PEG对PLA/PBS共混物结构与性能的影响

通过熔融共混法制备了聚乳酸/聚丁二酸丁二醇酯/聚乙二醇(PLA/PBS/PEG)共混物,研究了PEG组分对PLA/PBS共混体系微观结构、流变性能、结晶性能、动态力学性能以及冲击性能的影响。结果表明,将PEG组分添加到PLA/PBS共混物中,能够降低PBS分散相的尺寸,均化分散相尺寸分布,增强界面结合。与PLA/PBS共混物相比,PLA/PBS/PEG共混物的复数黏度大幅度降低。由于PEG对PLA和PBS分子链同时具有增塑作用,使PLA/PBS/PEG共混物的结晶能力远大于相应的PLA/PBS共混物,最高结晶度可达17. 4%。通过测试,动态力学性能结果表明,PEG组分能够降低共混体系中PLA组分的玻璃化转变温度,并且促进PLA与PBS之间的相容性。此外,PLA/PBS/PEG共混物的冲击强度得到了显著提高,最高可达到4. 71 k J·m~(-2),比未添加PEG组分的PLA/PBS共混物提高了25. 3%。     

聚乳酸/改性甘蔗纤维复合材料的制备与性能分析

以低分子量聚乙二醇(PEG)为增塑剂,马来酸酐改性的甘蔗纤维(MSF)为成核剂,采用熔融共混的方式制备PLA/MSF/PEG复合材料,并对复合材料的结晶行为、晶体形貌、力学和表面亲水性进行研究。结果表明:表面改性的MSF可作为异相成核剂,显著提高PLA的结晶能力;增塑剂PEG和成核剂MSF的协同加入,能够进一步提高PLA的结晶速率,并增大球晶尺寸。增塑剂PEG的加入,能够明显提高PLA/MSF/PEG的断裂伸长率,但使复合材料的拉伸强度和模量下降。与PLA/PEG共混物相比,PLA/MSF/PEG共混物具有更高的拉伸强度和模量。PLA/MSF(3%)/PEG(10%)的综合性能较好,与纯PLA相比断裂伸长率提高468.7%,拉伸强度降低48.7%左右。因此,增塑剂PEG与改性纤维MSF协同改性,使PLA/MSF/PEG共混物具有更优异的力学性能和结晶性能,能够进一步扩大PLA材料的应用范围。     

星型聚氨酯增韧改性聚乳酸3D打印线材

以聚醚三元醇为星型结构单体,采用本体预聚法合成具有可加工性的星型聚氨酯(SPUR),将其用于聚乳酸(PLA)的增韧改性,制备高韧性PLA/SPUR共混材料的3D打印线材,并采用熔融沉积成型(FDM)技术制备高韧性3D打印制品。结构表征及性能测试结果表明,当聚醚三元醇含量为3%时,合成的SPUR3分子量最高、综合性能最佳,将其与PLA进行共混,可显著提升PLA的断裂伸长率和冲击强度。当SPUR3含量为10%时,断裂伸长率最大,达336%,是PLA断裂伸长率的37.7倍;当SPUR3含量为30%时,共混物的冲击强度达到52.368 kJ/m2,是PLA冲击强度的31.8倍。SPUR3的混入还提高了PLA的结晶温度,降低了其储能模量和玻璃化转变温度,通过控制SPUR3的含量可以调控共混物的韧性和强度。所制备的打印线材表面均比较光滑,均能通过FDM工艺正常打印成产品。     

聚乳酸/液态聚异丁烯共混物的研究

为了改善聚乳酸(PLA)材料的脆性,且不影响其可降解性,选择了低分子量液态聚异丁烯(LPIB)和PLA进行共混改性,研究了LPIB用量对PLA/LPIB共混物性能的影响。结果表明,LPIB可提高PLA的韧性,但降低了其拉伸强度,当LPIB质量分数为12%时,共混物的缺口冲击强度达到最高,为5.3 k J/m2,比纯PLA提高了近一倍;LPIB在PLA中起到异相成核的作用,可提高其结晶度。采用扫描电子显微镜观察了共混物的微观形态,发现PLA与LPIB两相是分离的。为提高两者的相容性,采用缩水甘油酯(GMA)接枝LPIB(LPIB-g-GMA)作为增容剂,并研究了其用量对PLA/LPIB/LPIB-g-GMA共混物性能的影响。结果表明,LPIB-g-GMA对PLA/LPIB共混物有一定的增容作用,可使其相界面变得模糊,相容性有明显提高;当PLA,LPIB与LPIB-g-GMA的质量比为88/2/10时,PLA/LPIB/LPIB-g-GMA共混物的缺口冲击强度和拉伸强度达到最大,与未加LPIB-g-GMA的共混物相比,分别提高了20.7%和13.8%;少量LPIB-g-GMA的加入会提高PLA/LPIB/LPIB-g-GMA共混物的结晶度,但其用量过高时,会降低共混物的结晶度。     

