PAN纤维共聚单体作用机理的光电离质谱研究

本工作以丙烯腈/衣康酸（IA）二元共聚原丝以及丙烯腈/IA/丙烯酸甲酯（MA）三元共聚原丝为研究对象，利用热重分析仪（TG）和热解-同步辐射真空紫外光电离质谱（Py-SVUV-PIMS）对其热稳定化过程进行研究。TG结果表明，氮气气氛下，二元共聚原丝（PAN/IA）和三元共聚原丝（PAN/IA/MA）分别呈现三阶段和两阶段的热分解过程，其中PAN/IA的第一和第二阶段均对应PAN线型分子链的断裂，但前者是由自由基环化反应放热引发的，后者则是由正常温度下的热分解所致，而单体MA的加入显著抑制了自由基环化反应，使得PAN原丝的热稳定化能够以单体IA诱导的离子型环化反应为主较平缓地进行，相应的热失重过程也由两阶段转变为了单阶段。Py-SVUV-MS的实验结果表明，两种共聚PAN原丝在程序升温过程中会生成包括含氮小分子、丙烯腈单体及低聚物、成环化合物在内的三类主要热解产物，对比各类产物的生成趋势和产量，推断单体MA通过降低PAN结构的规整度，使其无定形化，从而增加环化反应的引发点，促进PAN原丝向稳定的预氧丝转变，同时由典型热解产物——甲基丙烯腈的生成路径可知，MA本身并不参与PAN大分子的环化反应，属于中性共聚单体。空气气氛下，CO₂的产量差异也间接证明了MA单体能够有效提升PAN纤维的固碳能力，采用三元共聚方法制得的PAN纤维热稳定性能更佳。     

High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

Preparation of branched polyacrylonitrile through self‐condensing vinyl copolymerization

Branched polyacrylonitrile (PAN) was prepared through a self‐condensing vinyl copolymerization of acrylonitrile and 2‐(2‐bromopropionyloxy)ethyl acrylate (BPEA). The branched architecture of the product was confirmed by NMR spectra and the average degree of branching (DB ) was estimated. Through a comparison of the intrinsic viscosity of the product with that of its linear analogue, the contraction factor g′ was calculated. It was found that the viscosity of the branched PAN was obviously lower that that of linear PAN. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

KMnO4改性对聚丙烯腈原丝结构和性能的影响

用KMnO4对聚丙烯腈原丝进行化学改性处理,并通过傅立叶变换红外光谱仪、X射线衍射仪、示差扫描量热仪等测试手段研究了改性前后原丝的反应动力学,热性能,化学结构以及晶体结构的变化.结果表明,聚丙烯腈原丝经KMnO4改性处理后,环化反应所需的激活能降低,使原丝能在比较低的温度下开始环化反应,同时环化反应的放热量也有所增加;由于KMnO4的催化作用,使得改性处理后的PAN原丝形成了-C=C-共轭结构;经KMnO4改性后原丝的晶体尺寸有所减小,这样有利于预氧化阶段氧的扩散,促进预氧化阶段的结构转变.     

填充聚丙烯腈复合型浆粕的摩擦/密封复合材料

本文对采用特殊加工工艺使聚丙烯腈浆粕均匀地包覆在聚丙烯腈短切纤维的表面形成的复合型浆粕在摩擦、密封材料中的应用进行了初探。结果发现，复合型浆粕用于摩擦材料中，与树脂基体间的粘合性能优异，材料强度较高，不易剥落，具有较稳定的摩擦磨损性能；用于无石棉密封橡胶板，制得的密封板均匀、有弹性、强度高、耐热。聚丙烯腈复合型浆粕取代石棉或芳纶浆粕用于增强摩擦材料、密封材料等复合材料中，具有优异的综合使用性能和加工性能，具有较高的性价比。     

Fundamental parameters affecting electrospinning of PAN nanofibers as uniaxially aligned fibers

Electrospinning with a collector consisting of two pieces of electrically conductive substrates separated by a gap has been used to prepare uniaxially aligned PAN nanofibers. Solution of 15 wt % of PAN/DMF was used tentatively for electrospinning. The effects of width of the gap and applied voltage on degree of alignment were investigated using image‐processing technique by Fourier power spectrum method. The electrospinning conditions that gave the best alignment of nanofibers for 10–15 wt % solution concentrations were experimentally obtained. Bundles like multifilament yarns of uniaxially aligned nanofibers were prepared using a new simple method. After‐treatments of these bundles were carried out in boiling water under tension. A comparison was made between the crystallinity and mechanical behavior of posttreated and untreated bundles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4350–4357, 2006     

正交试验法在PAN原丝纺丝工艺中的应用

利用正交设计方法确定了PAN湿法纺丝过程中影响原丝性能最主要的因素。结果表明 :以计量泵转速、凝固浴温度、负拉伸以及蒸汽拉伸倍数作为考察对象 ,影响原丝性能的最显著因素是蒸汽拉伸倍数 ,其次是负拉伸。以负拉伸、第二拉伸、第三拉伸以及蒸汽拉伸的倍数作为考察对象 ,影响原丝性能最显著的是蒸汽拉伸倍数 ,负拉伸几乎没有影响。利用正交实验结果 ,适当调节蒸汽拉伸倍数 ,制得强度为 6.5～ 7.0cN/dtex ,线密度为 1.1～ 1.3dtex的原丝     

硫氰酸钠法明胶改性腈纶的研究

采用丙烯腈对明胶接枝改性 ,然后与聚丙烯腈共混纺丝的方法 ,制备了明胶改性腈纶 ,研究了改性比 (明胶 /丙烯腈 ,质量比 )和明胶含量对明胶改性腈纶机械性能、吸湿保水性能的影响。研究结果表明 ,当改性比为 0 .7～ 2 .0 ,明胶含量不超过 5 .0 %时 ,改性腈纶具有良好的机械性能 (断裂强度大于 3 .1c N/dtex) ,可以满足后纺加工的需要 ;改性腈纶纤维亲水性能良好 ,随着改性比的减小、明胶含量的增加 ,其回潮率和保水率都逐渐增大。     

悬浮法合成聚丙烯腈高吸水性树脂

以偶氮二异丁腈为引发剂，用悬浮聚合法合成了交联聚丙烯腈，然后对其进行水解，得到了高吸水性聚丙烯腈。交联剂用量和水解条件对树脂吸水倍数的影响很大。树脂吸去离子水倍数为420倍，平均粒径为250μm。     

Polyacrylonitrile/Nylon 6 Blends: Preparation and Characterization

Summary: Polyacrylonitrile (PAN) particles with micro‐size ranges (0.15–2 μm) were prepared by emulsion and dispersion polymerizationa and in supercritical carbon dioxide media. The PAN particles were blended with Nylon 6 (PA6) at 220 °C by using a miniature mixer; it was found that melt‐mixing was possible for PAN‐rich compositions as high as 70 wt.‐%. Blends were characterized by scanning electron microscopy, IR, viscosity measurements, differential scanning calorimetry, and dynamic mechanical thermal analysis (DMTA). The size and shape of original PAN particles were retained in PAN/PA6 blends. The useful range to blend PAN particles size was less than 1 μm in terms of shape retention of the PAN particles in blends. Blends with 40 wt.‐% PAN content were found to be melt‐processable. The elastic modulus was higher for PAN/PA6 blends than pure PA6.

SEM photograph of PAN‐SC/PA6 blend with a 40/60 weight ratio.