聚乳酸切片的纺丝工艺研究

以聚乳酸切片为原料,通过熔融纺丝—拉伸两步法制得聚乳酸纤维,研究纺丝温度、纺丝速度、拉伸倍数对聚乳酸纤维性能的影响。结果表明,聚乳酸有良好的成纤能力,纺丝速度、纺丝温度的变化对聚乳酸纤维的相对分子质量均有显著影响。     

三叶异形聚乳酸纤维的熔融纺丝及其性能研究

以特性粘数1．51 dL／g的聚乳酸(PLA)为原料,采用三叶异形喷丝板一步法熔融纺丝制备出异形度为52％的三叶异形PLA纤维,研究了其热性能和机械性能。结果表明,PLA纤维的断裂强度和初始模量随拉伸倍数的增加而提高,经4倍拉伸,其断裂强度为2．39 cN／dtex,初始模量为17．27 cN／dtex。由于PLA的慢速冷却结晶过程,纤维在成形过程中形成不同晶层厚度的结晶结构。纺丝过程中纤维皮层结构受到更大的拉伸取向作用,并在纤维表面出现一定游离原纤化结构。     

熔融纺丝法研究LDPE的拉伸流变性能

采用熔融纺丝法研究了低密度聚乙烯(LDPE)熔体的拉伸流变性能。LDPE熔体强度随温度升高而下降;适当降低拉伸黏度可提高熔体的可拉伸性;随拉伸应变速率升高拉伸应力上升,而拉伸黏度下降;拉伸应力和拉伸黏度都随温度的升高呈下降趋势;提高挤出速率可得到较低的拉伸应力和拉伸黏度。     

聚乳酸熔融法纺丝原料选择的研究

采用1H-NMR、13C-NMR、DSC和GPC等研究方法对3种不同的熔融纺丝原料用的聚乳酸进行了分析。研究结果表明:聚乳酸的消旋性即光学活性、残存单体量会影响到聚乳酸的热性能,进而影响聚乳酸的熔纺性能。尤其是当聚乳酸的立体规整性过差时,就会呈现非晶聚合物的特性,无法进行熔融纺丝。     

熔融纺丝法研究聚乙烯熔体的拉伸流变性能

采用熔融纺丝法研究了低密度聚乙烯（PE-LD）、线形低密度聚乙烯（PE-LLD）和高密度聚乙烯（PE-HD）熔体的拉伸流变性能。结果表明,PE-LD、PE-LLD和PE-HD熔体的熔体强度都随温度的升高而下降;随着拉伸应变速率和温度的升高,PE-LD、PE-LLD和PE-HD熔体的拉伸黏度下降;随着挤出速率的提高,相同应变速率下,PE-LD、PE-LLD和PE-HD熔体的拉伸应力和拉伸黏度都有所降低。     

聚乳酸的流变性能研究

用XLY-Ⅱ型流变仪在剪切速率为2 000s-1-10000s-1的范围内研究了PLA的流变性能。结果表明PLA是一种非牛顿流体,其表观粘度随剪切速率的增加而下降,且对高剪切速率比较敏感。PLA的粘流活化能较低,表明受温度影响较小。     

聚氯乙烯纤维熔融纺丝工艺及性能研究

采用熔融纺丝技术制备聚氯乙烯(PVC)初生纤维,经过75~95℃水浴拉伸3~8倍制得PVC纤维,研究了不同增塑剂含量的PVC体系的流变性和热稳定性,通过X射线衍射和小角X射线散射分析了拉伸条件对PVC纤维结构及力学性能的影响。结果表明:PVC熔体符合切力变稀行为;增塑剂加入量越多,PVC分子间作用力越小,PVC熔体流动性越好,PVC体系热稳定性较好;PVC纤维后处理工艺拉伸倍数越大,PVC纤维结晶长周期越小,取向诱导新的结晶结构出现,分子间作用力增大,PVC纤维的强度越大;相同拉伸倍数下,后拉伸温度越高,PVC纤维强度越大;适宜PVC体系配方为PVC与邻苯二甲酸二辛酯及邻苯二甲酸二丁酯的质量比为100∶40∶20,其他添加剂若干,此配方的PVC初生纤维在95℃水浴中拉伸8倍,所得的纤维其断裂强度为1.04 c N/dtex,断裂伸长率35.78%。     

