聚硫醚醚酮(砜)芳香环状低聚物的合成与自由基开环聚合

在“拟高稀释”条件下,通过亲核缩聚反应高产率地合成了含硫醚键的芳香醚环状低聚物.应用核磁、GPC和激光质谱(MALDI-TOFMS)等手段对环状低聚物的结构进行了确认,并研究了环状低聚物的组分分布.聚硫醚醚酮环状低聚物在硫醚自由基的引发下进行快速熔融聚合,得到热稳定性很好的高分子量线性聚合物.     

短链支化对低分子量聚乙烯结晶及熔融行为的影响

研究了金属茂催化的低分子量支化聚乙烯和线性聚乙烯的结晶及熔融行为 ,发现支化聚乙烯的结构与线性聚乙烯相同为正交结构 ,但晶格略有膨胀 .支链的存在对熔融行为影响不大 ,两种聚乙烯的熔点均随结晶温度的升高而非线性增加 ,表现出低分子量样品的共同特征 .但支链的存在对结晶行为却有很大的影响 ,主要是由于支链的存在降低了晶体的结晶速率从而影响结晶过程 ,使得低分子量的支化聚乙烯的结晶行为与高分子量线性聚乙烯的结晶行为相似而与低分子量的线性聚乙烯不同 .动力学分析表明 ,低分子量的支化聚乙烯的结晶生长方式的转变温度比同等分子量的线性聚乙烯降低了约 2 0℃     

定量体积排除色谱测定高分子双水相系统的组成和分子量分布

利用定量体积排除色谱研究葡聚糖-聚乙二醇双水相系统相分离后上下两相中2种高分子组分的含量、分子量和分子量分布.由定量体积排除色谱法得到的两相组成(即系线端点)与用浊点滴定法得到的浊点曲线几乎完全重合,二者仅在靠近临界点的聚乙二醇富集相有一定偏差.同时,利用体积排除色谱测得两相中葡聚糖和聚乙二醇的分子量和分子量分布.结果表明,由系线端点得到的体系两相共存线与浊点曲线的偏差是由于相分离过程中,不同分子量的高分子组分在两相的非均匀分配造成的.聚乙二醇分子量分布较窄,发生相分离后,在两相的分子量和分子量分布相差不大.而葡聚糖分子量分布较宽,在相分离后两相中的分子量和分子量分布具有较大差异,即葡聚糖组分在葡聚糖富集相中的分子量显著高于其在聚乙二醇富集相中的分子量.随着葡聚糖-聚乙二醇体系初始浓度的增加,两相中葡聚糖的分子量差异变大.定量体积排除色谱可以准确得到高分子双水相系统的相平衡数据及两相中2组分的分子量和分子量分布信息,其结果不仅为深入理解葡聚糖-聚乙二醇-水三元溶液的相平衡提供基础,而且为双水相系统在萃取分离中的应用提供理论指导.     

非对称加外给电子体调控聚丙烯分子链结构

通过在反应器间加入不同的外给电子体,控制Ziegler-Natta催化剂催化丙烯聚合反应,并对聚丙烯立构规整度分布、超高分子量聚丙烯组分以及共聚单体分布情况进行了研究,结果表明,应用此方法可获得立构规整性分布受控、超高分子量组分含量高以及橡胶相增韧效果好的聚丙烯树脂.     

稀土络合催化聚合的顺-聚丁二烯的双峰分子量分布

用渗透压、粘度和尺寸排斥色谱方法研究了稀土络合催化聚合的顺丁橡胶在聚合过程中分子量和分子量分布的变化。络合催化剂中不同结构的烷基铝组分在聚合过程中起着不同的作用。对实验数据所作的分析指出,使用烷基铝和氢化烷基铝混合物组成的络合催化剂,聚合至高转化率时的聚丁二烯将出现双峰分布。烷基铝和氢化烷基铝的相反行为指示,聚合机理互有差异,而且不能简单地以链转移常数的不同来解释。     

EVA流动改进剂的分子量及分子量分布对大庆原油流变性的影响

研究了两类醋酸乙烯酯（ＶＡ）含量不同的乙烯－醋酸乙烯酯共聚物（ＥＶＡ）流动改进剂的分子量（Ｍｎ：１０３００～２５８０Ｎ和分子量分布（ｄ：１．４５～３．９）对大庆高蜡原油低温流动行为的影响。实验结果表明，在８０克原油中含有２００ＰＰｍ分子量或分子量分布不同的各种ＥＶＡ流动改进剂都不同程度改善了大庆原油的低温流变性。当改进剂分子量分布相近时，改进剂的改进效果存在某一最佳分子量；当改进剂分子量相近并处于最佳分子量范围内时，则窄分布改进剂的效果比宽分布的改进剂为佳。反之，以宽分布改进剂为宜。     