聚酰胺66/改性耐热聚乳酸共混物的力学性能和结晶行为

采用熔融共混和注射成型制备了改性耐热聚酰胺66/聚乳酸（PA66/PLA）共混物,经热处理后,探讨了PLA含量对共混物的断口样貌形态、力学性能以及结晶性能的影响。结果表明,PLA与PA66具有一定的相容性,当PLA的含量不超过10 %（质量分数,下同）时,PA66/PLA共混物的拉伸强度在PA66的93 %以上,其断裂伸长率对比PLA得到了倍数级的增长,是PLA断裂伸长率的8.6倍;当PLA的含量不超过20 %时,共混物的结晶性能变好,提升结晶速率,缩短结晶时间,结晶度有所提高;但当PLA的含量超过20 %以后,共混物的拉伸强度则出现了不同程度的降低。     

多元环氧扩链剂对聚乳酸等温结晶行为及力学性能的影响

采用多元环氧扩链剂(ADR)对聚乳酸(PLA)进行熔融扩链改性,得到PLA/ADR共混物。采用差示扫描量热仪(DSC)对共混物的熔体等温结晶行为进行表征和分析。结果表明:在110~120℃温度范围内,ADR的加入提高了PLA熔体的结晶速率;随着ADR用量的增加,PLA等温结晶速率明显提高,半结晶时间缩短。结合熔体流动速率和偏光显微镜分析,从分子运动能力和熔体黏度的角度解释了ADR对PLA等温结晶行为的影响机理。此外,研究了结晶度变化对PLA/ADR共混物拉伸性能和维卡软化温度(VST)的影响。当PLA/ADR(100/1.0)共混物的结晶度由1.7%提高到32.2%时,其拉伸强度由55.6 MPa提高到63.2 MPa,VST由61.9℃提高到156.9℃。结晶度的增大有利于PLA/ADR共混物力学性能和耐热性能的进一步提高。     

改性油茶壳粉增强聚乳酸3D打印材料性能研究

以废弃油茶壳（COS）为原料,经过碱和硅烷偶联剂处理后,制得改性COS。将改性COS与聚乳酸（PLA）经熔融共混挤出、拉丝,制备适用于熔融沉积成型（FDM）的改性COS/聚乳酸（PLA）3D打印材料,对其力学性能、热学性能、打印性能等进行探讨。结果表明：采用碱和硅烷偶联剂改性COS,可以显著提高COS的初始热分解温度,也提高改性COS/PLA 3D打印材料的热稳定性。当改性COS的质量分数为3%,改性COS/PLA 3D打印材料的弯曲强度和拉伸强度最大分别为66.97 MPa和53.57 MPa,相比纯PLA分别提高15.19%和12.05%,而且聚合物的结晶度提高15.6%。通过FDM 3D打印技术成功制备了个性化艺术品,打印效果良好。     

成核剂与增容剂调控聚乳酸/聚丙烯复合材料的结晶与力学性能研究

通过熔融共混法制备聚丙烯/聚乳酸(PP/PLA)复合材料,研究成核剂癸二酸二苯基二酰肼(TMC-300)和增容剂聚丙烯接枝马来酸酐(PP-g-MAH)对PP/PLA复合材料的结晶行为、热学性能、力学性能的影响。结果表明,TMC-300能够显著提高PP/PLA共混物的结晶速率和结晶度,降低球晶尺寸,并改善复合材料的力学性能。当TMC-300添加量为0.5%时,共混物的熔点从163.9℃提高到168.6℃,结晶度达到44.2%,比纯PP/PLA提高25.6%,拉伸强度和冲击强度分别增加了13.33%,49.86%。当增容剂与成核剂并用时,增容剂可改善PLA链段运动能力,并提供更多的成核位点,进一步促进PLA的结晶性能,且结晶的分布由海岛式结构变为双连续相结构,复合材料的拉伸强度比纯PP/PLA提升了19.25%。     

聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究

采用熔融共混法制备聚乳酸／聚（3?羟基丁酸?co?3?羟基戊酸酯）（PLA/PHBV）,以及分别添加苯乙烯?甲基丙烯酸缩水甘油酯共聚物（ADR）、柠檬酸三丁酯（TBC）的共混物PLA/PHBV/ADR和PLA/PHBV/TBC,通过注塑和熔融沉积成型（FDM）技术制备了标准测试样条,研究了添加ADR和TBC后对PLA/ PHBV共混材料及三维（3D）打印样品热学性能和力学性能的影响。结果表明,PHBV结晶度均降低,加入ADR的注塑样品断裂伸长率最大提高到32 %,加入TBC的注塑样品拉伸强度和冲击强度提高,断裂伸长率提高到2.8 %;加入ADR的3D打印制品拉伸强度降低,断裂伸长率提高,添加TBC的3D打印制品相容性得到了明显的提升,通过扫描电子显微镜（SEM）观察无明显的颗粒相,拉伸强度在改性前后无明显变化。     

PLA/PHBV共混3D打印线材的制备及性能研究

采用熔融共混法制备了聚乳酸/聚(3-羟基丁酸-co-3-羟基戊酸酯)(PLA/PHBV)共混物,用熔融沉积成型(FDM)技术制备了三维(3D)打印标准测试样条,研究了PLA/PHBV质量比对PLA/PHBV共混物及3D打印线材性能的影响。结果表明,PLA/PHBV共混材料是完全不相容的体系,随着PHBV含量的增加,PLA/PHBV共混物以及3D打印制品的拉伸强度下降,但断裂伸长率有所提高;弯曲强度及冲击强度均先上升后下降;注塑样品的拉伸强度最大可达43.31 MPa,断裂伸长率可达5.37%;3D打印制品的拉伸强度最大可达49.16 MPa,断裂伸长率可达7.41%;PLA/PHBV共混物以及3D打印制品淬断断面呈现典型的"海岛"分布,PHBV相均匀的分散在PLA基中;随着PHBV含量的增加,注塑样条的断面逐渐变得粗糙,打印制品层与层之间空隙减小,填充率上升,黏结性能提高。     

聚乳酸/环氧大豆油共混物的性能

聚乳酸（PLA）与环氧大豆油（ESO）经熔融共混制得具有高韧性的PLA/ESO共混物,并研究了ESO含量对PLA微观形态、力学和流变性能的影响规律。结果表明：ESO可显著降低PLA的熔体黏度,提高PLA的韧性;PLA/ESO共混物在低ESO含量（10%）时为部分相容,而在高ESO含量（20%和30%）时发生了相分离,从而使共混物的断裂伸长率和冲击强度随ESO含量增加先增大后减小,且分别在ESO含量为20%和15%时达到最大值,约为PLA的17倍和2.9倍,而拉伸强度则随之减小。     

Processing and characterization of supercritical CO2 batch foamed poly(lactic acid)/poly(ethylene glycol) scaffold for tissue engineering application

Both poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) are biodegradable polymers, blending PLA with PEG is expected to toughen PLA matrix while maintaining its biodegradability. In this study, PLA/PEG blends in different ratios were prepared through triple‐screw extruder, and the foaming behavior was investigated using supercritical carbon dioxide as physical blowing agent. The mechanical, thermal, rheological properties, and crystallization behavior were also studied. By the incorporation of PEG, the impact strength of the PLA/PEG blends improved by 98% with the specimens fractured in a ductile mode. The crystallization process of the blends was accelerated, and the crystallinity was significantly increased to 45.1%. The viscoelasticity of the PLA/PEG matrix was weakened, and the cells tended to break at the cell wall during cell expansion; thus, a highly interconnected structure with a maximum porosity of 82.3% was obtained. Moreover, the PLA/PEG blends exhibited higher cell densities and smaller cell size, compared to their neat counterparts. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3066–3073, 2013     

Biodegradable poly(lactic acid)/poly(butylene succinate)/wood flour composites: Physical and morphological properties

