The influence of resin characteristics on the high speed melt spinning of isotactic polypropylene. I. Effect of molecular weight and its distribution on structure and mechanical properties of as-spun filaments

The fine structures and tensile mechanical properties were characterized for high speed melt spun filaments prepared from three polypropylenes with melt flow indices in the range 12–300. It was found that spinnability and the resulting structure and properties are affected by both the weight average molecular weight and the polydispersity of the polymer. Higher tenacities, with consequent lower percent elongation to break, could be achieved by spinning the narrow molecular weight distribution polymers at high spinning speeds. This effect was associated with the development of higher birefringence in these samples. Modulus did not correlate with birefringence in the present study, but it was found to be controlled by the nature and level of crystalline order developed in the filaments.     

The influence of isotacticity,ethylene comonomer content,and nucleating agent additions on the structure and properties of melt-spun isotactic polypropylene filaments

The influence of isotacticity, ethylene comonomer content, and nucleating agent additions on the structure and properties of melt-spun polypropylene filaments was studied for a series of polypropylenes having similar resin melt flow rates (MFR ≌ 35), average molecular weights, and polydispersities. In general, increasing the degree of isotacticity increases crystallinity and tensile modulus of the spun filaments, while increasing the copolymer content has the opposite effect. Nucleating agent additions also lead to greater crystallinity, but, under certain conditions, the addition of a nucleating agent can lead to lower tensile modulus in spite of higher crystallinity. For given spinning conditions, the tensile strength increased slightly with increased copolymer content but was little affected by tacticity in the range studied. Nucleating agent additions lowered the tensile strength of spun filaments. The effects of nucleating agents on the filament modulus and tensile strength were traced to their ability to raise the crystallization temperature and reduce the level of molecular orientation generated in the filaments. The reasons for the observed behavior are discussed. © 1996 John Wiley & Sons, Inc.     

Melt spinning of metallocene catalyzed polypropylenes. II. As‐spun filament structure and properties

The melt spinning of metallocene catalyzed isotactic polypropylene (miPP) resins was investigated. The as‐spun filament properties from six miPP resins were studied with melt flow rates (MFR) between 10 and 100, and a Ziegler–Natta catalyzed isotactic polypropylene (zniPP) resin with a MFR of 35 was studied for a comparison. Generally, as the molecular weight increased the filament density increased, the birefringence decreased, the tensile strength decreased, and the elongation to break increased. As the spinning speed increased, the density, birefringence, tensile strength, and crystalline and noncrystalline orientation functions generally increased. However, the low MFR miPP and the zniPP resin had decreases in the birefringence and tensile strength with an increase of the spinning speed. The miPP resins were found to have breaking tensile strengths up to 50% higher than the zniPP resin at similar spinning speeds. The observed fiber properties were explained based on the nature and orientation of noncrystalline portions of the fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3237–3247, 2001     

Process–structure–property relationship of melt spun poly(lactic acid) fibers produced in the spunbond process

We report on the process–structure–property relationships for Poly(lactic acid) (PLA) filaments produced through the spunbond process. The influence of spinning speed, polymer throughput, and draw ratio on crystallinity and birefringence of fibers were evaluated. We established that increasing spinning speed increases crystallinity and birefringence of fibers. We also investigate the role of fiber structures on fiber tensile properties—breaking tensile strength, strain at break, initial modulus, and natural draw ratio. An increase in spinning speed leads to a higher breaking tensile strength, higher initial modulus and lower strain at break. We have shown an almost linear relationship between breaking tensile strength of PLA fibers and birefringence. This indicates that improved tensile properties at high spinning speeds can be attributed to enhanced molecular orientation. The dependency of fiber breaking tensile strength and strain at break on spun orientation were explained with natural draw ratio, as a measure of spun orientation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44225.     