涤纶树脂废料在粉末涂料中的应用

粉末涂料是60年代发展起来的一种具有低公害、涂装工艺简单、原料利用率高、涂层坚固、有较好装饰性、使用安全等特点的新型材料。作者利用涤纶树脂(简称PET树脂)生产过程中所产生的废料来制备改性的PET树脂作为粉末涂料的原料。 PET废料为块状物或丝状物,分子量约为20000左右,熔点为535K左右。根据对涂料的要求,须将PET废料降解至分子量约5000。其工艺过程为:向反应釜中PET废料的熔融液加入丙二醇、丙三醇和醋酸锌(催化剂)等,不断搅拌下在533K反应两小时,冷却后即为浅     

PLLA/PDLA立构复合晶体的结晶、熔融行为

以水为引发剂合成了两种构型不同的左旋聚乳酸和右旋聚乳酸,运用DSC研究了分子量较低的PLLA/PDLA立构复合聚乳酸晶体的多重熔融行为,观察到随着180℃等温时间的增加,PLLA/PDLA共混物的立构复合晶体的熔点和熔融峰面积呈现震荡性变化行为,进一步的DSC和在线X射线研究结果显示,聚乳酸立构复合晶体多重熔融峰的震荡行为来自于晶体中就近生长的过量异构体链段的调整过程。     

聚对苯二甲酸乙二酯的熔融双峰

未拉伸聚对苯二甲酸乙二酯(PET)、单轴拉伸PET、双轴拉伸PET在不同条件下热处理,并进行了DSC热分析、X-射线衍射分析、红外分析。结果表明:熔融双峰现象起因于DSC等速升温过程中PET的部分熔融和重结晶;低温峰是等温热处理过程中形成的不完善微晶的熔融峰,高温峰是重结晶后较完善的微晶的熔融峰;在等速升温过程中,PET晶胞参数不变、晶格完善、晶粒增大,并且规则折迭链增加,但晶粒随温度增大的过程中出现低谷。     

成核剂对聚丙烯熔融行为的影响

成核剂对聚丙烯熔融行为的影响陈彦徐懋（中国科学院化学研究所高分子物理开放实验室北京１０００８０）关键词成核剂，聚丙烯，平衡熔点聚合物的熔融过程受分子量大小、分子量分布、分子链构型（等规度、分子结构单元的键接序列）、不同的结晶晶型、不同的热历史等...     

Random grafting statistics in graft distribution analysis

Graft distribution functions have been derived from random grafting statistics. Among the functions, the weight fraction of ungrafted backbone chains, the molecular weight distribution of the ungrafted backbone chains and the GPC apparent molecular weight distribution of the graft copolymer have been found to agree with experimental values determined for a graft copolymer system in which grafting was expected to be random. The other functions, which are not directly measurable, are therefore probably also correct. In analytical work the entire set of graft distribution functions may be computed for a graft copolymer system from the following experimental data: (1) molecular weight distribution of the starting backbone chains; (2) the chemical composition of the mixture of the graft copolymer and ungrafted backbone; (3) the graft side-chain molecular weight distribution, which may be assumed to be identical to that of the ungrafted homopolymer separable from the reaction mixture.     

基团转移聚合新引发剂——1-(N,N-二甲氨基)-1-三甲基硅氧基丁烯-1的合成与性质的研究

本文报道了一种新的基团转移聚合引发剂——1-(N,N-二甲氨基)-1-三甲基硅氧基丁烯-1,对由其引发的GTP、其引发活性、与催化剂及单体用量比对聚合速度、分子量分布的影响进行了研究,得到了分散性较小的实测分子量和理论分子量相近的PMMA。     

基团转移聚合新引发剂——1-(N,N-二甲氨基)-1-三甲基硅氧基丁烯-1的合成与性质的研究

 本文报道了一种新的基团转移聚合引发剂——1-(N,N-二甲氨基)-1-三甲基硅氧基丁烯-1,对由其引发的GTP、其引发活性、与催化剂及单体用量比对聚合速度、分子量分布的影响进行了研究,得到了分散性较小的实测分子量和理论分子量相近的PMMA。     

