自由基活性聚合及其最新进展

本文介绍了实现自由基活性聚合的动力学、热力学条件及可能的途径。在这些条件下自由基保持稳定的低浓度，增长链自由基与休眠种处于动力学平衡动态，可有效地控制聚合反应，使聚合反应具有聚合物分子量随反应时间、单体转化率成线性增长关系及所得聚合物分子量分布较窄的特征，并且在加入第二单体时可继续生成嵌段共聚物。     

单体极性对甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸钠无皂乳液共聚合的影响

研究了少量甲基丙烯酸钠（ＮａＭＡ）存在下单体极性对甲基丙烯酸甲酯（ＭＭＡ）／丙烯酸丁酯（ＢＡ）无皂乳液共聚合的影响．单体极性降低，使粒径减小、聚合速率提高、乳液表面张力和粘度降低、粒子表面电荷密度增大、聚合物分子量提高．ＭＭＡ／ＮａＭＡ无皂乳液聚合物只呈现一个玻璃化温度Ｔｇ，ＢＡ／ＮａＭＡ无皂乳液聚合物呈现两个Ｔｇ，ＭＭＡ／ＢＡ比为２∶１～１∶２的ＭＭＡ／ＢＡ／ＮａＭＡ无皂乳液聚合物呈现四个Ｔｇ，这是由于粒子外面相对富含ＯＳＯ－３和ＣＯＯ－基聚合物的亚层溶解了较多的水，使ＢＡ向粒子中心扩散，ＭＭＡ向外扩散，造成组成差异和相分离而引起的．     

聚硅烷亚芳弹性体的凝胶渗透色谱测量

用简易GPC柱研究了在未知合适的Mark-Houwink 系数的情况下,通过GPC和特性粘度的数据,同时计算出宽分布硅烷亚芳弹性体聚合物的分子量和这种类型聚合物的 Mark-Houwink 系数的方法。装柱填料为多孔硅胶球,理论塔板数 4200—5500块/米以上,塔板高度 0.7—0.9毫米。其分子量分布宽度指数在2左右。素炼后,分子量分布变窄,分子量下降。     

拟合粘度曲线法研究高聚物的长链支化

本文介绍了用计算机试误法拟合粘度曲线,讨论支化参数的方法,本法可以同时确定支化临界分子量和支化程度,在此基础上可以同时得到支化参数及平均分子量、分子量分布.以聚乙烯标准参考物:SRM 1475(线型)、1476(支化物)及镍催化顺式聚丁二烯为对象介绍了上述方法.     

丙烯腈的悬浮聚合

<正> 适用于普通溶液纺丝加工成形的聚丙烯腈(PAN)的分子量一般在5—8万范围内,近年来发展起来的冻胶纺丝方法使得(?)>4.0×10~5的超高分子量PAN也可以纺丝成形,成为制备高强高模PAN纤缎的有效方法之一。随着PAN材料应用领域的开拓,合成超高分子量的PAN是一个首要解决的问题。     

Influence of isotacticity and molecular weight on the properties of metallocenic isotactic polypropylene

The relationships between structure and properties have been established for isotactic polypropylene, iPP, homopolymers synthesized by metallocene catalyst systems. These iPPs exhibit different isotacticity degrees and molecular weights, and several thermal treatments during their processing have been applied. The most important factor affecting the structure and properties of these polymers is the isotacticity content. The thermal treatment, i.e., the rate of cooling from the melt, is also important and a clear molecular weight effect has been also found for the sample with lowest M_w. These factors affect the thermal properties, the degree of crystallinity and, therefore, the structural parameters and the viscoelastic behavior. A slow cooling from melt favors the formation of the γ phase instead of the α modification. The storage modulus, Young modulus and microhardness values increase as crystallinity does, independently of the origin of this increase: higher isotacticity or application of a slow crystallization from the melt.     

从聚丙烯流动曲线估算分子量分布

聚丙烯的控制降解技术由于能够带来很好的经济效益，国内外都在进行研究．其中分子量分布是一个重要数据，它对于聚丙烯的注塑、纺丝、薄膜等加工过程都有重要的影响．分子量分布一般用重均分子量Mw和数均分子量Mn之比D=Mw/Mn来表征，称为分子量分布指数．它可以     

The Degree of Disorder in Hardwood Kraft Pulps Studied by Means of LODP

The amount of disordered material in two types of hardwood kraft pulps was estimated by determining the weight loss at the point where the levelling-off degree of polymerisation (LODP) was reached. The pulps used were commercial pulps viz (1)one conventional birch kraft and (2)one mixed hardwood (MHW) kraft pulp that had been prehydrolysed prior to cooking. The results indicated that the hemicellulose xylan is closely associated with the cellulose in commercial birch pulps. It is therefore only possible to use LODP as a measure of the crystallite length of hardwood cellulose in highly purified pulps, such as prehydrolysed kraft pulp. A model explaining the LODP-results is proposed.     

An analytical solution of a newly proposed peak broadening equation and extension of polydispersities to higher molecular weight averages in size exclusion chromatography (SEC)

Summary Herein is reported an analytical solution to the peak broadening or peak dispersion/flattening equation based on the recently proposed Instrumental Spreading Shape Function and its application to correction for imperfect resolution (inadequate peak separation and/or excessive peak broadening) for higher molecular weight averages. The relationship of these higher MW averages with the familiar Weight Average and number average molecular weights is also discussed. Criteria for perfect resolution are specified and a true molecular weight calibration curve is accordingly defined.     

Thermal analysis study of the effect of molecular weight on constrained amorphous phase in poly(phenylene sulfide)

We report a thermal analysis study of the effect of molecular weight on the amorphous phase structure of poly(phenylene sulfide), PPS, crystallized at temperatures just above the glass transition temperature. Thermal properties of Fortron PPS, having viscosity average molecular weights of 30000 to 91000, were characterized using temperature modulated differential scanning calorimetry (MDSC). We find that while crystallinity varies little with molecular weight, the heat capacity increment at the glass transition decreases as molecular weight decreases. This leads to a smaller liquid-like amorphous phase, and a larger rigid amorphous fraction, in the lower molecular weight PPS. For all molecular weights, constrained fraction decreases as the scan rate decreases.This research is supported by the U. S. Army Research Office through contract DAAH04-96-1-0009. The authors thank Hoechst Celanese for providing different molecular weight Fortron samples and Dr. George Collins for providing sample information. The authors acknowledge the assistance of Elizabeth Oyebode and Leonardo Grimaldi with sample preparation and MDSC work.