高分子科学第一课教学点滴

高分子科学是蓬勃发展的高分子材料工业的理论基础,对其深刻理解、灵活运用是进行高分子工业实践的前提条件,然而当前高分子专业学生中存在对高分子科学不感兴趣或者"偏见"现象,影响了高分子科学的教学效果和后续实践,因此,开展高分子科学教学研究,对培养具备深厚高分子科学理论与应用兴趣的专门人才具有重要意义。作者阐述了为激发学生长久、自主学习兴趣进行的高分子科学第一课教学改进体会,即强调高分子材料的价值宣讲、突出高分子知识的应用特性和演义高分子科学丰富历史,结合知识性、故事性和实际性多维度教学,引导同学们走近高分子、走进高分子、爱上高分子。     

功能高分子

本文简述了功能高分子的发展,合成途径以及所谓的高分子效应。对该领域内所涉及的各类功能高分子的性质、合成、应用及发展前景等作了概要介绍。内容包括具有分离功能的高分子、高分子试剂、高分子催化剂、光活性高分子、磁性高分子、能量转换及储能材料、生物医用材料、高分子药物、高分子液晶及一些其他功能高分子材料。     

我国高分子化学的研究现状和基金的管理导向

高分子化学是高分子科学的三大分支领域(高分子化学、高分子物理、高分子工程)之一,它的学科领域覆盖了聚合反应研究、高分子合成及高分子改性.由于高分子化学肩负着为高分子学科提供新高分子化合物的首要任务,因此是高分子科学的基础.我国从事高分子化学研究的科研人员,约占全部从事高分子研究人员的65%,因引高分子化学研究也是我国高分子科学研究队伍的主流(见表1).我国的高分子化学研究涉及新聚合反应及新聚合方法研究、聚合反应动力学研究、功能高分子的分子设计和     

从诺贝尔奖看高分子百年*

从高分子学科确立到现在已经经历了整整一个世纪。围绕高分子领域的历次诺贝尔奖,重点回顾了“高分子”概念的确立、高分子合成化学、高分子理论、功能高分子等领域的里程碑事件,分析了高分子学科的未来发展趋势。     

高分子共混物中氢键的作用Ⅱ.氢键对高分子共混物性能的影响以及引入方法

高分子共混物中氢键的存在能促进共混组分具有更好的可混和性.因此,研究高分子共混物中的氢键对高分子的共混改性具有重要的理论和实用价值.本文是<高分子共混物中氢键的Ⅰ.氢键的特征描述以及影响因素>的下篇,将继续介绍高分子共混物中氢键的作用,主要包括氢键对高分子共混物性能的影响以及主要的引入氢键的方法.特别地,本文通过将高分子共混物分为合成高分子与合成高分子共混物,合成高分子与天然高分子共混物以及合成高分子与其它物质共混物,总结了氢键存在对共混物性能的影响.     

高分子科学的近期发展趋势与若干前沿

分别按高分子合成化学、高分子科学与生命科学的交叉研究、光电磁活性功能高分子、超分子组装与高级有序结构构筑、高分子物理与高分子物理化学、高分子加工新原理、新方法等,对高分子科学近期主要发展趋势和若干前沿方向做一综述.     

高分子物理课程中影响高分子柔顺性因素的教学实践

针对高分子物理课程中影响高分子链柔顺性的高分子链结构方面因素的讲授,结合不同高分子材料的用途,形象地说明了高分子链柔顺性对高分子材料性能的影响,使学生真切地了解到高分子链的柔顺性决定了高分子材料的不同用途,这种理论联系实际的教学方法避免了抽象的死记硬背,可以加深学生的感性认识,取得了良好的教学效果。     

从高分子化学与衣食住行到高科技发展

本文围绕国际化学年的主题,介绍高分子科学与人类衣食住行、国民经济各个方面的密切关系,结合高分子发展历程、高分子产业现状和高分子学科前沿与发展趋势,概述了高分子科学与技术的基本情况。     

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。     

电光高分子研究进展

电光高分子是二阶非线性光学材料的重要组成部分,目前的研究重点主要在于合成具有高二阶非线性光学效应和取向稳定性以及低光学损耗的电光高分子,以满足高性能光学器件的制作要求。最近,电光高分子的设计与合成已经取得了很大的进展,例如结合"位分离"原理,利用高分子良好的加工性,获得了一些具有较好综合性能的高分子,可以较为有效地将小分子发色团的高β值转换为高分子大的宏观电光效应。本文综述了近几年来电光高分子的研究进展,主要包括线型电光高分子、树枝状电光高分子和超支化高分子。     

