Thermal Degradation of Fractionated High and Low Molecular Weight Polyisobutylene

A series of thermal degradation studies on polyisobutylene has been carried out at relatively low degradation temperatures using samples of high purity, both fractionated and unfractionated, and of both high and low molecular weight. Rate curves of the high molecular weight polymer show maximums while those of the low molecular weight polymer show large initial rates which steadily decrease with increased volatilization. Rates of degradation of all samples become similar with increased volatilization. Rate studies indicate strong random initiation with the initial rate of volatilization showing very little dependence on molecular weight. The drop in molecular weight with increased degradation and the lack of broad maximums at moderate values of conversion shows the influence of an appreciable amount of transfer and a low kinetic chain length. The rate of degradation is found to be much faster than that of polypropylene or polyethylene probably because polyisobutylene disproportionates and forms radicals more easily. Equations are suggested for these degradation reactions.     

Change in the Molecular Weight Distribution of Gelatin by a High Pressure Slurry Jet

Abstract

Physical and photographic properties of gelatin depend on the molecular weight distribution of the gelatin, which it is important to control. We controlled the molecular weight distribution of gelatin by pressurizing the sample gelatin solution and jetting it at high velocity from a nozzle to a collision plate. II was found that this method teas effective in controlling the molecular weight distribution of gelatin and in preparing a gelatin which contains mainly ± and β components and few high and low molecular weight components.     

Preparative Chromatography and Analysis of Molecular Weight Fractions of Gelatin

Preparative scale gel filtration chromatography has been used to isolate different molecular weight fractions of gelatin for subsequent chemical analysis. The broad molecular weight distribution of gelatin was fractionated into four regions corresponding to high molecular weight, beta, alpha and low molecular weight material. Characterization of the isolated fractions included molecular weight distribution, amino acid composition, total active sulphur measured by cysleic acid analysis after oxidative hydrolysis and analysis of the pyridinoline crosslinks. A limed bovine ossein gelatin was characterized by these ttxhniques.     

不同相对分子质量聚乙二醇的热氧降解行为

3种不同相对分子质量的聚乙二醇(PEG)在80℃经过不同的老化时间,均发生了不同程度的热氧降解。采用红外光谱法、凝胶渗透色谱法和核磁共振波谱法研究了不同相对分子质量聚乙二醇热氧降解的行为及降解产物结构,定量表征了不同相对分子质量聚乙二醇的降解程度。结果表明,老化时间越长,3种PEG降解生成的小分子酯类化合物越多。其中PEG10000最稳定,不易发生热氧降解,PEG800降解程度最大。     

Degradation of Gelatin in Historical Photographs

Abstract

In order to study age related changes in photographic gelatin toe analysed black-and-white roll film before and after accelerated ageing and samples of naturally aged glass plate negatives. Two-dimensional gel electrophoresis (2D-PACE) was used to separate collagen chains In the gelatin by isoelectric point (pi) and molecular weight. The results shoiv that the x-chatns break down into smaller fragments on ageing. Amino acid analysis ivas performed to examine the oxidative deterioration of gelatin. It shows that the amount of lysine decreases with age.     

高分子量聚碳硅烷的合成及其表征

以常压合成的低分子量聚碳硅烷(PCS)为原料,分别在470℃高压及常压下反应一定时间,制备了高分子量PCS先驱体。研究了反应时间对：PCS分子量及其分布、软化点、Si—H键含量及可纺性的影响。研究表明,随着反应时间的延长,PCS低分子量部分逐渐减少,高分子量部分逐渐增加,分子量分布逐渐变宽,从而PCS分子量逐渐增大,软化点逐渐升高,Si—H键含量逐渐降低,可纺性逐渐变差。在相同的反应时间下,高压比常压对PCS分子量的增长更有利。在470℃高压或常压下反应时间2～3h时,可获得分子量高、可纺性良好的PCS先驱体。     

高分子量聚乙交酯的合成及表征

以辛酸亚锡为催化剂,十二醇为分子量调节剂,经乙交酯开环聚合合成了高相对分子量的聚乙交酯(PGA)。研究不同催化剂含量、调节剂含量和反应时间对合成反应的影响。通过改变催化剂含量,合成特性黏数达3.848 dL/g的PGA;固定催化剂含量,通过改变调节剂含量,得到特性黏数在2.278 dL/g～3.218 dL/g范围内可调的PGA。用红外光谱,核磁共振,X射线衍射(XRD),差示扫描量热(DSC)和热重分析(TGA)表征其结构和性能。结果表明,PGA是一种半结晶聚合物,结晶度达48.72%,其熔融温度在222℃～224℃之间,具有良好的热学性能。     