This work sought to improve the toughness and thermal stability of poly(lactic acid) (PLA) by incorporating poly(butylene succinate) (PBS) and wood flour (WF). The PLA/PBS blends showed a PBS‐dose‐dependent increase in the impact strength, elongation at break, degree of crystallinity, and thermal stability compared to the PLA, but the tensile strength, Young's modulus, and flexural strength were all decreased with increasing PBS content. Based on the optimum impact strength and elongation at break, the 70/30 (w/w) PLA/PBS blend was selected for preparing composites with five loadings of WF (5–30 phr). The impact strength, tensile strength, flexural strength, and thermal stability of the PLA/PBS/WF composites decreased with increasing WF content, and the degree of crystallinity was slightly increased compared to the 70/30 (w/w) PLA/PBS blend. Based on differential scanning calorimetry, the inclusion of PBS and WF into PLA did not significantly change the glass transition and melting temperatures of PLA in the PLA/PBS blends and PLA/PBS/WF composites. From the observed cold crystallization temperature of PLA in the samples, it was evident that the degree of crystallinity of PLA in all the blends and composites was higher than that of PLA. The PLA/PBS blend and PLA/PBS/WF composite degraded faster than PLA during three months in natural soil, which was due to the fast degradation rate of PBS. POLYM. COMPOS., 38:2841–2851, 2017. © 2016 Society of Plastics Engineers     

聚乳酸微纳复合泡孔的结构与性能研究

通过熔融共混制备聚乳酸（PLA）/聚（己二酸丁二酯?对苯二甲酸丁二酯）（PBAT）共混物。以环氧扩链剂（CE）为相容剂,研究了CE含量对共混物的流变行为、结晶行为的影响,并研究了CE含量为5份的共混物在冷结晶温度下的发泡行为以及泡沫的拉伸性能。结果表明,共混体系的相容性、结晶速率随着CE含量的增加而增加、可发性提高,在添加了5份CE的共混物中得到了微纳复合泡孔,泡孔密度达到10¹³ 个/cm³,相对于PLA泡沫,共混物泡沫的断裂伸长率提高了40 %。     

Thermo‐rheological and interfacial properties of polylactic acid/polyethylene glycol blends toward the melt electrospinning ability

The electrospinning ability of PLA/PEG system at the melt state was investigated through the viscoelastic parameters obtained from dynamic shear and extensional rheometers. PLA and PEG were melt‐blended at various composition ratios. Effect of PEG concentration on the PLA thermal behavior was studied by the differential scanning calorimetry (DSC). According to DSC and wide‐angle X‐ray diffraction, the PLA crystallinity increased and the crystalline structure became more completed (α‐crystal form) in the presence of PEG. Viscoelastic parameters such as zero‐shear viscosity and relaxation time as an indication of elasticity were obtained. The results revealed enhanced polymer chain mobility and disentanglement ought to plasticizing effect of PEG. The critical content of PEG about 20–30 wt % at which the solid–liquid phase separation occurred was in good agreement with the viscoelastic properties. Hence, more than 20% PEG the elasticity diminished and the melt strength became zero. The interfacial tension of the PLA and PEG estimated through the rheological and morphological parameters evidenced the good miscibility of PLA/PEG system at the melt electrospinnig temperature. While the high viscose samples (η₀ > 1800 Pa/s) PLA and PLA/PEG (95/5) were not spinnable at the spinning temperature of 180 °C, blends containing 10–30% PEG were easily spun. The finest and continuous fiber mats were obtained by electrospinning of PLA/PEG (80/20) blend (d_f = 4.8 ± 0.8 μm). More than the critical concentration of PEG (Φ > 30%), lacking the elasticity suppressed the melt electro‐spinnability of PLA/PEG. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44120.     

