干法纺聚酰亚胺纤维的结构与性能

以均苯四甲酸二酐、4,4'-二氨基二苯醚、3,3'-二氨基二苯醚为原料,以N,N-二甲基乙酰胺为溶剂,制得聚酰胺酸(PAA)纺丝液,采取干法纺丝制得PAA初生纤维,将PAA初生纤维经过300~380℃的热处理后,得到聚酰亚胺(PI)初生纤维,在400℃下对PI初生纤维进行热拉伸,最终得到PI纤维,研究了热处理温度、热拉伸倍数等对PI纤维的结构与性能的影响,比较了PI纤维与P84纤维和芳纶1313的性能。结果表明:在300~380℃的热处理温度下,随着温度升高,PI纤维的力学性能降低,最佳热处理温度为300℃时制得的PI初生纤维于400℃下进行热拉伸3.0倍,所得PI纤维的断裂强度为5.8 c N/dtex,初始模量为69.4c N/dtex,其力学性能优于P84纤维及芳纶1313;PI纤维在空气中失重5%和10%的温度分别为560,570℃,其起始分解温度高于P84纤维和芳纶1313,热性能更好;PI纤维经高温热拉伸,纤维内部分子链沿纤维轴向高度取向,表现出典型的取向诱导结晶效应。     

聚酰亚胺干法纺丝油剂的研制

研制了一种适用于干法纺聚酰亚胺纤维工艺的油剂,其原料廉价易得,使用效果好。性能测试表明:该油剂具有较好的抗静电性能、摩擦性能、润湿性能和热稳定性能,使用该油剂得到的成品纤维的性能指标要优于使用日本进口油剂的纤维。     

聚(氨酯-酰亚胺)的合成与应用研究进展 Ⅰ.聚(氨酯-酰亚胺)的合成技术

聚(氨酯-酰亚胺)是结合了聚氨酯和聚酰亚胺两种材料的优点而发展起来的一种新型聚合物材料。作者介绍了聚(氨酯-酰亚胺)的合成技术,总结了聚(氨酯-酰亚胺)的主要应用。     

聚(氨酯-酰亚胺)的辐射交联研究

介绍了辐射交联聚(氨酯-酰亚胺)的制备基础,并讨论了双键封端聚(氨酯-酰亚胺)的辐射交联以及辐射交联OVS-PUI泡沫的制备,还阐述了制备辐射交联聚(氨酯-酰亚胺)的其他方法。     

共聚聚酰亚胺纤维的制备及其性能研究

采用4,4’-二氨基二苯醚和1,6-己二胺(HDA)为二胺单体,与均苯四甲酸酐(PMDA)在二甲基乙酰胺(DMAc)中共聚得到聚酰胺酸(PAA)纺丝原液,通过干法纺丝工艺路线纺制PAA初生纤维,利用热酰亚胺化制备了共聚型聚酰亚胺(PI)纤维;通过红外光谱分析、动态力学分析、热重分析、X射线衍射等手段分析了PI纤维的力学性能及热性能。结果表明:红外光谱分析发现HDA的长亚甲基链引入到PI的链中;当HDA质量分数为20%时,PI纤维的断裂强度和模量分别为5.1 cN/dtex和76 cN/dtex;动态力学和热重分析发现,纤维的玻璃化转变温度为315～380℃,热稳定性在400℃以上;纤维经热处理后聚集态结构存在一定的有序性。     

干法纺丝制备聚碳硅烷纤维中残留溶剂含量的影响因素

研究了聚碳硅烷纤维纺丝线上残留溶剂含量的影响因素.结果表明:在纺丝线上距离喷丝孔约0.3 m之内,溶剂的挥发主要由对流和闪蒸过程控制,残留溶剂含量呈指数速率减小,且溶剂挥发量约为纺丝线上溶剂挥发总质量的80%～90%;纺丝原液浓度的增大、纺丝甬道温度的升高和纺程的增加有利于残留溶剂含量的降低,而纤维直径的增大则会提高残留溶剂含量.较佳的纺丝条件为:纺丝原液中聚碳硅烷的质量分数为65%～68%,纺程0.3～1.5 m,纺丝甬道温度为室温.     

