环化聚丁二烯链结构的NMR研究

用Ｈ－ＨＣＯＳＹ谱证实环化聚丁二烯的多环序列末端存在三取代双键。解析Ｃ－ＮＭＲ谱表明残存的线形分子中仍然含有丁二烯的反１，４和１，２－单元。利用Ｈ－ＨＣＯＳＹ谱提供的信息对环化聚丁二烯的Ｈ－ＮＭＲ谱峰进行了归属，定义了参数Ｐ，Ｑ推导出环化度Ｘ和环化率Ｙ的计算公式，讨论了环化度Ｘ环化率Ｙ与参数Ｐ，Ｑ之间的关系，用上述方法处理了几个环化聚丁二烯的Ｈ－ＮＭＲ谱。     

1,3-戊二烯阳离子聚合过程中环化反应的研究

以ＡｌＣｌ３和（ＣＦ３ＳＯ３）３Ａｌ为引发剂，ＣＨ２Ｃｌ２为溶剂，在２０℃聚合了１，３ 戊二烯（ＰＤ）．对聚合物（ＰＰＤ）的结构分析表明，（ＣＦ３ＳＯ３）３Ａｌ生成的聚合物具有较高的环化度．聚合物的环化过程是通过两种机理，分子内链转移机理和阳离子引发机理，后者可以通过加入ＤｔＢＰ得到抑制．ＡｌＣｌ３引发的聚合反应中环化过程以前一种机理为主，而（ＣＦ３ＳＯ３）３Ａｌ则以后一种机理为主．通过阳离子引发的环化反应主要发生在ＰＰＤ１，２单元侧基双键上     

环化顺1，4－聚丁二烯浓溶液的流动行为

大多数线型高聚物浓溶液的流动行为呈现非牛顿性，线型顺１，４－聚丁二烯（ＬＢＲ）亦然，而环化顺１，４－聚丁烯（ＣＢＲ）的浓溶液在浓度达１７．８％时仍表现为牛顿流体。ＣＢＲ溶液的临界缠结浓度明显地高于ＬＢＲ，ＣＢＲ分子链间的缠结效应比ＬＢＲ弱得多，这是ＣＢＲ的分子链结构特征所致。     

环化顺1,4—聚丁二烯浓溶液的流动行为

大多数线型高聚物浓溶液的流动行为呈现非牛顿性，线型顺１，４－聚丁二烯亦然，而环化顺１，４－聚丁烯的浓溶液在浓度达１７．８％时仍表现为牛顿流体。ＣＢＲ溶液的临界缠结浓度明显地高于ＬＢＲ、ＣＢＲ分子链间的缠结效应比ＬＢＲ弱得多。这是ＣＢＲ的分子链结构特征所致。     

YBCO超导体中B位元素替代的簇模型的计算研究

电计算电荷分布讨论了元素的氧化态，指出ＹＢＣＯ中不存在Ｃｕ＾３＾＋，计算得到Ｂ位的Ｂａ，Ｓｒ等元素有负电荷，直接解释了Ｂａ３ｄ，Ｂａ４ｄ束缚能ＸＰＳ测定的“反常”结果。同时指出Ｂ位元素与其配位氧原子形成电子库，其容量由Ｂ位原子上负电荷大小标志，它与Ｏ２ｐ空穴相关，还讨论了Ｙ／ＢＣＯ中一些化学键的性质，它们可能与高温超电性相关联。     

混合微乳液的增敏作用研究：Cd（Ⅱ）—5—Br—PADAP的分光光度测定

研究了在Ｏ／Ｗ混合微乳液ＳＤＳ－ＯＰ／ｎＣ４Ｈ９ＯＨ／ｎ－Ｃ７Ｈ１６／Ｈ２Ｏ介质中，Ｃｄ（Ⅱ）－５－Ｂｒ－ＰＡＤＡＰ的显色反应。结果表明显色反应的灵敏度较单一的ＳＤＳ微乳液，单一的ＯＰ的微乳液，混合ＳＤＳ－ＯＰ胶束的介质中，具有更好的增敏作用和稳定性，Ｃｄ浓度在０－５μｇ／１００ｍＬ范围内符合比尔定律。方法用于废水和环境水样中微量Ｃｄ的测定，结果满意。     

