尺寸排除色谱扩展因子的分子量依赖性与填料的孔洞表面结构

用聚苯乙烯标样作为探针,对多种SEC柱的分离和扩展效应作同时的校准,扩展因子随探针分子量的增加而增大,增大的幅度与SEC填料的孔洞表面结构有关。大孔径多孔硅球的比表面积较低,孔洞表面比较平滑,溶质分子在孔洞中运动时阻碍粳少,高分子量聚苯乙烯(M?10~6)的扩展因子只比低分子量(M?10~3)的大2—3倍。交联聚苯乙烯型凝胶的比表面积较大,表面比较粗糙,高分子量探针的扩展因子要比低分子量的高出几十倍,显示溶质分子在孔洞中运动所受阻碍较大。后一现象可用有机交联凝胶永久性孔洞的骨架表面具有自由链端得到说明。     

尺寸排除色谱扩展因子的保留体积依赖性

尺寸排除色谱扩展函数的方差即尺寸排除色谱柱中单分散高分子峰的扩展因子,以窄分布聚苯乙烯标样用分子量分离和扩展效应同时标准的方法作了测量。简单的理论分析导出了一个方程以表示扩展因子的保留体积依赖性,其中包括四个具有明确物理意义并可实验测量的参数。该方程与实验数据符合得相当好,并解释了扩展因子极值出现的条件。     

关于气相渗透法仪器常数对分子量依赖性的讨论

<正> 编委会: 见到高玉书等同志《关于气相渗透法仪器常数对分子量的依赖性》一文(高分子通讯,1980年第2期,112页)。鉴于文献报道的不一致,笔者曾进行同类工作。所用仪器是西德“KNAUER”V.P.O.仪;溶剂为苯(45℃)、氯仿(37℃)、丙酮(37℃),选用10种标样(M=144—2,10×10~4),其中五种单分散聚苯乙烯为进口系列标样,≤1.06,已知的数据曾用中国科学院化学研究所研制的F-1双室型沸点升高仪验证。现讨论如下。     

用单-检测器的尺寸排除色谱同时测量嵌段共聚物的组成和分子量

 本文建议了一种使用具有单一检测器的常规尺寸排除色谱仪同时测量嵌段共聚物纽成和分子量的方法。方法要求测定原试样的特性粘数和尺寸排除色谱图,而检测器只对嵌段共聚物两个组份之中的一个有响应。首先用均聚物标样定出尺寸排除色谱柱的响应常数和分子量分离校准曲线。原试样的实验谱图用解叠方法得到共聚物和均聚物的两个组成峰。借助响应常数和普适校准原则计算得到共聚物的组成和分子量。本法应用于苯乙烯-硅氧烷嵌段共聚物的分析得到满意结果。     

用单-检测器的尺寸排除色谱同时测量嵌段共聚物的组成和分子量

本文建议了一种使用具有单一检测器的常规尺寸排除色谱仪同时测量嵌段共聚物纽成和分子量的方法。方法要求测定原试样的特性粘数和尺寸排除色谱图,而检测器只对嵌段共聚物两个组份之中的一个有响应。首先用均聚物标样定出尺寸排除色谱柱的响应常数和分子量分离校准曲线。原试样的实验谱图用解叠方法得到共聚物和均聚物的两个组成峰。借助响应常数和普适校准原则计算得到共聚物的组成和分子量。本法应用于苯乙烯-硅氧烷嵌段共聚物的分析得到满意结果。     

炭分子筛的制备及表面结构

以大庆石油焦为原料，采用KOH活化法，考察了碱炭比、活化温度、活化时间对吸附性能的影响，确定最佳工艺条件，碱炭比4∶1、活化温度800 ℃、活化时间2 h。并制得比表面积大于3 000 m2/g的超级活性炭。通过热处理得到孔径均一(中孔率＞85%)，比表面积大于1 500 m2/g的炭分子筛；再用表面氧化方法，得到表面酸度适宜（150 ℃～240 ℃之间为弱酸，240 ℃～340 ℃为中强酸，340 ℃～450 ℃为强酸分布）的催化剂载体。炭分子筛与传统氧化铝比较具有酸度分布广泛等特点,因较好的酸强度分布，可以增强载体与金属离子之间的作用力，增加负载量。因此，经氧化后的炭分子筛更适于作催化剂载体。     