聚酰亚胺干法纺丝参数对性能影响因素的研究

阐述并详细分析了聚酰亚胺干法纺丝过程中影响性能的各个因素,提出了确保纺丝顺利进行的原液粘度、原液存储条件及喷丝板形式。指出有利于纺丝正常进行的原液粘度约为4 500 P.s;原液应在高于室温及隔绝空气条件下储存;喷丝板直径>0.4 mm,长径比为1∶3以上。     

聚氨酯-酰亚胺泡沫的制备及性能表征

以3,3′,4,4′-二苯甲酮四酸二酐(BTDA)、多亚甲基多苯基异氰酸酯(PAPI)、聚醚多元醇4110(P-4110)为单体,采用PI预聚体法制备了聚氨酯-酰亚胺泡沫。采用化学滴定法研究了反应时间和反应温度对预聚体合成反应的影响,并通过红外光谱、电子万能试验机和热重对产物的结构、力学性能和热稳定性进行了表征。结果表明当预聚反应时间为60min,反应温度为70℃时,BTDA的转化率最佳;聚氨酯-酰亚胺泡沫的力学性能和热稳定性优于聚氨酯泡沫。     

熔融纺丝法制备聚醚砜纤维

将聚醚砜(PES)树脂进行熔融纺丝,制得PES纤维,对PES树脂的可纺性、PES纤维的拉伸条件、力学性能、热性能、阻燃性能进行了研究。结果表明：PES树脂在熔融温度380℃,卷绕速度300m/min的条件下,可纺性较好;PES纤维适合在较低温度和较低速度下拉伸,在30℃下低速拉伸,PES纤维可拉伸3倍,其强度可达2．30cN/dtex;PES纤维的热稳定较好,其初生纤维的起始分解温度为442．15℃;PES纤维的阻燃性能较好,极限氧指数为26．9%。     

溶胶共混纺丝制备水性中间相沥青基碳纤维

以针状焦(GNC)为原料,采用混酸一步氧化法制备水性中间相沥青(AMP)、混酸两步氧化法制备改进水性中间相沥青(FHAMP),分别与聚丙烯腈(PAN)共混溶解于二甲基亚砜(DMSO)形成溶胶,然后以稀硫酸为凝固剂,经溶胶纺丝、直接炭化制得水性中间相沥青基碳纤维;研究了AMP和FHAMP的溶解性、流变性、可纺性,以及相应的碳纤维的结构与性能。结果表明:相比AMP,FHAMP的粒径显著减小,氧化程度更高,能更好地溶解于DMSO;引入PAN,可有效提高AMP和FHAMP溶胶的可纺性;在纺丝温度50℃时,PAN质量分数为10%的AMP溶胶及PAN质量分数为8%的FHAMP溶胶均有较好的可纺性,连续收丝长度超过1 000 m,FHAMP溶胶的纺丝稳定性更好;相比由AMP得到的碳纤维,由FHAMP得到的碳纤维截面结构较为致密,纤维直径减小至23.09μm,杨氏模量和拉伸强度分别提高至33 GPa和0.29 GPa。     

Aromatic poly(1,4-phenylene-1,3,4-oxadiazole) fibers by dry jet-wet spinning

Fibers of poly(1,4-phenylene-1,3,4-oxadiazole) have been prepared by dry jet-wet spinning sulfuric acid solutions of the polymer. Polymer was prepared by polymerizing terephthalic acid and hydrazine dihydrochloride in 30% fuming sulfuric acid and directly spinning the resulting solution. Dry jet-wet spinning allows greater flexibility in conditions than does wet spinning in that spinneret temperature and coagulation bath temperature are independent of one another. Therefore, coagulation may be at temperatures well below those needed at the spinneret to maintain a flowing, extrudable solution. Another common advantage of dry jet-wet spinning is application of draw to the extruded fiber before coagulation, but in this system, drawing the fiber before coagulation was shown to be a disadvantage. Fiber properties were maximized by spinning with a spinneret temperature of 58–73°C into a coagulation bath at 3–4°C and with an air gap of 1/4 in. Water as a coagulation medium allowed operation at speeds up to 40 m/min, while with 50% sulfuric acid less than half that speed was reached. Application of draw ratios of 3/1 on the coagulated but still swollen fiber combined with high-temperature treatments at low draw ratios (1.05/l) gave maximum fiber properties–tenacity 6 g/denier, elongation 20–25%, and modulus 200–240 g/denier.     

Preparation of high-strength poly(vinyl alcohol) fibers by crosslinking wet spinning

High-strength poly(vinyl alcohol) (PVA) fiber was obtained by the crosslinking wet-spinning technique, which is an improved technique of the conventional non-crosslinked type wet-spinning of PVA. High tensile strength as well as high Young's modulus was achieved by introduction of the borate ion-aided crosslinks during the coagulation process. The drawability of the as-spun fiber greatly depends on the fiber thickness. The thinner the fiber, the higher the drawability. Since thinner fiber is subject to a very high shear rate on extrusion, the crosslinks introduced are believed to maintain topological memory of the oriented chains, which have a low density of entanglements. This allows drawing the fiber to a higher draw ratio. The strength and Young's modulus of the resultant highly drawn PVA fiber were achieved to be 22 g/d (2.3 GPa) and 430 g/d (50 GPa), respectively. The mechanism of the spinning was discussed and the spinning condition was carefully examined in order to optimize the final mechanical properties of the PVA fibers.     