健康人及尿石患者头发中微量元素的相关性研究

用ＩＣＰ－ＡＥＳ测定了尿石症高发现地区－广东省东莞市尿石症患者发中Ｃａ，Ｍｇ，Ａｌ，Ｃｄ，Ｃｏ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｕ，Ｍｏ，Ｚｎ，Ｂａ，Ｓｒ等十三种微量元素，并和健康人进行比较，经ｔ检验发现：Ｂａ，Ｃｄ，Ｍｏ，Ｓｒ，Ｍｎ，Ｚｎ和Ｍｇ／Ｃａ比值间存在显著性差异。     

ZnHZSM－5上脱氢环化芳构化过程的探讨

以正己烷、环己烷、甲基环戊烷、１－己烯和环己烯等分子探针反应，考察了单Ｂ酸型ＨＺＳＭ－５、Ｚｎ－Ｌ酸型ＺｎＮａＺＳＭ－５和双中心型ＺｎＨＺＳＭ－５（Ｂ酸和Ｚｎ－Ｌ酸）催化剂的性能，探讨了Ｂ酸中心和Ｚｎ－Ｌ酸中心在芳构化过程中的作用．实验结果表明，Ｂ酸中心有利于环化，Ｌ酸中心有利于脱氢芳构化．单具Ｂ酸或Ｚｎ－Ｌ酸中心催化剂上，直链烃分子的芳构化性能较差，当两种中心同时存在时，双功能互相促进，加快芳构化过程．文中还对Ｃ６分子脱氢环化芳构化过程进行了讨论     

阳离子型微乳液对镉（Ⅱ）—[4—（2—吡啶偶氮）—间苯二酚]的增敏作用

以十六烷基三甲基溴化铵／正戊醇／正庚烷／水微乳液为介质进行Ｃｄ（Ⅱ）－ＰＡＲ江度法测定，与以相同含量ＣＴＭＡＢ胶束体系比较，测定灵敏度增加，某些试验条件更为宽容，通过测定显色剂在水胶束相和水－微乳液中的分配系数ＫＤ，初步探讨了微乳液增敏作用机理。     

YBCO超导体中B位元素替代的簇模型计算研究

由计算电荷分布讨论了元素的氧化态，指出ＹＢＣＯ中不存在Ｃｕ￣（３＋），计算得到Ｂ位的Ｂａ，Ｓｒ等元素有负电荷，直接解释了Ｂａ３ｄ，Ｂａ４ｄ．束缚能ＸＰＳ测定的“反常”结果。同时指出Ｂ位元素与其配位氧原子形成电子库，其容量由Ｂ位原子上负电荷大小标志，它与Ｏ＿（２ｐ）空穴相关。还讨论了Ｙ／ＢＣＯ中一些化学键的性质，它们可能与高温超导电性相关联。     

聚甲基丙烯酸环氧丙酯的改性及其光敏性能的研究

<正> 以远紫外线作曝光光源的光刻技术具有较高的分辨率及设备简单等优点,已在国际上引起了广泛的重视。聚甲基丙烯酸环氧丙酯(PGMA)作为负性电子束抗蚀剂有较高灵敏度(4×10~(-7)库仑/平方厘米)和良好的分辨率(0.5微米)。但以远紫外线曝光时它成为光降解型且敏度低,然而在此体系中引进对光敏感的肉桂酰基团后,能使它从原     

Relationship between the retention characteristics on an alumina column and physico-chemical parameters of some environmental pollutants