Effect of molecular weight on high-speed melt spinning of nylon 6

An extensive experimental study of the structure and properties developed in as-spun nylon 6 filaments is reported. Five polymers representing different molecular weights in the range 25,000–73,000 g/mol (viscosity average) were studied. These polymers were melt spun over a range of spinning speeds using an air drag type of drawdown device. Maximum take-up velocities achieved were in the neighborhood of 4000 m/min. The structure and properties of the as-spun filaments were characterized using density, DSC, WAXS, SAXS, birefringence, and tensile tests. The structural characteristics and properties of the filaments are strongly dependent on molecular weight. Generally, higher molecular weight leads to higher modulus and filament tenacity and lower elongation to break in the as-spun filaments. The structural changes with molecular weight are rather complicated; the complications are explained in terms of changes of crystallization rate and attainable crystallinity.     

Properties of high‐speed spun high molecular weight poly(ethylene terephthalate) filaments

High‐speed spinning of high molecular weight poly(ethylene terephthalate) (PET) having an intrinsic viscosity of 0.98 dL/g was performed at the take‐up velocity range of 2.5–5.5 km/min. The structure of the as‐spun filaments was analyzed by density, birefringence, WAXS, DSC, boiling water shrinkage, and tensile properties. Stress‐induced crystallization takes place above 3 km/min, which is confirmed by the steep increase in density, the growth of the crystal size, melting point increase, and the decrease in boiling water shrinkage. The plot of crystallinity versus birefringence shows that crystallinity increases drastically after birefringence reaches the value of about 0.075. A comparison with the data of other researchers will clearly present the effects of molecular weight on the properties of PET filaments spun at high speed, for example, the take‐up velocity range of the steep increase in density for high molecular weight PET is lower than that for low molecular weight PET by about 1 km/min. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1283–1291, 1999     

熔纺PE⁃UHMW/PE⁃HD共混纤维的力学性能和晶体结构研究

通过熔融纺丝工艺制备了拉伸强度为1.13 GPa的超高分子量聚乙烯（PE?UHMW）/高密度聚乙烯（PE?HD）共混纤维。采用差示扫描量热仪（DSC）、扫描电子显微镜（SEM）、X射线衍射仪（XRD）、声速取向测试、纤维强度测试等方法研究了初生丝和纤维的晶体结构及力学性能。结果表明,将PE?UHMW与低熔体流动速率（MFR）的PE?HD共混后,提高了共混纤维的分子链取向度、结晶度及力学性能;由高度取向的分子链形成的晶粒可以在轴向上被有效拉伸,形成更规则和致密的晶体结构,从而提高了纤维的力学性能。     

Melt spinning of metallocene catalyzed polypropylenes. I. On‐line measurements and their interpretation

The melt spinning of metallocene catalyzed isotactic polypropylene resins was investigated. The details are presented for on‐line studies performed on six miPP resins with melt flow rates (MFRs) between 10 and 100 and a Ziegler–Natta catalyzed isotactic polypropylene resin with a MFR of 35 for comparison. The on‐line studies indicated that, as the molecular weight and polydispersity increased, crystallization occurred closer to the spinneret at higher crystallization temperatures and under lower spin line stresses. Further, as the spinning speed increased, crystallization occurred closer to the spinneret at higher crystallization temperatures because of increased stress in the spin line. These observations were interpreted in terms of an increased rate of crystallization caused by increased molecular orientation in the spin line with increasing molecular weight and increasing spinning speed. This “stress‐enhanced” crystallization was further interpreted in terms of an increased rate of crystal nucleation. It was further concluded that the narrower molecular weight distribution of metallocene resins was the primary factor that produced differences in the structure and properties of fibers spun from these resins compared to those of Ziegler–Natta catalyzed resins of similar weight‐average molecular weight or MFR. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3223–3236, 2001     

Melt spinning of isotactic polypropylene: Structure development and relationship to mechanical properties

An extensive experimental study of structure development during the melt spinning of polypropylene and is as-spun polypropylene filaments is reported. Five polymers representing different molecular weights and polymerization methods were studied. WAXS, SAXS, and birefringence measurements were used to characterize the structure of the filaments. Spinning through air gives rise to monoclinic crystalline structures and spinning into cold water, the paracrystalline smectic form. Both crystalline and amorphous orientation factors were found to correlate with spinline stress for the different polymers studied. Mechanical properties of as-spun fibers such as modulus, yield strength, tensile strength, and elongation to break also correlate with spinline stress.     