MOLECULAR STRUCTURES AND CRYSTAL PACKINGS OF STYRYLDIAZINES

Journal of Structural Chemistry - Crystal structures of three isomeric styryldiazine derivatives (E)-2-(3,4-dimetoxystryl)pyrazine, (E)-2-(3,4-dimetoxystryl)pyrimidine, and...     

大比表面积炭质吸附剂的表面及孔隙发展

以石油焦为原料研究了采用KOH活化法制备大比表面积炭质吸附剂时表面及孔隙的发展。实验发现虽然KOH加入量 ,水乙醇溶液中乙醇含量和提高热处理终温以及延长热处理时间都使比表面积增大 ,但是水乙醇加入总量的增加则导致比表面积下降。KOH加入量以 60～ 75%为宜 ,此时其利用率在 40 0m2 g以上。孔隙分布研究表明水乙醇加入总量 ,乙醇含量和热处理温度的提高都使 1～ 2nm微孔孔容及其在 1～ 2 0nm微孔孔容中所占比率增加。实验发现大比表面积炭质吸附剂的比表面积与碘值之间存在一定相关性。由于碘值不存在N2 吸附BET比表面积的过高估计现象 ,因而这给用碘值来更合理评价大比表面积炭质吸附剂的相对吸附能力提供了可能。     

SIMULTANEOUS CALIBRATION OF MOLECULAR WEIGHT SEPARATION AND COLUMN DISPERSION OF SEC WITH CHARACTERIZED POLYMER STANDARDS

With the aid of the theoretical relationship between the calibration relation of a SEC column for the monodisperse polymer species under ideal working condition and the effective relations between the molecular weight and the elution volume for characterized polymer samples, a computational procedure for simultaneous calibration of molecular weight separation and column dispersion is proposed. From the experimental chromatograms of narrow MWD polystyrene standards and broad MWD 1,2-polybutadiene fractions the spreading factors of a SEC column was deduced by the proposed method. The variation of the spreading factor with the elution volume is independent upon the polymer sample used.     

用多分散高聚物标样作凝胶色谱的分子量分离和扩展效应同时校准

根据凝胶色谱柱在理想工作条件下单分散高分子组分的校准关系与多分散试样的实效关系之间的理论联系,建议了一种简单的觅数方法,同时作凝胶色谱柱的分子量分离和扩展因子的校准。用本法从窄分布的聚苯乙烯和宽分布的1,2-聚丁二烯级分的实验谱图得到的所用凝胶色谱柱的扩展因子与淋出体积间的关系相互重合,与试样种类无关。     

壳聚糖浓溶液流变性质研究──分子量的依赖性

壳聚糖浓溶液流变性质研究──分子量的依赖性王伟，徐德时（中国科学院长春应用化学研究所高分子物理开放实验室长春１３００２２）关键词壳聚糖，浓溶液，粘度，零剪切粘度，分子量作者曾研究了一些外部条件对壳聚糖浓溶液流变学性质的影响，如浓度、温度、溶剂性质、外...     

煤粉在热分解过程中比表面积和孔隙结构的变化

用氮气等温吸附（７７Ｋ）方法测量了四种不同煤粉在热分解过程中的ＢＥＴ比表面积和孔隙结构。结果表明，不同煤种的比表面积在热分解过程中其变化有着相似的规律。在热分解温度低于５００℃时，煤粉所释放的挥发份主要来自煤粒外表面。当热分解温度高于５００℃后，煤粉释放出的挥发份主要来自煤粒内部深处。在８００℃时，由于煤的塑性，煤粒的部分孔减小和关闭，使其比表面积以及孔隙明显减少。在热分解温度高于８５０℃后，煤粉的比表面积随温度升高而急剧增大。     