The retention behavior of 16 environmental pollutants was studied on alumina and porous graphitized carbon (PGC) columns using n-hexane as eluent. The relationship between the logarithm of the capacity factors determined on the alumina column and the physico-chemical characteristics of the solutes was elucidated by principal component analysis (PCA) followed by two-dimensional nonlinear mapping. The 12 original variables can be reduced to four with only a 10% loss of information. The logarithm of the capacity factor formed a cluster with the hydrogen donor and acceptor properties of the solutes and their Taft's constant on the two-dimensional nonlinear map of PC loadings indicating that both steric and electronic parameters play a considerable role in the retention mechanism on alumina support. Alcohols, aromatics and chlorinated alkanes formed separate clusters on the two-dimensional nonlinear map of PC variables suggesting that their retention mechanism may be different on the alumina column. Solutes were not retained on the PGC surface proving that under normal-phase conditions the retention capacity of alumina can be higher than that of PGC.     

Determination of branching in polyethylene and poly(vinyl chloride) using pyrolysis gas chromatography

A series of polyethylenes (PE), reduced poly(vinyl chlorides), and precursor poly(vinyl chloride) (PVC) systems were studied by pyrolysis–gas chromatography (PGC) and by pyrolysis–hydrogenation–gas chromatography (PHGC). The branch content of these polymers has been interpreted on the basis of previously established literature information. Low-density PE (LDPE) was found to contain a significant number of ethyl branches. The pyrolysis results on an LAH-reduced PVC series gave significant insight on PVC microstructure. It was determined that the short-chain branches in PVC are mainly one carbon long. Some ethyl side chains and virtually no butyl branches were found in this experimental PVC series. The effect of chain branching on the pyrolysis of PVC is to increase fragmentation. The benzene/toluene ratio, along with relative amounts of benzene and naphthalene formed, may be used to indicate the relative degree of branching in this system. The application of PGC and PHGC have thus been shown to successfully extend analytical work on PE and PVC and to provide microstructural information.     

Formation of polyimide from benzophenonetetracarboxylic acid diester complexes with different diamines. 4. Gas-chromatographic study of thermal cyclization of complexes

Thermal cyclization of H complexes is characterized by one rate constant which significantly distinguishes it from thermal cyclization of polyamido acids. The degree of completion of thermal cyclization of the H complex and its rate are determined by diffusion processes related to the structure of the H complex and mobility (softening) of the system during thermal cyclization.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1006–1011, May, 1991.We would like to thank V. V. Shamanin for discussing the results.     

Chromatographic study of terpene derivatives on porous graphitic carbon stationary phase with beta-cyclodextrin as mobile phase modifier

The stoichiometric coefficients and apparent formation constants (Kf) of alpha-terpineol, thymol, geraniol and linalool complexes with beta-cyclodextrin (beta-CD) were determined using HPLC with a porous graphitic carbon (PGC) chromatographic support. Measurements were performed with four different methanol-water mobile phases. All the terpene derivatives under study form 1:1 guest-CD complexes. Graphs of Kf as a function of the mobile phase composition appeared different from those classically described for RP-C18 and suggest that the PGC stationary phase could play an active role in the complexation process. Solute-CD inclusion and solute-stationary phase interactions may be involved in this specific behavior.     

Chromatographic retention behaviour of n-alkylbenzenes and pentylbenzene structural isomers on porous graphitic carbon and octadecyl-bonded silica studied using molecular modelling and QSRR