聚乳酸/聚乙醇酸共混合金界面改性研究

用熔融共混挤出法制备了不同配比的聚乳酸(PLA)/聚乙醇酸(PGA)共混合金,并分别加入环氧型扩链剂ADR 4370F进行对比分析,通过拉伸性能测试、弯曲性能测试、缺口冲击强度测试、扫描电子显微镜(SEM)和差示扫描量热(DSC)仪研究了共混合金力学性能、相容性和结晶性能。结果表明:与纯PLA和纯PGA相比,PLA/PGA共混合金的相容性差,导致力学性能降低,纯PLA、纯PGA和70%PLA/30%PGA合金的拉伸强度、弯曲强度、断裂伸长率和缺口冲击强度分别为58.6 MPa,123.5 MPa,8.52%,9.0 J/m;91.9 MPa,157.6 MPa,7.9%,5.2 J/m;41.2 MPa,91.2 MPa,3.8%,2.0 J/m。PLA和PGA可以互相加快结晶速度,加入环氧型扩链剂可以改善合金的相容性,上述四个力学性能可相应提高到49.2 MPa,96.0 MPa,4.5%,4.3 J/m,而且降低了PLA和PGA的结晶度。另外,向PLA中加入1%PGA时,PGA可以充当PLA的成核剂,使PLA的冷结晶温度降低10℃左右,结晶度提高1.3%。     

Crystallization and phase separation in blends of high stereoregular poly(lactide) with poly(ethylene glycol)

The effect of cooling rate on crystallization and subsequent aging of high stereoregular poly(lactide) (PLA) blended with poly(ethylene glycol) (PEG) was studied by thermal analysis and by direct observation of the solid state structure with atomic force microscopy (AFM). Blending with PEG accelerated crystallization of PLA. When a PLA/PEG 70/30 (wt/wt) blend was slowly cooled from the melt, PLA crystallized first as large spherulites followed by crystallization of PEG. The extent of PLA crystallization depended on the cooling rate, however, for a given blend composition the PEG crystallinity was proportional to PLA crystallinity. The partially crystallized blend obtained with a cooling rate of 30 °C min⁻¹ consisted of large spherulites dispersed in a homogeneous matrix. The blend was not stable at ambient temperature. With time, epitaxial crystallization of PEG on the edges of the spherulites depleted the surrounding region of PEG, which created a vitrified region surrounding the spherulites. Further from the spherulites, the homogeneous amorphous phase underwent phase separation with formation of a more rigid PLA-rich phase and a less-rigid PEG-rich phase. Decreasing the amount of PEG in the blend decreased the crystallization rate of PLA and increased the nucleation density. The amount of PLA crystallinity did not depend on blend composition, however, PEG crystallinity decreased to the extent that PEG did not crystallize in a PLA/PEG 90/10 (wt/wt) blend.     

PLA/PTW共混物的制备及性能研究

聚乳酸(PLA)/乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PTW)以不同比例通过双螺杆挤出机反应性挤出制备。对PLA/PTW共混物的力学性能、热性能、流变性能和动态力学性能进行了研究。力学结果表明,添加5%的PTW时,共混物的冲击强度为纯PLA的4倍左右,明显改善了PLA的柔韧性。热性能测试结果表明PTW的加入抑制了PLA的结晶能力,提高了PLA/PTW共混物的热稳定性。动态力学测试表明PLA与PTW之间有一定的相容性。     

异氰酸酯对聚乳酸/热塑性聚氨酯共混物性能的影响

以4,4^′-二苯基甲烷二异氰酸酯（MDI）为反应增容剂，采用熔融共混法制备了不同MDI含量的聚乳酸/热塑性聚氨酯（PLA/TPU）共混物，采用傅里叶变换红外光谱仪（FTIR）、万能试验机、冲击试验机、扫描电子显微镜（SEM）、差示扫描量热仪（DSC）和旋转流变仪对共混物力学性能、微观形态、热性能和流变性能进行了研究。结果表明：MDI可以有效改善共混物的力学性能，当MDI质量分数为1%时，共混物力学性能最佳，缺口冲击强度为40.0kJ/m²，断裂伸长率为214.1%，与未加MDI的共混物相比，分别增加了4.3倍和5.8倍，拉伸强度稍有下降（47.6MPa）；SEM表明，MDI的加入提高了共混物的相容性，加入MDI后，共混物的断面由海-岛结构变为核-壳包覆结构，相界面作用力增强；DSC测试表明，共混物的玻璃化转变温度、冷结晶温度和熔融温度随着MDI含量的增加而升高；流变测试表明，MDI质量分数的增加，共混物呈现更显著的剪切变稀行为，推测共混反应机理为：MDI质量分数的增加，体系内依次发生PLA的扩链、支化和TPU的交联。