Melt spinning and drawing of 2‐methyl‐1,3‐propanediol‐substituted poly(ethylene terephthalate)

The structure and properties of fibers prepared from copolymers of poly(ethylene terephthalate) (PET) in which 2‐methyl‐1,3‐propanediol (MPDiol® Glycol is a registered trademark of Lyondell Chemical Company) at 4, 7, 10, and 25 mol% was substituted for ethylene glycol were studied and compared with those of PET homopolymer. Filaments were melt spun over a range of spinning conditions, and some filaments that were spun at relatively low spinning speeds were subjected to hot drawing. The filaments were characterized by measurements of birefringence, differential scanning calorimetry (DSC) crystallinity, melting point, glass transition temperature, wide‐angle X‐ray diffraction patterns, boiling water shrinkage, tenacity, and elongation to break. Filaments containing 25 mol% MPDiol did not crystallize in the spinline at any spinning speed investigated, whereas the other resins did crystallize in the spinline at high spinning speeds. However, compared with PET homopolymer, increasing substitution of MPDiol reduced the rate at which the crystallinity of the melt spun filaments increased with spinning speed and reduced the ultimate crystallinity that could be achieved by high‐speed spinning. The rate of development of molecular orientation, as measured by birefringence, also decreased somewhat with increasing MPDiol content. Shrinkage in boiling water decreased at high spinning speeds as the amount of crystallinity increased; however, the shrinkage decreased more slowly with increase in spinning speed as MPDiol content increased. Tenacity also decreased slightly at any given spinning speed as MPDiol content increased, but there was no significant effect on elongation to break. The addition of MPDiol in amounts up to 7 mol% increased the maximum take‐up velocity that could be achieved at a given mass throughput. This result indicates that the use of higher spinning speeds could potentially increase the productivity of melt spun yarns. Copolymer filaments spun at low speeds were readily drawn to produce highly oriented fibers with slightly less birefringence, crystallinity, and tenacity than similarly processed PET homopolymer. Preliminary dyeing experiments showed that the incorporation of MPDiol improved the dyeability of the filaments. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2598–2606, 2003     

Influence of the addition of lubricant on the properties of poly(ether ether ketone) fibers

A high‐temperature lubricant genioplast pellets (GPPS) was used in order to improve the processing behavior of poly(ether ether ketone) (PEEK) resin and high‐performance PEEK fibers were produced by melt‐spinning. The rheological properties of spinning material, morphology, mechanical, and thermal properties of PEEK fibers were characterized by using a polymer capillary rheometer, scanning electron microscopy, single fiber electronic tensile strength tester, wide‐angle X‐ray diffraction and thermal gravimetric analyzer, respectively. The results indicated that the introduction of lubricant GPPS decreased the melting viscosity of PEEK resin and improved spinnability of PEEK resin without sacrificing its thermal properties. The filaments are cylindrical with smooth surface and uniform diameter. The optimized content of GPPS was determined to be 1.0 wt% by balancing the decreased torque and changes of the mechanical properties. The strength and modulus of PEEK fibers were 420 MPa and 3.6 GPa, respectively. This should be due to the improvement in spinnability, followed by the enhancements in the orientation and crystallization of PEEK fibers in the process of drawing and annealing. POLYM. ENG. SCI., 53:2254–2260, 2013. © 2013 Society of Plastics Engineers     

Structure development in melt spinning of poly(ethylene‐co‐octene) filaments with various comonomer contents

