高分子结构与性能关系原理-结构层次的意义

高分子结构是高分子性能的重要物质基础,对其结构进行合理的划分,有助于准确把握高分子物理知识体系的内在脉络。高分子结构层次的划分不仅要思考静态时特定质点在空间的堆砌特征,而且也要考虑结构出现运动或是变化的基本单元。按照质点尺度的不同,高聚物的结构可以分为单一高分子结构(链结构)、多个高分子结构(凝聚结构)和多种高分子结构(织态结构)三个主要层次。其中,化学因素所确定的链结构层次包括相对分子质量以及构造、构型等同分异构体形式;物理因素所确定的结构层次为高分子局部质点集合在空间的堆砌和排列;链段是容易被忽视、但又是最为重要的运动(变化)单元。     

夯实基础、理清脉络、充实内容,讲透高分子结构

高分子结构是高分子性能的基础,高分子结构知识也是学生学习高分子科学知识的起点与基础,高分子结构包含一、二、三、四级结构,一级结构具有更重要的基础性决定作用,是高分子结构的基础;二级结构的多样性是高分子特性的重要表现,它与一级结构一起共同决定高分子的高次结构与性能。在高分子物理的教学过程中,注重高分子结构的基础作用,用清晰的高分子结构知识脉络,辅以已经市场检验的具有优异性能的高分子产品的结构知识,讲解高分子结构对其性能的决定性作用,可以夯实学生对高分子结构基础性作用的认识,达到讲透高分子结构的目的。     

《高分子物理》课程中结合碳纳米管的案例教学研究

碳纳米管分子结构、性能与传统的液晶高分子材料具有非常多共性之处,是《高分子物理》课程教学中极具代表性的学科前沿教学案例。本文以碳纳米管为案例教学对象,从结构、物理和力学性能以及溶液相行为等方面,对碳纳米管与棒状刚性结构液晶高分子材料进行类比;在此基础上,将教学知识点延伸至借鉴芳纶纤维等液晶纺丝技术制备高取向度碳纳米管纤维的新方法,并对比分析碳纳米管纤维与有机纤维性能特点。通过合理设计课程主线、优选教学内容,培养学生的自主学习、学科交叉创新能力,激发学生学习的能动性,提高授课效果和教学质量。     

由橡胶材料看高分子物理知识点的综合运用

高分子物理是高等院校高分子材料与工程专业的一门重要的专业基础课。橡胶是一种具有优异性能的高分子材料,橡胶材料的结构与性能在很多方面综合了高分子物理的知识。在高分子物理课程的教学过程中,我们穿插了橡胶的一些具体实例,通过向学生介绍橡胶的结构、分子运动、性能以及交联,串联与橡胶材料相关的高分子物理知识点,以增强学生对这些知识点的感性认识,加强其对高分子物理基本概念和基础理论的掌握,取得了较好的教学效果。     

非高分子专业《高分子化学与物理》教学中的几点体会

高分子科学已渗透于各个领域与学科,形成了一个无法替代的交叉学科,因此,工科化学或材料相关专业纷纷开设高分子相关课程。《高分子化学与物理》作为哈尔滨工程大学材料化学专业的主干课之一,包括高分子化学和高分子物理两个侧面,其中高分子化学部分侧重高分子合成的基本理论知识,高分子物理部分则侧重于高分子的结构与性能。本文分析了高分子化学与物理的课程特点,总结了在课堂教学中采取的行之有效的措施和教学尝试,介绍了在课堂教学过程中,如何导入心理教育,提高学生的学习兴趣。     

高分子物理教学中“结晶”概念的讲解

高分子物理是高等院校高分子材料与工程专业的一门重要的专业基础课。"结晶"是高分子聚集态结构中重要的概念。巨大的分子量及长链状分子结构使高分子的结晶过程与小分子相比愈加复杂。在高分子物理课程的教学过程中,通过一定的逻辑架构向学生介绍结晶与有序、链柔性、玻璃化温度之间的关系并串联与结晶相关的一些概念(如结晶度、结晶温度、熔点以及结晶速率),使学生在初学阶段对高分子晶态结构建立起科学的认知体系。实践证明,通过这种教学方式,绝大多数同学都能较好地理解并掌握这部分教学内容。     

试论高聚物结构与性能关系的三个层次

高分子物理的基本任务之一就是探求高聚物的结构与性能,揭示结构与性能之间的内在联系及其基本规律。高聚物结构与性能的关系应该包含3个层次:通过分子运动联系的"分子结构与材料性能"关系、通过产品设计联系的"凝聚态结构与制品性能"关系和通过凝聚态物理知识联系的"电子态结构与材料功能"关系。传统教材上仅讲授"结构与性能关系",有相当的局限性,需要在研究生阶段补充有关"凝聚态结构与制品性能"关系和"电子态结构与材料功能"关系的课程。     

关于高分子物理的实体和立体教学

基于高校教育大众化趋势和工科及非物理专业学生的学习基础,本文在综合分析个体的认知规律和高分子物理的课程特点基础之上,提出了实体和立体化的高分子物理教学理念和大纲,即围绕高分子链统计、运动的特点,从结构和性能检测的感官认识出发来理解抽象的物理概念,在科研训练、实习实训、文献研讨等多层次多形式的学习中加深巩固对高分子物理知识的理解。     

凝炼“高分子物理”本科教学内容的核

要较为深刻地认识聚合物,学习并掌握"高分子物理"课程是十分必要的。那么,在打基础的本科阶段,"高分子物理"究竟要教些什么?对此,本文提出"高分子物理"课程本科教学内容有其核心部分,即结构单元形成的长链因各种相互作用所呈现的不同微观结构和形态、外场作用下聚合物微观结构和形态的变化、宏观响应行为及其之间的关系。作者以为,采用涵盖基本内容的统编经典教材,授予学生一个基本的核和不断地自我学习的有效方法,可由此臻于对"高分子物理"较为深入的理解、恰当运用乃至于发扬光大。     

面向工程教育的高分子物理

"高分子物理"教育是以物理、化学、数学等学科知识为基础,面向工程教育的高分子物理课程面临着与理科教育不同的培养对象和不同的培养目标。本文以华南理工大学"高分子材料与工程"专业发展历程和教学改革为例,结合"高分子物理"自身的特点和定位,提出了"高分子物理"要在工程教育的各专业课程之间起桥梁作用,建立理论与实践结合的高分子物理课程。就目前工程教育的"高分子物理"面临的多元化就业和职业化课程的矛盾、工程教育和行业对接的矛盾、教学方式方法课程深度和广度的矛盾、通选基础课程和专业基础课程缺乏有效结合的矛盾等进行了分析和讨论。     

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.     

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.     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.