高分子量二元丙烯腈聚合物的合成及性能

设计合成了双功能共聚单体3-酰胺基-3-丁烯酸甲酯(MMPA),以二元共聚合代替传统的三元共聚合,采用水相悬浮聚合的方法制备超高分子量丙烯腈二元共聚物作为碳纤维前驱体。采用傅里叶红外变换光谱仪、差示扫描量热分析仪和热失重分析仪详细研究了单体配比对聚合物相对分子质量、结构及预氧化性能的影响,结果表明,共聚单体MMPA的加入使预氧化温度由240℃降低至213℃,且投料中随着MMPA含量的增加预氧化温度降低,预氧化程度加深,合成的共聚单体MMPA能够有效改善丙烯腈聚合物的预氧化性能,宽化放热峰,避免放热集中;水相悬浮制备得到的丙烯腈聚合物相对分子质量高达106.7×10~4,有利于提高碳纤维的力学性能。     

D-Amino Acids in Non-gelling Components of Gelatin

Abstract

As a possible cause of the non-gelling property of the sol fraction of gelatin, we considered that higher D-amino acid content should result in decreased formation of helices. The sol fractions ivere extracted from gelatin gels and hydrolyzed to amino acid mixtures. The rates of reaction with D-amino acid oxidase (D-AOX) were recorded for thehydrolyzates. For a comparison, residual gels were also treated similarly. The sol fractions always gave higher results than the residual gels for the three types of gelatin examined. The result also showed that the rates obtained from the sol fractions were in the order: limed ossein > limed hide > acid pigskin.

To examine the reliability of this procedure the D-form content for each amino acid in the sol from the limed hide gelatin was compared with that of the residual gel. The contents in the sol were higher than those in the residue for most of the amino acids which racemized. The results indicate that the increased racemization of amino acids on the extraction of gelatin from raw materials is a cause of the non-gelling property.     

A High Viscosity Gelatin

Abstract

The viscosity of gelatin solutions may he increased by the addition of polysaccharides such as carrageenan. The rheology of such a high viscosity mixture is described.     

高分子量聚丙烯酰胺的聚合

以双官能度氧化还原体系为主,配合其他引发剂组成复合引发体系,引发丙烯酰胺均聚.采用自由基聚合方法制备高分子量聚丙烯酰胺.考察引发剂浓度、单体浓度以及温度等因素对聚合反应的影响,最终确定最优化工艺条件.     

溶液自由基法高分子量聚丙烯腈的合成

采用以偶氮二异丁腈(AIBN)为引发剂,丙烯腈(AN)与丙烯酰胺(AM)在二甲亚砜(DMSO)溶剂中的自由基溶液共聚合,考察了单体浓度,单体配比,引发剂含量,反应温度和聚合时间等对共聚反应的影响。分别用称量法和乌氏黏度计测定了反应的转化率和聚合物的相对分子质量,用红外光谱对聚合物的结构进行了分析。研究结果表明,提高反应温度及引发剂含量,则转化率升高,分子量下降。单体浓度越高,分子量及转化率均可提高。这符合自由基聚合的一般规律。通过工艺优化,共聚物的转化率可达90%以上,黏均分子量约21万。     

Heat Capacities of Polyethylene IV. High Molecular Weight Linear Polyethylene

A high molecular weight linear polyethylene sample has been studied by adiabatic calorimetry from 10 to 380 K. Two broad temperature regions of unusual spontaneous temperature drift have been observed. The phenomena occurring around 240 K are similar to that observed in other polyethylene samples studied in this series, and are presumed to be caused by the relaxational processes in the amorphous phase. The weak exothermic behavior occurring around 160 K is presumed to be caused by the stabilization of the quenched sample.     

超高分子量聚乙烯磨粒磨损性能及机理的研究

本文利用ＭＬＳ－２３胶轮磨损试验机对超高分子量聚乙烯（ＵｌｔｒａＨｉｇｈＭｏｌｅｃｕｌａｒＷｅｉｇｈｔＰｏｌｙｅｔｈｙｌｅｎｅ）的磨粒磨损性能进行了研究。考察了磨损圈数（磨损时间）、载荷对其耐磨性的影响。通过扫描电子显微镜（Ｓ６００）对其磨损表面形貌的观察，作者指出：超高分子量聚乙烯磨粒磨损的主要机理是犁耕和亚表层脆性断裂。     