An experimental study of the spinnability and the variation in crystallinity and orientation of melt spinning of poly(ethylene‐co‐octene) with different contents of comonomers was carried out. The spinning behavior of these polymers was investigated under different draw‐down ratios and temperatures and correlated to spinline stress. The melt‐spun filaments were characterized by wide‐angle X‐ray diffraction birefringence, and differential scanning calorimetry. S‐1 is a high‐density polyethylene and S‐2, S‐3, and S‐4 have 16, 22, and 38 wt % octene. An orthorhombic unit cell was found in all four polymers, but a dominant hexagonal structure (perhaps mesophase) was found for the highest octene level (S‐4). The orientation factors for the a‐, b‐, and c‐axis of the orthorhombic crystal structure and a‐axis of the hexagonal phase were then calculated. The crystalline orientation behavior of the lower octene copolymers (S‐1, S‐2, and S‐3) are similar and can be represented as a “row‐nucleated“ structure. However, the orientation behavior of S‐4 was different. The uniaxial mechanical properties were also measured. The Young's modulus and tensile strength generally increased with birefringence for all polymers. With increasing content of octene, the Young's modulus showed a decrease from semicrystalline thermoplastic toward an elastomer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 9–22, 2004     

超高相对分子质量PPTA树脂及其高模量芳纶的研究

对高相对分子质量聚对苯二甲酰对苯二胺(PPTA)树脂进行了表征,开展了添加超高相对分子质量PPTA树脂与普通相对分子质量PPTA树脂共混进行液晶纺丝得到高强度和高模量芳纶的结构表征与性能试验,同时对芳纶的力学性能与其PPTA树脂相对分子质量的关系进行了研究。结果表明,芳纶的力学性能与其PPTA聚合体的相对分子质量紧密相关,如果PPTA树脂的相对分子质量不够高,加上液晶纺丝和高模量热处理过程分子链的进一步降解,高模量芳纶的制备就无法实现。在系统研究PPTA聚合反应规律,特别是聚合诱导相互转变规律及其影响因素研究基础上,通过调控连续聚合的反应条件,在1 000 t/a连续聚合生产线上制备出比浓对数粘度高达9.2 dl/g的超高相对分子质量PPTA树脂;用超高相对分子质量PPTA树脂与通用级PPTA树脂(比浓对数粘度6.8 dl/g)混合进行纺丝,制备出高强度的芳纶,并进一步热处理得到高强度和高模量的芳纶。     

3-巯基丁酸酯对MBS树脂相相对分子质量及PVC/MBS力学性能的影响

通过添加3-巯基丁酸酯合成了一系列树脂相相对分子质量变化的甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物(MBS树脂)。并将其与聚氯乙烯(PVC)树脂进行熔融共混,测试了PVC/MBS合金的力学性能。结果表明,链转移剂3-巯基丁酸酯用量越多,MBS树脂相的相对分子质量越低,PVC/MBS合金的熔体流动速率越高、加工流动性越好、冲击强度越低,但对拉伸强度影响不大。这对开发系列MBS树脂具有重要指导意义。     

Effect of service temperature on structure and mechanical properties of polyamide 6 & 66 tyre cords

The effect of service temperature on chemical structure and mechanical properties of polyamide 6 & 66 tyre cords was studied over the broad range of 50–200 °C and for a period of 16 h. The heat treatment of cords at below 100 °C and above 120 °C was found to reduce their tensile properties considerably. The changes in properties above 120 °C were caused by increase in width of the molecular weight distribution curve as ascertained by gel permeation chromatography (GPC) studies and increase in irregularity of the polymeric chains as ascertained by birefringence studies; this appears to be due to the fact that, by raising the temperature, both chain folding and chain scission occur. Since there was deformation of the amorphous regions as ascertained by FTIR spectroscopy and birefringence studies, the changes in properties below 100 °C were attributed mainly to the effectiveness of thermal oxidation and annealing in the amorphous phase. In other words, the degree of crystallinity increased, the tyre cord became brittle, and breaking load and elongation at break were decreased. The lower reduction of tensile properties at an intermediate temperatures of 100–120 °C was caused by the lower polydispersity and irregularity in the polymeric chains, in comparison with higher temperatures and less crystallinity than lower temperature treatments.     