The dry spinning of dibutyrylchitin fibers

Dibutyrylchitin was prepared by treatment of krill chitin with butyric anhydride in the presence of perchloric acid as a catalyst of reaction carried out at 25 to 30°C. Dibutyrylchitin is easily soluble in several organic solvents, such as acetone, alcohols, methylene chloride, and dimethylformamide. Samples of polymers with molecular weights high enough to form fibers were obtained, and dibutyrylchitin fibers were made by a simple method of dry spinning its 20 to 22% solutions in acetone. Select properties of dibutyrylchitin fibers were investigated. It was found that dibutyrylchitin fibers had tensile properties similar to or better than those of chitin and some chitin derivatives described in the literature. An attempt to convert dibutyrylchitin fibers to chitin fibers was made. It was found that chitin fibers with good tensile properties could be obtained by alkaline hydrolysis of dibutyrylchitin fibers without destroying the fiber structure. © 1995 John Wiley & Sons, Inc.     

Physical properties of poly(vinyl alcohol) fibers prepared from wet spinning/multi-step drawing

The preparation of poly(vinyl alcohol) (PVA) fibers by multi-step drawing was examined. The high draw ratio was attained when the drawing just before melting point was repeated. The influences of the draw ratio on mechanical and thermal properties of the fibers were studied. We utilized the wide angle x-ray diffraction (WAXD) as a medium to observe the erystallinity and the orientation of PVA fibers to study their effects on the physical properties of the fibers. With various coagulation bath concentration, both the tenacity and Young's modulus of fibers would increase as the draw ratios increased, the elongation would decrease at the same time. The tenacity was able to reach 41.0 cN/tex with the Young's modulus being 856.2 cN/tex; also, as the draw ratios increased, both crystallinity and orientation would increase. The crystallinity was about 67.2 % and the orientation was about 86.4%.     

Structure and properties development in poly(phenylene sulfide) fibers,part I: Effect of material and melt spinning process variables

The detailed research study of manufacturing PPS fibers using melt spinning and further enhancement of tensile properties by drawing and annealing experiments, a study lacking as of today in open scientific literature, was the focus of this research. This article discusses the effect of polymer molecular weight (MW) and melt spinning process variables on the structure and properties development in melt spun fibers manufactured from proprietary Fortron® linear PPS resins. Structure‐properties relationship was studied using several characterization tools like tensile testing, differential scanning calorimetry, polarized light optical microscopy, and wide‐angle x‐ray scattering. Changes in dynamic mechanical behavior of as‐spun fibers manufactured from resins of varying MW and different melt spinning take‐up speeds were also studied. The study showed that by a combination of higher MW of the polymer and spinning at higher take‐up speeds, tensile properties of as‐spun PPS fibers can be improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of a gel spinning process for high‐strength poly(ethylene oxide) fibers

This article describes a new gel‐spinning process for making high‐strength poly(ethylene oxide) (PEO) fibers. The PEO gel‐spinning process was enabled through an oligomer/polymer blend in place of conventional organic solvents, and the gelation and solvent‐like properties were investigated. A 92/8 wt% poly(ethylene glycol)/PEO gel exhibited a melting temperature around 45°C and was highly stretchable at room temperature. Some salient features of a gel‐spun PEO fiber with a draw ratio of 60 are tensile strength at break = 0.66 ± 0.04 GPa, Young's modulus = 4.3 ± 0.1 GPa, and a toughness corresponding to 117 MJ/m³. These numbers are significantly higher than those previously reported. Wide‐angle x‐ray diffraction of the high‐strength fibers showed good molecular orientation along the fiber direction. The results also demonstrate the potential of further improvement of mechanical properties. POLYM. ENG. SCI., 54:2839–2847, 2014. © 2014 Society of Plastics Engineers     

Mass transfer during dry spinning of fibers

The present investigation considered the transfer of mass during fiber formation with the dry spinning process, both experimentally and theoretically. Experimental data taken for the dry spinning of poly(methyl methacrylate)-benzene solutions were treated with the equation of continuity of species. Two solutions of this equation were applied to the data. The first, an analytical solution with a number of restraints and assumptions, yielded good, semiquantitative results. The other solution determined by numerical analysis with fewer restraints yielded calculated data which predicted exactly the behavior of average fiber solvent concentration.