PHB/PLLA/PEO共混纤维的晶态结构与拉伸性能研究

采用溶液干纺法制备了聚β-羟基丁酸酯/聚乳酸/聚氧乙烯(PHB/PLLA/PEO)共混纤维,研究了PHB/PLLA/PEO初生纤维的晶态结构、在50℃和110℃下拉伸后共混纤维的力学性能及表面形态。结果表明:PHB与PLLA在PHB/PLLA/PEO共混纤维中的晶型均为α晶型;初生纤维经50℃和110℃拉伸2倍后,纤维的断裂强度均有所增加,断裂伸长率减小,50℃拉伸的纤维断裂强度高于110℃拉伸,其断裂方式均为韧性断裂;w(PEO)为5%,PHB/PLLA质量比为1:1,50℃拉伸2倍的PHB/PLLA/PEO共混纤维断裂强度为0.471 cN/dtex,断裂伸长率为34.05%     

PHB/PLLA共混电纺纤维可纺性的研究

采用静电纺丝法制备了聚β-羟基丁酸酯/左旋聚乳酸(PHB/PLLA)共混纤维,探讨了静电纺丝工艺及PHB/PLLA共混电纺纤维的可纺性。结果表明:对共混溶剂氯仿/N,N-二甲基甲酰胺(CF/DMF)体系,随DMF在共混溶剂中含量增加,PHB/PLLA纤维形态由连续的纤维变为微球;对CF溶剂体系,随纺丝溶液浓度增加,PHB/PLLA纤维形态从微球状变为珠状体,再变成纺锤体,最后形成连续纤维;适宜的PHB/PLLA共混电纺纤维的工艺条件如下:PHB/PLLA质量比为1∶1,溶剂为CF,电纺溶液质量分数为4%,推进速度为0.15 mm/min,板间距17 cm,电压18 kV。     

多级结构PHB基电纺纤维膜的制备及性能研究

以聚β-羟基丁酸酯(PHB)为基体,左旋聚乳酸(PLLA)和聚氧乙烯(PEO)为第二组分,采用多层静电纺丝法制备了三层复合的PHB/PLLA/PHB,PHB/PEO/PHB,PHB/PLLA/PEO多级结构PHB基纤维膜,研究了多级结构PHB基纤维膜的形貌、结晶行为、热性能和亲水性能。结果表明:多级结构纤维膜中PHB组分的平均直径为770~790 nm,PEO的平均直径为280~290 nm,PLLA的平均直径为400~410 nm;PHB,PLLA组分在多级结构纤维膜中的晶型均为α晶型,PEO组分为单斜晶型,多级结构PHB基纤维膜中各组分的热性能没有受到影响;多级结构纤维膜的亲水性由强到弱的顺序依次为PHB/PEO/PHB纤维膜、PHB/PEO/PLLA纤维膜、PHB/PLLA/PHB纤维膜、PHB纤维膜,多级结构可改善PHB电纺纤维膜的亲水性。     

生物可降解PHB材料的研究

综述了通过物理共混改性和化学结构改性2种不同方式来改善聚羟基丁酸酯（PHB）的材料性能,包括与天然原料、无机填料和生物降解树脂共混以及嵌段/接枝化学结构改性制备增强复合材料的最新研究进展,并对PHB未来的应用前景进行展望。     

聚乳酸/聚羟基烷酸酯全生物降解共混物研究进展

介绍了聚乳酸(PLA)/聚羟基烷酸酯(PHA)全生物降解共混物研究进展,包括PLA/聚羟基丁酸酯(PHB)共混物、PLA/β-羟基丁酸酯与β-羟基戊酸酯共聚物(PHBV)共混物等,其中重点介绍了其相容性与相态结构、结晶性能、热性能、力学性能、降解性能等方面的研究成果。     

PLLA/聚氧乙烯/改性纳米二氧化钛复合材料制备

以左旋聚乳酸(PLLA)、聚氧乙烯(PEO)、改性纳米TiO2为原料,通过熔融共混、热压成型法制备了PLLA/PEO/改性纳米TiO2复合材料,分别采用傅立叶变换红外光谱,电子拉力试验机,广角X射线衍射仪等对改性纳米TiO2的结构及复合材料的力学性能、结晶性能进行表征,并研究了复合材料在NaOH溶液中的降解行为。结果表明,向PLLA/PEO共混物中加入质量分数为1%的改性纳米TiO2能起到增强增韧的作用,并能显著改善复合材料的结晶性能。在NaOH介质中的降解结果表明,复合材料的降解速率随改性纳米TiO2用量的增加而增大,当纳米TiO2质量分数为5%时,复合材料的降解速率最大。     