High performance cellulose fibers regenerated from 1-butyl-3-methylimidazolium chloride solution: Effects of viscosity and molecular weight

In the present study, we focused on several factors affecting the utility of 1-butyl-3-methylimidazolium chloride (BMIMCl) for obtaining higher performance fibers. The dependence of the spinnability and tensile strength of the fibers on the zero-shear viscosity of the spinning solutions was investigated based on differences in the molecular weight of the cellulose, pulp concentration, and the pH of BMIMCl. We demonstrated an appropriate viscosity range of 2000–4000 Pa s⁻¹ (100 °C) for spinning dopes to obtain good spinnability and high tensile strength. The pH of the BMIMCl and the molecular weight of the cellulose clearly impacted tensile strength. The high molecular weight of cellulose contributed to high mechanical properties of the regenerated cellulose fibers. Optimizing the molecular weight and concentration of the cellulose based on the appropriate viscosity allowed us to prepare high performance cellulose fibers with a tensile strength of 1.15 GPa and a Young's modulus of 42.9 GPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48681.     

WINGS系统纺预取向丝的结构与性能稳定性分析

以WINGS(Winding Integrated Gadet Solution)纺丝系统和传统ACW(Advanced Craft Winde)r纺丝系统为研究对象,比较同一纺丝位不同丝饼间预取向丝(POY)在相同纺丝条件下的结晶度、双折射率、力学性能、沸水收缩率等的变化规律。研究发现,WINGS纺丝系统同一纺丝位不同丝饼间POY的双折射率、结晶度、断裂强度、断裂伸长率、初始模量及沸水收缩率各值的变化率(CV值)均低于传统ACW工艺生产的POY的值,表明WINGS纺丝系统制得的POY有更稳定的结构和性能。     

Effect of initial take-up speed on properties and structure of as-spun and drawn/heat-set poly(ethylene terephthalate) filaments

The effect of initial take-up speed on the properties and structure of both as-spun and drawn/heat-set poly(ethylene terephthalate) filaments was characterized through measurements of birefringence, percent crystallinity, tensile properties, high temperature shrinkage, loss tangent temperature dependence, DSC melting behavior, and wide-angle (WAXS) and small-angle X-ray scattering (SAXS). While a steady trend toward improved as-spun filament orientation and tensile properties occurred with increasing initial take-up speed, the reduced drawability of these more structured precursor filaments resulted in corresponding drawn/heat-set filaments that were of relatively lower overall orientation and tensile strength. The observed trends in tenacity, initial modulus, and high temperature shrinkage of the drawn/heat-set filaments appeared to be well correlated with the extent and distribution of amorphous phase rigidity as perceived through inferences made from the loss tangent temperature dependence. The WAXS patterns of the drawn/heat-set samples indicated that these filaments all possess a well-developed and highly oriented crystalline structure. Application of a simple two phase model allowed the determination of an amorphous orientation factor, which for the drawn/heat-set filaments was generally found to decrease as the draw ratio imposed in order to achieve comparable levels of elongation to break decreased. The SAXS patterns of the drawn/heat-set filaments indicated that comparable long period spacings exist in all cases and that a transition from a four-point pattern to a two-point bar-shaped pattern occurred when the precursor filament possessed some significant amount of as-spun crystallinity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2115–2131, 1998     

高分子量PET／60PHB热致性液晶共聚酯的结构与性能

研究了固相缩聚过程中PET/60PHB共聚酯结构性能的变化。随着反应的进行,分子量增大,分子量分布宽度指数变小;玻璃化温度略增,熔融温度增加幅度较大;热稳定性明显提高。预聚体中主要存在PET的低共熔物或部分同二质晶,固相缩聚反应使PET结晶消失,PHB结晶形成并完善。固相缩聚大大改善了共聚酯的可纺性,用[η]为0.95dL/g的共聚酯制得断裂强度达到高强范围(1GPa)的初生纤维。