UHMWPE/聚烯烃共混物的性能及其熔融纺丝研究

将超高相对分子质量聚乙烯(UHMWPE)与共混组分聚烯烃(PB)按一定质量比计量,并加入质量分数为0.3%的抗氧剂1010,在双螺杆挤出机上共混造粒,研究了PB的用量对UHMWPE/PB共混物熔点和流变性能的影响;采用实验室熔融纺丝装置对UHMWPE/PB共混物进行纺丝,拉伸得到UHMWPE/PB共混纤维,研究了共混纤维的形貌、结晶性能和力学性能。结果表明:在共混温度为230~290℃时,UHMWPE/PB共混物可实现宏观上均匀共混;共混物具有介于两共混组分熔点之间的单一熔点,共混物熔点随UHMWPE含量的提高而提高;共混物熔体属假塑性流体,270~320℃条件下,随UHMWPE含量的增加,UHMWPE/PB共混物结构黏度指数逐渐增加,黏流活化能逐渐减小,共混物的熔体黏度对温度不敏感;当UHMWPE/PB质量比为1∶1,纺丝温度为310℃时,共混物具有良好的可纺性,经过19倍的后拉伸,所获得的UHMWPE/PB共混纤维直径为45μm,断裂强度可达16.4 c N/dtex,初始模量约190.0 c N/dtex。     

耐高温聚醚砜熔融纺丝的可纺性研究

采用熔融纺丝法制备耐高温聚醚砜(PES)纤维,对PES切片的热性能、流变性能以及可纺性进行了研究,并对PES初生纤维的力学性能和表面形貌进行了表征。结果表明:PES具有良好的热稳定性能和较宽的加工温度范围,其起始热裂解温度为530.8℃,适宜熔融纺丝;PES熔体是一种典型的剪切变稀型流体,对剪切速率和温度变化较为敏感;纺丝工艺对PES的可纺性影响显著,PES在100℃干燥6 h,螺杆三区温度分别为330,340,345℃,喷丝板温度345℃,喷丝板压力约2.4 MPa,卷绕速度170 m/min的条件下,PES初生纤维的综合性能优异、纤维粗细均匀、表面光滑。     

各向同性煤沥青纺丝原料的流变性能与纺丝

煤沥青原料的纺丝,是碳纤维制造过程中加工成型的关键步骤。在纺丝过程中,要严格控制煤沥青熔体的粘度、纺丝温度、压力、卷绕速度等主要参数。这些参数均为熔体的流变性能所控制。因此,研究煤沥青熔体的流变性能,从理论上和实践上对煤沥青纺丝都有重要的指导意义。     

Effect of solution concentration in microfiltration properties of PLA mats produced by solution blow spinning

In order to remediate the difficulty of access to safe drinking water by 1/3 of the world population, mats produced by solution blow spinning (SBS) have a great potential for use in liquid filtration due to their small pores and high porosity, being capable of filtrating water by retaining particles and even microorganisms. In this context, this work aims the production and characterization of poly (lactic acid) mat obtained by SBS to be morphologically, thermally, and mechanically evaluated, as well as to observe water flux properties. The correlation between structure-processing-properties is an important part of the work, which shows that lower concentration of polymeric solution leads to mats with smaller average fiber diameter, greater crystallinity, impacting on their greater tensile strength. The water flux performance shows that mats obtained from higher polymer concentration solutions present less resistance to the water flow, which indicates larger pore diameters.     