Calculation of molecular weight distributions for polymers undergoing random crosslinking and scission

A simple, practical calculation procedure has been developed for predicting the changes in molecular weight distribution of a polymer undergoing random crosslinking and/or degradation. Simulations of the random crosslinking and degradation of narrow and broad Poisson-type distributions have been made. The results agree with those calculated from Kimura's analytical solutions to Saito's general equations after a correction has been made for a mathematical error in Kimura's solution. This method can be applied to determining the probabilities of crosslinking and scission for any arbitrary molecular weight distribution expressed in tabular form. The importance of using narrow distribution samples to estimate crosslinking from changes in molecular weight distribution is graphically demonstrated.     

Gel-permeation chromatography of polydimethylsiloxanes

The molecular weight distributions of three polydimethylsiloxanes (PDMS) have been determined by gel-permeation chromatography (GPC), by gas–liquid chromatography (GLC), and by precipitation fractionation. The GPC data are greatly improved by correction for band spreading. For a high molecular weight polymer the corrected distribution agrees closely with the theoretical molecular weight distribution calculated from polymerization kinetics.     

Monitoring thermo-oxidative degradation of polypropylene by CRYSTAF and SEC-FTIR

Samples of a polypropylene homopolymer have been degraded and analysed with regard to chemical composition, molecular weight distribution and chemical composition distribution. FTIR shows the progress of degradation and a decrease in molecular weight can be observed from SEC. CRYSTAF shows that the chemical heterogeneity of the samples broadens with continuing degradation. SEC-FTIR reveals that the degraded species are mainly found in the low molecular end of the molecular weight distribution. The spatial heterogeneity of the degradation process has been proven by the analysis of abrased layers.     

极性单体阴离子型聚合反应产物的分子量分布

关于任意官能度多官能团引发剂瞬时引发并有单体链终止的阴离子型聚合反应体系,本工作通过非稳态动力学分析,求得了分子量分布函数和平均聚合度的一般表示式,讨论了单体的最大消耗量和聚合物的官能度分布问题,建立了从反应的初始条件和单体转化率计算产物的各种分子参数的方法。上述理论结果适用于甲基丙烯酸甲酯等极性单体在极性溶剂中的阴离子型聚合反应。数值计算的结果表明:当引发剂的官能度为2时,除了少数例外,所得聚合物的分子量分布一般具有双峰。     

Solution of Fujita's equation for equilibrium sedimentation by applying Tikhonov's regularizing functions

The Fujita equation relating molecular weight distribution to concentration of solution subjected to centrifugal forces in equilibrium proved to be an improperly posed problem in the Hadamard sense. Application of Tikhonov's regularizing functions leads to a good approximate solution of Fujita's equation. Such functions have been applied to a monomodal and a bimodal molecular weight distribution, and approximate results have been computed.     

铟在聚乙二醇-硫酸铵双水相体系中的分配

研究了稀散元素铟在有配合剂PAR（4－（2－吡啶偶氮）－间苯二酚）存在和无PAR存在的聚乙二醇PEG－（NH4）2SO4双水相体系中的分配行为。讨论了酸度、PEG分子量、PEG浓度及温度等因素对铟分配比的影响，发现酸度对分配比的影响最大，随着PEG分子量的增加及温度的上升分配比逐渐增大；随着PEG浓度的增加分配比逐渐减小。     

Selective degradation of nylon 6,6. I. Description of the degradation technique and preliminary morphological characterization

A technique for the selective degradation of amorphous regions in nylon 6,6 is reported. Samples of unoriented film and single-crystal mats have been subjected to selective degradation by refluxing in hydrazine. Weight loss, viscosity-average molecular weight, density, and small-angle x-ray scattering of these samples were monitored as a function of time of degradation. In addition, selected samples have been investigated by gel permeation chromatography (GPC) and transmission electron microscopy. Based on the results of these investigations it is concluded that the reported degradation technique is unique in that the debris is not monodisperse in molecular weight distribution. The Weight loss, density, small-angle x-ray scattering, and microscopy data demonstrate that the unordered or noncrystalline regions of the material are removed upon treatement. However, the relatively high molecular weight and broad molecular weight distribution of the debris indicate that regular folds at lamellar surfaces are intact after degradation treatment.