醇(PEG)对聚乳酸(PLA)增塑改性的影响。采用转矩流变仪、万能试验机、差示扫描量热分析、动态力学、热重分析、旋转流变仪等测试表征方法对共混材料的增塑效果、力学性能、热行为、流变行为进行分析。实验结果表明,PEG可有效增塑PLA,PEG相对分子质量越低增塑效果越好,可以使PLA的塑化时间从250 s降低到128 s;加入PEG后,共混物的拉伸强度下降,断裂伸长率提高,PEG相对分子质量越低,拉伸强度下降越明显;PEG的加入使PLA的T_g和T_(cc)降低20℃左右,而T_m有所提高,其中低相对分子质量PEG可以更好地促进PLA结晶,但是随着PEG的加入共混体系的热分解温度降低,相对分子质量越低,热分解温度降低越明显;流变实验表明共混体系的复数黏度(η*)、储能模量(G')及损耗模量(G')的变化随PEG相对分子质量的减小下降越明显。     

Electrospray Encapsulation of Hydrophilic and Hydrophobic Drugs in Poly(L‐lactic acid) Nanoparticles

An electrospray method is developed for preparation of beclomethasone‐dipropionate‐ and salbutamol‐sulfate‐loaded biodegradable poly(L ‐lactic acid) nanoparticles. Different set‐up parameters for electrospraying are examined on particle size, and preparation conditions are optimized for producing spherical‐drug‐loaded nanoscale particles by controllable processing parameters. Polylactide (PLA)–drug nanoparticles with average diameters of around 200 nm are achieved in a stable cone‐jet mode with a flow rate of 4 µL min^?1, polymer concentration of 1%, and ammonium hydroxide content of 0.05%. Morphology and size of the drug–polymer nanoparticles are analyzed by scanning electron microscopy and transmission electron microscopy. Changes in the crystallinity of the PLA polymer and the model drugs are detected by X‐ray powder diffraction, and the absence of molecular interactions are confirmed by thermal analyses. The results indicate clearly that electrospraying is a potential method for producing polymeric nanoparticles and for encapsulating both hydrophilic and hydrophobic drugs efficiently into the nanoparticles.