The retention behaviour of a series of 15 n-alkylbenzenes and pentylbenzene structural isomers and benzene were investigated using porous graphitic carbon (PGC) and octadecyl-bonded silica (ODS) stationary phases. Shorter chain n-alkylbenzenes and benzene (n = 0–6), and all the pentylbenzene isomers were more strongly retained on ODS, although the selectivity was greater with PGC. For the pentylbenzene analytes the degree of branching in the alkyl chain at the position adjacent to the aromatic ring affects retention on PGC, with higher retention in less branched molecules. Molecular modelling studies have provided new insights into the geometry of aromatic π–π stacking interactions in retention on PGC. For alkylbenzenes with high branching at the position adjacent to the ring, the preferred geometry of association with the surface is with the branched chain directed away from the surface, a geometry not seen in the other alkylbenzenes. The most energetically favoured orientation for interaction between analytes and the PGC surface was found to be cofacial for toluene and ethylbenzene, whereas for other analytes this interaction was in a face-edge orientation. The alternative geometry of association observed with both toluene and ethylbenzene may explain the enhanced retention of these two analytes on PGC compared with their longer chain analogues. Quantitative structure–retention relationships revealed the importance of compactness in analyte structure during retention on PGC, with decreased compactness (associated with longer chain length and reduced chain branching) improving retention.     

呋喃甲基缩水甘油醚/二氧化碳共聚物的Diels-Alder反应

利用呋喃环侧基与单烯化合物所发生的Diels-Alder( DA)环加成反应,大幅度降低呋喃环在共聚物中的含量,从而制备出空气氛下稳定性较好的二氧化碳共聚物.研究发现DA反应的环加成程度越高,呋喃甲基缩水甘油醚/二氧化碳共聚物(PFGEC)的空气稳定性越好,当环加成程度超过70％时,可以得到稳定产物.DA反应条件对环加...     

The thermal transformation of an aromatic poly (amide), poly (ortho-oxyamide) and poly (benzoxazole)

The thermal behaviour of three aromatic polymers, poly(3,3-dioxy-4,4-diphenylmethane) (POA), poly(2,2-m-phenylene-5,5-dibenzoxazolemethane) (PBO) and a commercial poly-(phenyleneisophthalamide) (Phenylon) was studied by thermal analysis, i.e. DSC and TG. PBO was formed by the progressive thermocyclization of POA. By transforming POA into PBO the thermal stability was increased proportionally to the degree of cyclization, due to the stiffening of the polymer chain. PBO was found to be more thermally stable than Phenylon. The activation energies of the desorption of moisture, cyclization and thermal degradation of the polymers in both nitrogen and air were determined from non-isothermal TG data.     

Synthesis of a tetra(maleimide) as intermediate compound in a linear Diels–Alder polyaddition of bismaleimides with bis(2-pyrone)s

The tetrafunctional products 3 and 6 were synthesized via Diels-Alder reaction of bis(2-pyrone) with bismaleimides in mol ratio 1:7. The chemical structure of these products was determined by ¹H-NMR spectroscopy; the high degree of purity was confirmed by means of elemental analysis. The cyclization of the tetraimide 3 with 2 mol monopyrone 7 to the bicycle 8 was carried out. © 1995 John Wiley & Sons, Inc.     

Use of combined chromatographic methods including thin-layer chromatography for analysis of complex polymer systems. Determination of the polydispersity of block copolymers of styrene and methyl methacrylate by gel permeation, thin-layer and pyrolysis gas chromatography.

A combination of gel permeation chromatography (GPC), thin-layer chromatography (TLC) and pyrolysis gas chromatography (PGC) has been used for investigations of a polymethyl methacrylate-polystyrene-polymethyl methacrylate block copolymer. Continuous distribution of the polymer (40-mg sample) was attained according to the content of the styrene and methyl methacrylate units and of the block copolymer and according to the composition of the copolymer as functions of the hydrodynamic radius of the macromolecules. The polymer was subjected to a preliminary fractionation with an analytical gel chromatograph. The fractions were investigated by TLC, which permitted the separation of the block copolymer and the homopolymers. The composition of the fractions obtained by GPC and TLC was determined by PGC. As a result, it was possible to establish the composition of the block copolymer and its ratio to polymethyl methacrylate in each fraction. This investigation was based on a combination of highly effective fractionation by chromatographic methods with precise quantitative ratios obtained from Benoit's universal calibration graph and from determinations of the composition of the polymer fractions by PGC. The mechanism of the TLC of polymers, including the appearance of artefacts that distort the results of analysis, is also discussed.