PBAT/PLLA共混薄膜的热学、力学及阻透性能

采用熔融共混法制备聚对苯二甲酸己二酸丁二醇酯（PBAT）和L聚乳酸（PLLA）共混薄膜,探讨不同PLLA添加量（质量分数分别为10 %、20 %、30 %）对共混薄膜力学性能、热学性能、气体阻透性能的影响。结果表明,PBAT和PLLA共混属于不相容体系;随着PLLA的添加,共混薄膜的O2和CO2透过性能逐渐降低;当PLLA含量增加到30 %时,O2 透过系数(PO2)和CO2透过系数(PCO2)分别较PBAT薄膜降低了34.2 %和70.8 %,CO2/O2透过比（PCO2/PO2）由纯PBAT的10.20降低为4.52,提高了薄膜阻透性能;PLLA的添加改善了PBAT极易变形变曲现象。     

PBS/PHB共混合金的制备及其性能

采用双螺杆挤出机将聚羟基丁酸酯(PHB)与聚丁二酸丁二酯(PBS)熔融共混,制备了PBS/PHB合金,并研究了其性能。结果表明:PBS与PHB组成了热力学互容体系;随着PHB用量的增加,PBS/PHB合金的晶体形态为尺寸逐渐减小的环带球晶,合金的拉伸强度与韧性显著增加;PBS/PHB合金在紫外光老化后的抗冲击性能下降,但PHB含量高的合金在老化后仍具有较高的冲击强度。     

PLLA/PCL共混纤维的力学性能研究

本文以二氯甲烷为溶剂,采用离心纺丝制备出聚乳酸-聚己内酯纤维,通过FT-IR、DSC、SEM、接触角、拉伸测试表征了所得产品,并考察了浓度、配比、转速等条件对纤维结构和形貌的影响。最终得到性能优异的聚乳酸-聚己内酯离心纺丝纤维。研究结果表明:PLLA/PCL共混物为不相容体系,并相互限制对方的结晶行为;在PLLA/PCL共混体系中,PCL可作为PLLA结晶过程的异相成核剂,并促使PLLA的熔融重结晶;离心纺丝最佳纺丝液浓度为12%、最佳组分比(PLLA:PCL)为7:3、最佳离心转速为10 000r/min;PLLA/PCL共混物的接触角处于单组份值之间,表现为疏水性;PLLA/PCL的共混离心纺丝样品力学强度得到显著的增加,韧性也有一定程度的改善。     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

High molecular weight poly( -lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly( -lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

High molecular weight poly(l-lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly(l-lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

PLLA/PVA/PLCA三元共混体系分子间相互作用

聚L-乳酸(PLLA)及聚乙烯醇(PVA)由于其良好的生物相容性,在生物医学领域得到了广泛的关注。但聚乳酸由于其疏水性及缺乏反应位点而使其应用受到一定的限制。将聚乙烯醇与聚乳酸共混,不仅可以降低聚乳酸的成本,同时可以改善其亲水性,但由于其结构差异,存在严重的相分离现象。本研究将含有反应活性位点的乳酸-柠檬酸共聚物(PLCA)引入PLLA/PVA体系中,以期改善二者的相容性。通过红外光谱分析手段,研究了PLLA/PVA/PLCA体系中分子间的相互作用,并对不同组成体系的力学性能进行了分析及表征。结果表明,PLCA的加入使PLLA/PVA复合体系的相容性及力学性能得到了明显的改善。     

Immiscible PHB/PBS and PHB/PBSA blends: morphology,phase composition and modelling of elastic modulus

This paper reports the thermal, morphological and mechanical properties of environmentally friendly poly(3-hydroxybutyrate) (PHB)/poly(butylene succinate) (PBS) and PHB/poly[(butylene succinate)-co-(butylene adipate)] (PBSA) blends, prepared by melt mixing. The blends are known to be immiscible, as also confirmed by the thermodynamic analysis here presented. A detailed quantification of the crystalline and amorphous fractions was performed, in order to interpret the mechanical properties of the blends. As expected, the ductility increased with increasing PBS or PBSA amount, but in parallel the decrease in the elastic modulus appeared limited. Surprisingly, the elastic modulus was found properly described by the rule of mixtures in the whole composition range, thus attesting mechanical compatibility between the two blend components. This unusual behavior has been explained as due to co-continuous morphology, present in a wide composition range, but also at the same time as the result of shrinkage occurring during sequential crystallization of the two components, which can lead to physical adhesion between matrix and dispersed phase. For the first time, the elastic moduli of the crystalline and mobile amorphous fractions of PBS and PBSA and of the mobile amorphous fraction of PHB at ambient temperature have been estimated through a mechanical modelling approach. © 2021 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.     