Characterization of poly(L‐lactic acid) fibers produced by melt spinning

Biodegradable poly(L ‐lactic acid) (PLLA) fibers were processed by a two‐step melt‐spinning method (melt extrusion and hot draw) from PLLA with three different viscosity‐average molecular weights (494,600, 304,700, and 262,800). Before spinning, the polymer flakes were first milled into powders and dried under vacuum. Viscosity‐average molecular weight of PLLA following the fabrication process was monitored. Tensile properties of as‐spun and hot‐drawn fibers were investigated. Morphology of the PLLA fibers was viewed under a scanning electron microscope. Crystallinity of these fibers was assessed by thermogram analysis of differential scanning calorimetry. Results showed that the extent of decrease in the viscosity‐average molecular weight of PLLA dropped sharply by 13.1–19.5% during pulverization and by 39.0–69.0% during melt‐extrusion. The hot‐draw process in this study had a little effect on the viscosity‐average molecular weight of PLLA. Smoother fibers could be obtained for the die temperature at least 230°C for raw materials with higher crystallinity (more than 75%) and at least 220°C for raw materials with lower crystallinity (about 60%). The as‐spun fibers showed crystallinity of 16.5–22.8% and the value increased to 50.3–63.7% after hot draw. Tensile moduli of the as‐spun fibers were in the range of 1.2–2.4 GPa, which were raised to 3.6–5.4 GPa after hot draw. The final PLLA fibers with 110–160 μm diameters showed tensile strengths of 300–600 MPa. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 251–260, 2001     

PBT/PEG/LA可降解聚醚酯的合成及纺丝研究

采用对苯二甲酸二甲酯(DNT)、1,4-丁二醇(BDO)、聚乙二醇(PEG)和乳酸(LA)合成了聚对苯二甲酸丁二醇酯(PBT)/PEG/LA可降解聚醚酯,通过纺丝制备了PBT/PEG/LA共聚物纤维。结果表明:红外光谱和核磁共振分析所得聚合物为PBT/PEG/LA。PBT/PEG/LA共聚物在50℃真空预干燥5 h,80℃干燥5 h,控制纺丝温度高于聚醚酯熔点15～30℃可顺利纺丝,纤维质量良好。随着拉伸倍数、热定型温度或时间的增加,纤维的断裂强度提高.断裂伸长率下降。LA摩尔分数高,有利于纤维降解,但纤维熔点和断裂强度相应下降。     

EVA熔体流动速率对PLA/EVA共混物性能的影响

通过熔融共混法制备了聚乳酸（PLA）/乙烯-乙酸乙烯酯共聚物（EVA）共混物,采用SEM、DSC、旋转流变仪等研究了VA质量分数为28%,熔体流动速率（MFR）不同的EVA对PLA/EVA共混物性能的影响。结果表明,EVA熔体流动速率越小,其在PLA基体中分散越均匀,EVA颗粒粒径也越小。共混物的结晶度随EVA熔体流动速率的增大而增大,但PLA的玻璃化转变温度（Tg）基本不受EVA的影响。PLA/EVA共混物的复数黏度和储能模量均随EVA的熔体流动速率的增高而减小。力学性能测试结果表明,当EVA的质量分数为15%时,PLA的断裂伸长率明显升高,冲击强度约是纯PLA的2倍。     

PLA/POE-g-GMA共混物的制备及性能研究

采用熔融反应法制备乙烯-辛烯共聚物（POE）接枝甲基丙烯酸缩水甘油酯（GMA）（POE-g-GMA）,实现POE反应的官能化,通过反应共混的方法制备聚乳酸（PLA）/POE共混物,考察了POE和POE-g-GMA对PLA的力学性能和热性能及微观形态的影响。结果表明：POE-g-GMA要有适当的接枝率,增韧效果才显著,用0.6%～0.8%接枝率的POE-g-GMA增韧PLA,当POE-g-GMA质量分数达到20%时,共混物的缺口冲击强度提高到基体PLA的6倍左右;同时材料的热性能基本不受影响。POE与PLA间相容性不好,接枝后与PLA间相容性得到改善。     

