Resolving Inclusion Structure and Deformation Mechanisms in Polylactide Plasticized by Reactive Extrusion

A multiscale characterization approach is developed to resolve the structure of inclusions in polylactide (PLA) plasticized with acrylated poly(ethylene glycol) (acrylPEG) by reactive extrusion. Scanning transmission X‐ray microscopy (STXM) coupled with near‐edge X‐ray absorption fine structure (NEXAFS) nanospectroscopy demonstrates that these inclusions have a core–shell morphology. This technique also proves that the inclusions consist of polymerized acrylPEG (poly(acrylPEG)), which is also confirmed by elastic modulus measurement using an atomic force microscope. The shell consists of poly(acrylPEG)‐rich domains, while the core is less rich in the polymerized plasticizer. Upon drawing, the density of the inclusion's core and shell markedly decreases as shown by microcomputed X‐ray tomography measurements, and no inclusion–matrix debonding is observed. At the same time, sub‐micrometer cracks are noted between inclusions by STXM/NEXAFS imaging, which may result from the presence of crosslinking points restricting the local chain mobility. Novel knowledge about the reactive extrusion‐induced PLA structure is released.     

Using the solubility parameter to explain disperse dye sorption on polylactide

The solubility parameters of polylactide (PLA), poly(ethylene terephthalate) (PET), and various disperse dyes calculated according to the group contribution method were used to explain the low sorption of some disperse dyes on PLA but the high sorption of the same dyes on PET. It was found that the dyes with high sorption on PLA tended to have solubility parameters near that of PLA, which has a lower solubility parameter than that of PET. It was also found that the solubility parameter, which was calculated based on cohesive energy and molar volume at 25°C, was more appropriate for explaining dyeings at lower temperature, 100 and 110°C, than those at higher temperature, 130°C. Based on the finding that dyes with solubility parameters near that of PLA tend to have high sorption on PLA, general structures for disperse dye that may have high sorption on PLA were proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 416–422, 2005     

Structure‐rheology responses of polylactide/calcium carbonate composites

Polylactide (PLA) and calcium carbonate (CaCO₃) were melt blended using a twin‐screw extruder. The morphology of PLA/CaCO₃ composites was observed by scanning electronic microscopy. The linear and nonlinear shear rheological behaviors of PLA/CaCO₃ melts were investigated by an advanced rheology expended system. The results show that the CaCO₃ particles are evenly dispersed in the PLA matrix. The incorporation of low CaCO₃ content (<20%) causes the reduction of the storage moduli, loss moduli, and dynamic viscosities whereas high CaCO₃ content (>30%) leads to the increase of the storage moduli, loss moduli, and dynamic viscosities. The composites with high CaCO₃ content show pseudo‐solid‐like behaviors at low frequency. High CaCO₃ content also results in a significant increase of flow activation energy and a dramatic decrease of flow index n, which is in consistent with the more serious shear‐thinning tendency of high‐filled PLA composites melts. The particular rheological responses might be attributed to the formation and destruction of the percolating network. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

端羟基聚异戊二烯及其共聚物的合成与表征

以仲丁基锂为引发剂,引发异戊二烯本体负离子聚合,再用环氧丙烷甲醇终止法合成了端羟基聚异戊二烯;然后利用端羟基聚异戊二烯的活性端羟基,引发丙交酯的开环聚合制备了聚乳酸一聚异戊二烯共聚物,并采用IR、^1H—NMR、TG等测试手段对产品进行了表征。结果表明,通过改变仲丁基锂及环氧丙烷的用量,可合成相对分子质量及羟基含量可控的且1,4-结构质量分数超过87．5％的端羟基聚异戊二烯。     

壳聚糖涂层聚乳酸细胞微载体的制备和性能

采用氨解技术在聚乳酸微球表面引入自由氨基,再利用戊二醛将氨基转化为醛基,最后采用接枝涂层技术将壳聚糖固定到聚乳酸微球表面,制备了壳聚糖表面改性的聚乳酸细胞微载体.分别采用茚三酮法和乙酰丙酮-对二甲氨基苯甲醛法测定了聚乳酸微球表面的氨基和壳聚糖含量.发现氨基的量初始随氨解时间的延长而增大,达到最大(2.94×10-7mol/mg)后保持不变.与空白聚乳酸微球相比,软骨细胞在壳聚糖改性聚乳酸微球表面能够更有效地粘附和生长,分布更为均匀.     

碳纤维/环氧树脂脉管自润滑复合材料的制备及摩擦性能

以聚乳酸（PLA）为前驱体,碳纤维（CF）为增强体,通过经纬编织成PLA-CF复合纤维织物;以环氧树脂（EP）为基体,甲基硅油为润滑介质,采用前驱体蒸发（VaSC）技术和真空浸油方式分别制备了脉管自润滑环氧树脂（VAEP）材料和CF/VAEP复合材料。利用SEM对CF/VAEP复合材料的断面、摩擦面和对偶面形貌进行表征,以万能材料试验机和高速环块摩擦磨损试验机对CF/VAEP复合材料的力学和摩擦学性能进行了测试。结果表明:脉管结构和CF提升了EP的润滑性能和力学性能。当径向脉管密度为8孔/10 mm时,VAEP的摩擦系数和磨损率较纯EP分别降低了67.95%和85.71%;当径向脉管密度为8孔/10 mm,CF经纬丝束比为8/4时,CF/VAEP复合材料的拉伸强度、拉伸模量、弯曲强度、弯曲模量比相同径向脉管密度的VAEP分别提高了203.33%、44.16%、325.78%、311.37%。      

菜籽多肽脱苦工艺的初步研究

采用包埋法对菜籽多肽进行脱苦,初步研究了脱苦的包埋工艺,探索了影响包埋过程中的各种因素.实验结果表明:聚乳酸作壁材的最佳脱苦工艺条件为:聚乳酸浓度为0.04g/mL,明胶浓度5%,内水相/油相为1:5,吐温80浓度为0.4g/mL时,多肽的包埋率达到68.6%,微球有较好的外观形态;并且包埋后微球的热稳定性与菜籽多肽相比得到提高.     

Strain‐induced deformation mechanisms of polylactide plasticized with acrylated poly(ethylene glycol) obtained by reactive extrusion

This work aimed at identifying the tensile deformation mechanisms of an original grade of plasticized polylactide (pPLA) obtained by reactive extrusion. This material had a glass transition temperature of 32.6 °C and consisted of a polylactide (PLA) matrix grafted with poly(acryl‐poly(ethylene glycol)) (poly(Acryl‐PEG)) inclusions. pPLA behaved like a rubber‐toughened amorphous polymer at 20 °C, and its tensile behavior evolved toward a rubbery semicrystalline polymer with increasing temperature. The drawing of pPLA involved orientation of amorphous and crystalline chains, crystallization, and destruction of crystals. It was found that crystal formation and crystal destruction were in competition below 50 °C, resulting in a constant or slightly decreasing crystallinity with strain. Increasing temperature enhanced crystal formation and limited crystal destruction, resulting in an increased crystallinity with the strain level. Drawing yielded a transformation of the initial spherical poly(Acryl‐PEG) inclusions into ellipsoids oriented in the tensile direction. This mechanism may engender the formation of nanovoids within the inclusions due to a decreased density, assumed to be responsible for the whitening of the specimen. © 2015 Society of Chemical Industry