The toughening behavior of PLLA and its asymmetric PLLA/PDLA blends with lower optical purity

Linear poly(d ‐lactide) (PDLA) with various molecular weights is synthesized and incorporated into commercial poly(l ‐lactide) (PLLA) with different optical purities. And then, the crystallization, mechanical and thermal properties of the PLLA and PLLA/PDLA cast films are investigated. In the PLLA and PDLA/PLLA specimens with lower optical purity, few homochiral crystallites (HC) form in all the specimens and only a small amount of PLA stereocomplex crystallites (SC) are observed in the blends. The elongation at break of all the specimens is extraordinary high, >300%. Dynamic mechanical analyses indicate that the destruction temperature increases at first, and then depresses as enlarging the molecular weight of PDLA in these blends. For the PLLA and PLLA/PDLA with higher optical purity, more content of HC develops in neat PLLA, and both SC and HC produce in the PLLA/PDLA specimens. However, the strains of neat specimens and binary blends are much lower than that of specimens with lower optical purity. The specimens with higher optical purity exhibit higher destruction temperatures and lower loss factors. The high content of crystals (SC and HC) would act as the physical cross‐linking points and provide a key factor to impede the deformation of neat PLLA and binary blends during stretching, which should result in the fragile behavior of the PLLA and PLLA/PDLA blends with higher optical purity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44730.     

聚乙二醇/聚(β-羟基丁酸酯)/聚乙二醇三嵌段共聚物的合成与表征

为改进聚(β-羟基丁酸酯)(PHB)的结晶性和亲水性,通过聚乙二醇单甲醚(MPEG)的端酰氯基团和聚(β-羟基丁酸酯)的端羟基基团的官能团反应,制备了聚乙二醇/聚(β-羟基丁酸酯)/聚乙二醇三嵌段共聚物。通过红外光谱、核磁、X-射线衍射、差热分析和凝胶渗透色谱等手段,证明制备了嵌段共聚物。吸水实验表明,材料的亲水性得到了明显的改善。     

Crystallization behavior of poly(l-lactic acid) affected by the addition of a small amount of poly(3-hydroxybutyrate)

The miscibility, crystallization and subsequent melting behavior in binary biodegradable polymer blends of poly(l-lactic acid) (PLLA) and low molecular weight poly(3-hydroxybutyrate) (PHB) have been investigated by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide-angle X-ray diffraction (WAXD). DSC analysis results indicted that PLLA showed no miscibility with high molecular weight PHB (M_w = 650,000 g mol⁻¹) in the 80/20, 60/40, 40/60, 20/80 composition range of the PHB/PLLA blends. On the other hand, it showed some limited miscibility with low molecular weight PHB (M_w = 5000 g mol⁻¹) when the PHB content was below 25%, as evidenced by small changes in the glass transition temperature of PLLA. The partial miscibility was further supported by changes of cold-crystallization behavior of PLLA in the blends. During the nonisothermal crystallization, it was found that the addition of a small amount of PHB up to 30% made the cold-crystallization of PLLA occur in the lower temperature. Meanwhile, the crystallization of PHB and PLLA was observed in the heating process by monitoring characteristic IR bands of each component for the low molecular weight PHB/PLLA 20/80 and 30/70 blends. The temperature-dependent IR and WAXD results also revealed that for PLLA component crystallization, the disorder (α′) phase of PLLA was produced, and that the α′ phase changed to the order (α) phase just prior to the melting point.     

Miscibility of Crystalline/Amorphous/Crystalline Biopolymer Blends from PLLA/PDLLA/PHB with Additives

Miscibility of three biopolymers (PLLA, PDLLA and PHB) blends were investigated by POM, WAXD, FTIR, and DSC. DSC verified the thermal properties of biopolymer blend with PVAc as a compatibilizer, and TBC as plasticizer. Some change in glass transition temperature (T_g) of biopolymer blends from 60°C to 0.7°C. The spherulitic morphology of blend 9 changing by addition more PHB (50%), the results dendritic spherulites. The adding PHB to PLLA blends make certain shifting in the diffraction peak from 2 ? = 16.9° to 2 ? = 16.6° and the carbonyl group shifts from 1752 cm^?1 to 1732 cm^?1 in blends, demonstrating polar interactions between them.     

Effect of a small amount of poly(3‐hydroxybutyrate) on the crystallization behavior of poly(l‐lactic acid) in their immiscible and miscible blends during physical aging

The miscibility and effect of physical aging on the crystallization behavior of poly(l ‐lactic acid) (PLLA)/poly(3‐hydroxybutyrate) (PHB) blends with a small amount of PHB (≤10 wt%) have been investigated using differential scanning calorimetry and Fourier transform infrared spectroscopy. It is found that the miscibility of PLLA/PHB blends with a very small percentage of PHB can be modulated by varying the molecular weight of the PHB. That is, a PLLA/PHB blend with low‐molecular‐weight PHB is miscible, whereas that with high‐molecular‐weight PHB is immiscible. It is found that physical aging at temperatures far below the glass transition temperature can promote the cold crystallization kinetics of PLLA in PLLA/PHB blends with high‐molecular‐weight PHB rather than in those with low‐molecular‐weight PHB. These findings suggest that the effect of physical aging on the crystallization behavior of the main component in a crystalline/crystalline blend with a small percentage of the second component is strongly dependent on the miscibility of the blend system. Enhanced chain mobility of PLLA in the interface region of PLLA matrix and PHB micro‐domains is proposed to explain the physical aging‐enhanced crystallization rate in immiscible PLLA/PHB blends with high‐molecular‐weight PHB. © 2013 Society of Chemical Industry