聚乳酸/纳米蒙脱土纳米复合材料的制备与挤出发泡研究

采用熔融插层法制备了聚乳酸/有机改性纳米蒙脱土（PLA/OMMT）复合材料,对其复合结构、力学性能、热性能、动态流变性能进行了测试和表征,并研究了复合材料的挤出发泡行为。结果表明,不同含量的OMMT与PLA进行熔融插层会形成不同的插层与剥离结构;3 %的OMMT可以提高PLA的力学性能、改善热性能;OMMT能够提升PLA的熔体强度,同时在挤出发泡过程中起到成核剂的作用,并且能够减弱发泡剂气体向PLA熔体外部的扩散,从而提高PLA挤出发泡的效果。     

Studies on high‐speed melt spinning of noncircular cross‐section fibers. III. Modeling of melt spinning process incorporating change in cross‐sectional shape

A numerical analysis program for high‐speed melt spinning of flat and hollow fibers was developed. Change in cross‐sectional shape along the spin line was incorporated adopting a formulation in which energy reduction caused by the reduction of surface area was assumed to be equal to the energy dissipation by viscous flow in the plane perpendicular to the fiber axis. In the case of flat fiber spinning, the development of temperature distribution in the cross section was considered. It was found that the empirical equations for air friction and cooling of the spin line of circular fibers can be applied for the flat fiber spin line if the geometrical mean of long‐axis and short‐axis lengths was adopted, instead of fiber diameter, as the characteristic length for Reynolds number and Nusselt number. Three features expected through the high‐speed spinning of noncircular cross‐section fibers could be reproduced: (1) although cooling of the flat fiber spin line was enhanced, calculated tension at the position of solidification was not affected much by the difference in cross‐sectional shape; (2) change in cross‐sectional shape proceeded steeply near the spinneret; and (3) temperature at the edge became significantly lower than that at the center in the cross section of flat fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1589–1600, 2001     

Effect of liquid isothermal bath position in modified poly(ethylene terephthalate) PET melt spinning process on properties and structure of As-spun and annealed filaments

The ability to produce as-spun poly(ethylene terephthalate) (PET) filaments that possess previously unsurpassed levels of as-spun orientation and tensile properties was achieved through the implementation of a device described as a liquid isothermal bath (LIB). Although much has been published regarding the general effect of the LIB on various properties and structural features, the results of the present study further contribute to the continued development of this unique technology by investigating the positional dependence of the device, as well as the effect of a subsequent annealing process. Characterization methods employed in the present study included birefringence, percent crystallinity, tensile properties, loss tangent temperature dependence, DSC melting behavior, and wide-angle and small-angle X-ray scattering. Strong inferences drawn from the loss tangent temperature dependence indicate that all of the as-spun and annealed LIB filaments possess a more rigid amorphous phase than that present in either the as-spun or annealed no LIB filament and that the extent of rigidness appears to become more profound as the bath is operated at a position more distant from the spinneret. DSC melting endotherms of the as-spun LIB filaments consist of dual overlapping peaks, one component of which is believed to represent the presence of a novel extended chain type of crystalline structure. Application of a simple two phase model allowed for the quantitative evaluation of an amorphous orientation factor, which was found to range, depending on the bath position, from 1.7 to 3.9 times higher in the as-spun LIB filaments than that present in the as-spun no LIB filament. The annealing process was found to play an important role in facilitating the transformation from an as-spun highly oriented and predominantly amorphous structure to a well-defined semicrystalline fibrillar structure. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2051–2068, 1998     

聚乳酸熔融缩聚的研究

综述了近年来国内外聚乳酸熔融聚合的研究情况,概述了直接熔融缩聚、熔融-固相和熔融-扩链合成聚乳酸的研究,并研究探讨了熔融聚合中影响聚乳酸相对分子质量的因素。