聚合物薄膜玻璃化转变及其分子松弛行为的研究进展

随着纳米技术的发展,受限聚合物的玻璃化转变以及分子松弛行为受到了高分子物理学家的关注.由于纳米尺度效应,高分子薄膜的玻璃化转变以及分子松弛行为偏离于本体,呈现出尺寸依赖性.研究聚合物薄膜的玻璃化转变及其相关分子松弛行为对聚合物纳米材料的结构设计,进一步理解聚合物玻璃化转变的物理本质具有重要意义.本文总结了近20年来聚合物薄膜玻璃化转变行为的研究成果,介绍了薄膜分子松弛行为偏离本体的主要物理机制、聚合物薄膜分子运动能力的深度分布特征以及薄膜分子松弛行为的相关理论模型,并对该领域研究进行了展望.     

低分子量聚合物电解质的合成与性能

研究了低分子量梳状聚合物电解质的合成方法及结构，性能。首先合成了不同分子量的甲基丙烯酸聚乙二醇单甲醚酯，并进一步合成了分子量一万左右的梳状聚合物电解质，结果表明：反应严格按照反应方程进行，精制产物是非晶的梳状聚合物，本聚合物体系均存在两个玻璃化转变温度，一个在100℃左右，归属为梳状聚合物主链的玻璃化转变，另一个在－20摄氏度以下，归属于侧链玻璃化转变，在室温下侧链可以运动，有利于电活性物质的迁移和扩散，并用超微电极研究了该电解质的行为。     

非晶物理框架下开展聚合物玻璃化转变教学的思考与探索

玻璃化转变是高分子物理教学中的重要内容.一些高分子物理教科书将聚合物玻璃化转变简单描述为玻璃到高弹态的力学转变,可能局限了学生对玻璃化转变重要科学问题认识的深度、广度和想象空间,甚至造成一些学生认为只有聚合物才存在玻璃化转变.笔者注意到了这一问题,考虑将聚合物玻璃化转变放在非晶物理框架下进行讲授;强调玻璃化转变是非晶物...     

对聚合物玻璃化转变的几点新认识

基于聚合物玻璃化转变的定义,探讨了聚合物宏观单晶体和聚合物单链单晶的玻璃化转变问题,指出玻璃化转变的温度依赖性不服从普适的Arrhenius方程,可以把WLF方程看作是聚合物玻璃化转变的特有温度依赖关系。介绍了二维状态下聚合物可能的玻璃化转变。     

物理老化对聚甲基丙烯酸甲酯薄膜的玻璃化转变、银纹化特征及力学性能的影响

物理老化对聚甲基丙烯酸甲酯薄膜的玻璃化转变、银纹化特征及力学性能的影响沈静姝，叶卫君（中国科学院化学研究所北京１０００８０）关键词聚甲基丙烯酸甲酯，玻璃化转变，银纹化，物理老化银纹化是聚合物中特有的现象，在应力作用下，许多非晶聚合物、一些半结晶性聚合...     

红外光谱及二维相关光谱在讲解聚合物"玻璃化转变"概念的应用

玻璃化转变是聚合物的一种普遍现象,也是高分子物理教学过程中的一个重点内容.对玻璃化转变的本质进行深入透彻地讲解,有利于学生加深对高分子结构、高分子材料的性能和高分子链运动的统计学三个紧密相连部分的融会理解.针对目前教学过程中主要基于差示扫描量热法进行非晶态聚合物玻璃化转变温度概念讲解的不足,本论文交流了在教学过程中采用...     

含氟聚酰胺酸热亚胺化过程的扭辫分析

用扭辫分析(TBA)研究了含氟聚酰胺酸的热亚胺化过程,用聚合物链段运动有利于小分子生成物的扩散,因而对缩合反应发生影响的观点,解释了剧烈的亚胺化反应总是在玻璃化温度以上发生;还观察到亚胺化反应使聚合物链刚性增加,玻璃化温度逐渐由120℃升高到310℃。因而提出了分段熟化的合理生产工艺。 对TBA谱中的溶剂蒸发,玻璃化转变、玻璃态中的次级转变,予聚物的亚胺化反应等多重转变进行了分析,解释了溶剂和水对亚胺化过程的影响。     

两端系留纳米粒子聚合物的分子动力学模拟

两端系留纳米粒子聚合物是研究末端对聚合物链弛豫行为影响的优选分子模型.本文构建了两端系留纳米粒子聚合物模型,运用粗粒化分子动力学方法研究了两端系留纳米粒子聚合物的特征温度和弛豫行为,探讨了纳米粒子半径和聚合物链长对玻璃化转变温度、结晶温度和介电性能的影响.研究表明,聚合物两端纳米粒子的存在可延缓聚合物链的弛豫并促进结晶,使两端系留纳米粒子聚合物的玻璃化转变温度和结晶温度均增加.研究结果与相关的实验报道吻合,可加深对两端系留纳米粒子聚合物结构和性能的理解.     

含活性侧基马来酰亚胺/苯乙烯共聚物的合成与性能研究

合成了含活性侧基的苯乙烯/N-对羟苯基马来酰亚胺共聚物(SHMI),使某些具有特定功能的有机小分子接枝到聚合物主链上.用FTIR,NMR及GPC研究了其化学结构,并用DSC和TGA研究了其热转变和热降解性能.结果表明,SHMI是交替共聚物,其玻璃化转变温度(Tg)高达526K,于661K开始降解,降解动力学遵循Arrhenius方程,有良好的溶解成膜性能.     

反相色谱法表征聚苯乙烯磺酸的转变现象

1969年,Smidsrφd和Guillet就应用反相色谱法(IGC)测量聚合物的玻璃化转变温度。十几年来许多科学工作者研究了IGC测量聚合物玻璃化转变现象的各种影响因素,但应用IGC研究离聚物还属罕见。离聚物分子上带有离子基闭,分子间的相互作用比较复杂,我们曾用热激放电电流法(TSDC)等测量了本实验所用的聚苯乙烯磺酸(PSSA)样品的玻璃化转变现象。应用IGC法,不仅能够比较精密地测出不同磺化度     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

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.     

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.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.