SURFACE PROPERTIES OF SOME LOW MOLECULAR WEIGHT PROTEINS

Surface properties of four proteins having molecular weights less than 5,000 are reported at air/water and alumina/water interface at pH 7.0. Reversibility in the adsorption of these proteins at the alumina/water interface is tested. The adsorption on alumina/water interface has been found to be controlled by electrostatic interaction. Positive adsorption was obtained when protein and alumina surface had opposite charges and negative adsorption was obtained when both protein and surface had same charges. Of the four proteins reversibility in adsorption was observed with the one having the lowest molecular weight of 3100. The adsorption behavior apparently had no correlation with their surface hydrophobic!ty. Time dependent changes in air/water interfacial tension was observed for all the four proteins indicating time dependent loosening of compact protein structure and surface unfolding.     

壳聚糖浓溶液流变性质研究──分子量的依赖性

series of chitosan samlpes with 91% deacetylation but different molecular weight were obtained by varying the time of chitosan solution in acetic acid aqueous solution at 70℃.The viscosities and flow behavior of the concentrated solutions of chitosan were investigated in 10% (vol%) formic acid aqueous solution after the solutions were prepared for two days by using RPX-705 Rheopexy Analyzer.For each chitosan sample,at the concentration of 3.5 g/100ml,the log (ηr/η0)versus lgγη0,M curves superimpose each other within the same rheogramme. Then the relationship between log nr and lgM was studied under different shear rates.For the highest M sample, the experimental data deviate from the straight lines greatly. This was because the chitosan chain degradated in acid solution during dissolving. The molecular weights were measured in acid solution after two days of dissolving, they were right on their own straight lines. However,no obvious degradation was observed after two days in the same solution for the other lower M chitosan sam-ples. In addition, the plot of nr against M was not a straight line,probaly due to particular interaction of chitosan.     

鹤草酚的晶体结构和分子结构

鹤草酚晶体属三斜晶系,空间群为PI,晶胞参数为a=9.901(3),b=11.195(4),c=11.752(4)Å,α=80.74(3),α=75.66(3),γ=76.46(3)°,晶胞内分子数Z=2.用SyntexP3/R3型四圆衍射仪收集到2891个独立衍射强度.以直接法SHELXTL解出晶体结构.结构参数的修正采用了块对角矩阵最小二乘法,最后得偏离因子R=5.7%.晶胞中含有d-,l-两种对映体分子,它们彼此以I连系组成外消旋体.每分子中的两个六环分别同相邻的氧共面,其双面角为14.2°.两个六环通过碳(sp³)桥相连,并由于形成分子内氢键O-H…O(分别为2.705Å和2.745Å)而限制了自由转动.     

MOLECULAR WEIGHT DEPENDENCE OF THE MELTING BEHAVIOR OF POLY(ε-CAPROLACTONE)

Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found thatthe equilibrium melting points (T_m~0) of PCL samples depend on their molecular weights. Wide angle X-ray diffractionmeasurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were moreperfect than those of the low molecular weigh ones. These results demonstrate that the concentration of the end groups ofPCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (ΔH_u) wasdetermined to be 11.3 kJ/mol for PCL.     

辅助有机胺对介孔分子筛MCM-41合成及其性质的影响

采用阳离子表面活性剂十六烷基三甲基溴化铵为模板剂、硫酸铝为铝源、硅溶胶为硅源，分别使用中等链长的有机胺和正己烷作为辅助添加剂，用水热晶化法在碱性介质中合成了介孔分子筛MCM-41，通过XRD、N2吸附-脱附、SEM测试手段对得到的样品进行了对比表征分析。实验结果表明，除三乙胺外，向反应体系中加入适量的三正丙胺、三正丁基胺、三正辛胺和二异丁胺后，均能够使介孔 MCM-41的d100值和孔径增大，且具有较大的BET表面积（>1 000 m2/g）和孔容（>1 cm3/g）；加入正己烷后，也可以使得MCM-41孔径变大，但是和加入有机胺相比较，合成的样品具有较小的BET表面积（887.3 m2/g）和孔容（0.81 cm3/g）。