超高分子质量聚乙烯纤维研究进展

芳纶、碳纤维、超高分子质量聚乙烯纤维并称为世界三大高性能纤维.因其可作为尖端武器的重要基础材料以及在民用领域具有广阔的应用前景,因此得到了极大的关注.由于国内研发水平的差距和国外的技术垄断,我国高性能纤维的研发虽然取得了相关进展,但仍然需要大量的进口.加强对高性能纤维的研究,具有重要的战略意义.系统地介绍了超高分子质量聚乙烯纤维的优良力学性能、优异的耐化学介质性能、优异的耐冲击性能和防弹性能及相应的用途.回顾了超高分子质量聚乙烯纤维的产业发展历史,展望了它们的应用前景,并对其进一步的研究、开发提出了相关建议.     

超高分子量聚乙烯人工关节研究进展

人工关节是替代病变或损伤关节的植入性假体,除了应满足生物相容性要求外,必须具有足够的耐磨损性能、力学性能和抗氧化性能等。超高分子量聚乙烯因其自身优良的理化性能而被广泛应用于人工关节置换用材料。但随着超高分子量聚乙烯人工植入体使用时间的延长会导致其不同形式的失效,如磨损引起的骨质溶解,给骨科患者生活带来不便。综述了国内外提高超高分子量聚乙烯人工关节植入体综合性能而对材料进行改性处理的各种方法,包括辐照交联、热处理、加入抗氧剂等。最后总结了通过调控流动场诱导形成自增强结构,来改善人工关节植入体力学性能的最新进展,并展望了超高分子量聚乙烯人工关节高性能化的未来研究方向。     

高分子量热固性酚醛树脂的合成与性能

采用两步法,先合成热塑性酚醛树脂母体,再对其进行羟甲基化反应得到相对分子量800以上的热固性酚醛树脂。随树脂分子量增大,其凝胶时间缩短,在150℃可以实现<3 min内完全固化。同时随着原料Novolac树脂分子量增大,其改性后树脂溶液的黏度呈增长趋势,凝胶时间缩短;羟甲基化率(决定于甲醛用量)的增加可显著降低改性后树脂溶液的凝胶时间,但对溶液黏度的影响不明显;而反应时间在12 h后对于凝胶时间和溶液黏度影响很小。     

超高分子量聚乙烯摩擦学性能研究进展

综述了超高分子量聚乙烯(UHMWPE)在摩擦学领域的研究进展,着重评述了UHMWPE材料在人工关节方面的应用以及在减摩耐磨材料方面的研究,并提出了UHMWPE作为减摩耐磨材料在研究与应用方面几个亟待解决的问题.     

Weight and Weight Uniformity of Hard Gelatin Capsules Filled with Microcrystalline Cellulose and Silicified Microcrystalline Cellulose

ABSTRACT

The objective of this study was to investigate the weight and weight uniformity of hard gelatin capsules filled with microcrystalline cellulose (MCC) and silicified microcrystalline cellulose (SMCC) powdered formulations. A tamping-type encapsulation apparatus was used to fill the capsules. The four formulations that were tested included MCC alone, MCC blended with fumed silica, SMCC, and high-density SMCC (SMCC-HD). The mean capsule weight and the average variation in mean capsule weight of each formulation were determined. Both SMCC products exhibited better flow than the MCC alone, with SMCC-HD being the freest flowing of the powders investigated. Capsules filled with the SMCC products had higher fill weights than those containing the MCC powders. The SMCC-containing capsules exhibited the lowest variation in weight, although these findings were not significantly different from either of the MCC-containing capsules. Significantly higher weight variations were found in capsules filled with SMCC-HD. A relationship between Carr's compressibility index and capsule weight variation was found, with more compressible materials producing more uniformly filled capsules. No relationship could be established between powder flow and capsule weight uniformity. These findings suggest that powder flow may not be a critical parameter in ensuring capsule weight uniformity when the encapsulation equipment utilizes a tamping-type filling system.     

亚磷酸三苯酯扩链制备高分子量聚乳酸

以L-乳酸为原料,通过熔融缩聚法制备了分子量较低的聚L-乳酸(PLLA),采用亚磷酸三苯酯(TPPi)为扩链剂对其扩链增粘,研究了TPPi用量和反应时间对产物分子量的影响,得到了M-η为18.6万的高分子量PLLA,由13C-NMR和[α]25可证实其分子结构在扩链前后基本一致。DSC结果显示扩链后产物的熔点和结晶度与扩链前产物相近,TGA表明扩链后产物热稳定性增强。