正电子湮没技术（PAT）在高分子材料中的应用（下）

正电子湮没技术（ＰＡＴ）在高分子材料中的应用（下）李桂芝，施良和，叶美玲（中国科学院化学研究所高分子物理开放实验室，北京，１０００８０）３．４高分子导体高分子导体有两种：（１）靠共轭分子链导电的高分子；（２）因掺入小分子而具有导电作用的高分子。现在已...     

吡咯的连续气相聚合反应Ⅱ聚吡咯与两种通用高分子的导电复合物

研究以通用高分子聚己内酰胺（ＰＡ－６）及聚对苯二甲酸乙二醇酯（ＰＥＴ）为基质材料，用连续气相聚合的方法，使聚吡咯与之复合，可得到聚吡咯／ＰＡ－６（ＰＰｙ／ＰＡ－６）及聚吡咯／聚对苯二甲酸乙二醇酯（ＰＰｙ／ＰＥＴ）导电复合纤维，电导率最高可达１０－１Ｓ／ｃｍ，力学性能有所下降。     

聚苯胺/苯乙烯-丁二烯-苯乙烯复合材料伸长过程中的导电性变化

以简化物理模型为基础，用实测电流与理论电流之比来研究导电橡胶伸长中电导率的变化，并建立相应测试方法．聚苯胺（ＰＡｎ）／苯乙烯 丁二烯 苯乙烯三嵌段共聚物的复合物用现场乳液聚合法制备．此复合物可熔融加工（ＭＰ）和溶液加工（ＳＰ）．ＳＳＰ样为ＳＰ样用间甲酚二次掺杂处理制得．对ＰＡｎ质量分数为１１０％的复合物进行电导率随伸长变化测试结果表明：ＭＰ样随伸长增加其电导率显著提高，在伸长率为４５０％时，其电导率是初始值（σ０）的１５６倍；ＳＰ样在伸长过程中电导率随伸长而增加，在伸长率为５００％时，其电导率是σ０的５２倍；而ＳＳＰ样在整个伸长过程中电导率变化较小，σ０＜σ＜２σ０．可从复合物的聚集态结构解释以上现象．ＳＳＰ样在导电组分的含量接近逾渗域值时电导率随伸长迅速下降．而当导电组分含量高于逾渗域值时电导率随伸长表现出小的变化并具规律性，此规律性可用σσ０＝１＋ｋａ＋ｂｋ２经验公式来表达（ａ，ｂ为与含量相关的常数）．此结果是由于ＳＳＰ样中导电组分在二次掺杂过程中分子链间存在弱相互作用而自行组成导电网络     

溶致性液晶高分子聚苯并■唑的合成和结构与性能研究

用对羟基苯甲酸甲酯（乙酯）为原料，合成了自缩聚型单体４ 羟基 ３ 胺基苯甲酸盐酸盐，在多聚磷酸介质中经溶液缩聚，制得高分子量的聚苯并唑（ＡＢＰＢＯ），在聚合后期观察到明显的溶致性液晶高分子所特有的搅拌乳光现象，经推膜及干喷湿纺技术得到了ＡＢＰ ＢＯ的薄膜和纤维．在甲基磺酸溶液中测定了ＡＢＰＢＯ的特性粘数，用Ｘ ｒａｙ平板照相及Ｘ ｒａｙ衍射、ＦＴＩＲ、ＴＧＡ、动态粘弹谱仪等测定和研究了ＡＢＰＢＯ薄膜和纤维的结构和性能，抗张强度为１５５ＧＰａ，抗张模量为９０ＧＰａ，在氮气中起始分解温度为６５７３℃．结果表明ＡＢＰＢＯ是一种高性能的半刚性的溶致性液晶高分子材料     

新型梳状聚合物电解质的离子导电性 Ⅱ.侧链是分子量为550的聚乙二醇单甲醚

以乙烯／马来酸酐共聚物为骨架，聚乙二醇单甲醚（Ｍ＝５５０）为侧链，通过两步酯化，合成了梳状乙烯／马来酸酐共聚物多缩乙二醇酯，用ＩＲ、元素分析、交流复阻抗谱等对产物及其ＬｉＣｌＯ４盐复合物进行了研究。结果表明：所合成的产物为非晶的梳状聚合物，并严格按反应方程式生成半酯。盐浓度与电导率的关系在所研究的浓度范围内存在两个峰，一峰在Ｏ／Ｌｉ＋＝８；另一峰在Ｏ／Ｌｉ＋＝３０。用侧链ＰＥＯ玻璃化转变温度作Ｔ０，以ｌｏｇσ对１／Ｔ－Ｔ０作图，电导率与温度关系呈典型的ＶＴＦ行为，该体系室温电导率最高可达２．５８×１０－５Ｓ／ｃｍ。     

用于燃料电池的Bi2O3基稀土固体电解质的研制

合成了（Ｂｉ２Ｏ３）０．７５（Ｙ２Ｏ３）０．２５和（Ｂｉ２Ｏ３）０．６５（Ｇｄ２Ｏ３）０．３５固体电解质陶瓷材料；测试了其晶体结构，ＸＰＳ谱及在５００￣８００℃的离子电导率随温度的变化；组装了镀有ＺｒＯ２－Ｙ２Ｏ３保护膜的Ｂｉ２Ｏ３基稀土固体电解质燃料电池。     

双■唑啉化合物偶联聚酯的研究Ⅰ．双■唑啉化合物的合成及其性能

双唑啉化合物偶联聚酯的研究Ⅰ．双唑啉化合物的合成及其性能＊陈玉君杨始方方土游飞越潘鉴元（中山大学高分子研究所广州５１０２７５）关键词双唑啉，扩链剂，聚酯聚酯，包括聚对苯二甲酸乙二酯（ＰＥＴ）和聚对苯二甲酸丁二酯（ＰＢＴ）等的高性能化，要求提高其...     

双离子AB交联型聚醚类固体电解质及其电流变液的性能

将α，ω－双甲基丙烯酰氧基封端的聚乙二醇与高氯酸锂络合，分别用溶液聚合和反相悬浮聚合合成了双离子ＡＢ交联型聚醚类高分子固体电解质（ＡＢＣＰＥ２）及其组成的无水电流变（ＥＲ）液．研究了ＡＢＣＰＥ２本身的离子导电性和含ＡＢＣＰＥ２的ＥＲ液的活性和电性能，并用扫描电镜表征了ＥＲ液中的粒子．获得了离子导电率高达８．０×１０－５Ｓ／ｃｍ（２５℃）的高分子固体电解质和活性较高的无水ＥＲ液．     

联氨在d—过渡金属配合物的MTP（о—NO2）TBP修饰石墨电…

研究了Ｎ２Ｈ４在间－四（邻－硝基苯基）四苯并卟啉铁（Ⅲ）、钴（Ⅱ）、锌（Ⅱ）和镍（Ⅱ）配合物［ＭＴＰ（о－ＮＯ２）ＴＢＰ，简称ＭＴＢＰ］修饰石墨电极上的催化电氧化反应，测得该系列金属四苯并卟啉的催化活性的顺序为Ｃｏ（Ⅱ）ＴＢＰ＞ＣｌＦｅ（Ⅲ）ＴＢＰ＞Ｎｉ（Ⅱ）ＴＢＰ＞Ｚｎ（Ⅱ）ＴＢＰ≈石墨，考察了Ｃｏ（Ⅱ）ＴＢＰ和ＣｌＦｅ（Ⅲ）ＴＢＰ催化联氨电氧化反应的动力学过程。结果表明，ＯＨ＾－和Ｎ２Ｈ４在Ｃ     

HDPE/CB导电复合材料电-热平衡态电学行为

研究了ＨＤＰＥ／ＣＢ导电复合材料在不同环境温度下电－热平衡态的电学行为,发现其电流密度－电场强度－电导率（Ｊ－Ｅ－σ）关系曲线经临界点参量约化后可有效地重叠。根据自发热临界电流密度、电场强度以及电导率与材料线性电导率之间的标度关系,揭示了复合材料在不同温度下的导电机理的一致性及宏观电学行为与微观导电网络结构的相互关联性。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.