阴离子表面活性剂聚二硫二丙烷磺酸钠的合成

利用硫化钠与硫磺反应制备二硫化钠,然后将二硫化钠与1,3-丙磺酸内酯反应,合成了一种可作为电镀添加剂的阴离子表面活性剂——聚二硫二丙烷磺酸钠(SPS)。采用核磁共振氢谱对合成产物进行结构表征,确认了产物结构及产率。通过正交试验研究了产物产率与反应物配比、反应温度、溶剂加入量等因素之间的关系,找出了最优合成条件:第一步合成二硫化钠的反应中,硫化钠/硫磺物质的量比为1∶1.3,温度55℃,加水量18 mL;第二步合成SPS的反应中,1,3-丙磺酸内酯/硫化钠物质的量比为1.7∶1,温度40℃,溶剂量75 mL,产物的最高产率可达到95.8%。     

(±)-耳壳藻内酯的全合成研究(Ⅱ)

以2,6,6-三甲基环己-2-烯-1,4-二酮为原料, 经选择性羰基保护、Wittig反应、脱保护基、 腈基水解和还原等5步反应合成了目标化合物, 总产率可达6.0%.     

2,6-二羟基甲苯的合成

2;6-二羟基甲苯的合成;二羟基甲苯;间苯二酚;二氯乙烷;烷基化;甲酰化;黄鸣龙反应     

杀菌剂肟菌酯的合成工艺

以邻甲基苯乙酸为起始原料,经过氧化、酯化、肟化及溴代反应,最后与间三氟甲基苯乙酮肟缩合制备了杀菌剂肟菌酯.每步的反应产物均通过1 H NMR确认,总收率为17%.本工艺路线采用廉价的起始原料降低了生产成本,反应条件温和且易于控制,各步收率较高,有进一步研究与应用价值.     

Synthesis of 1-deoxy-D-galactohomonojirimycin via enantiomerically pure allenylstannanes

1-Deoxy-D-galactohomonojirimycin was synthesized in seven steps from optically pure allenylstannane 4 and L-lactate-derived aldehyde 5 in 48% overall yield. The key step was the Lewis acid catalyzed reaction of 4 and 5 to give the syn-amino alcohol in excellent yield and very high diastereoselectivity.     

An olefin cross-metathesis approach to vinylphosphonate-linked nucleic acids

[reaction: see text]. The synthesis of vinylphosphonate-linked nucleotide dimers has been achieved using an olefin cross-metathesis (CM) reaction as a key step. The 1,3-dimesityl-4,5-dihydroimidazol-2-ylidine-containing catalyst 5 (Grubbs' second-generation catalyst) was found to be the superior catalyst for this transformation. Both metathesis partners were readily available using known methodology, and the vinylphosphonate-linked dimer was produced with high levels of (E)-selectivity (>20:1) in 58% yield (70% based on recovered starting material).     

Catalytic enantioselective Reissert-type reaction: development and application to the synthesis of a potent NMDA receptor antagonist (-)-L-689,560 using a solid-supported catalyst.

Full details of the first catalytic enantioselective Reissert-type reaction are described. Utilizing the Lewis acid-Lewis base bifunctional catalyst 5 or 6 (9 mol %), the Reissert products were obtained in 57 to 99% yield with 54 to 96% ee. Electron-rich quinolines produced better yields and enantioselectivities than electron-deficient substrates. Kinetic studies indicated that the reaction should proceed via the rate-determining acyl quinolinium formation, followed by the attack of a cyanide. The catalyst does not facilitate the first rate-determining step; however, it strongly facilitates the second cyanation step. The reaction was successfully applied to an efficient catalytic asymmetric synthesis of a potent NMDA receptor antagonist (-)-L-689,560. A key step is the one-pot process using the Reissert-type reaction from quinoline 1f, followed by stereoselective reduction of the resulting enamine 2f. This step gave the key intermediate 20 in 91% yield with 93% ee, using 1 mol % of 6. The enantiomerically pure target compound was obtained through 10 operations (including recrystallization) in total yield of 47%. Furthermore, 6 was immobilized to JandaJEL, and the resulting solid-supported catalyst 11 afforded 20 in a comparable yield to the homogeneous 6, but with slightly lower enantioselectivity.     

微波辐射下5-取代-2-硫代海因衍生物的合成

微波辐射下, 由硫氰酸铵与α-氨基酸通过两步反应合成了11种5-取代-2-硫代海因衍生物, 并用¹H NMR, IR和元素分析确证了中间产物和终产物的结构. 对比常规加热方法, 微波辐射具有反应时间短(4 min), 每步反应产率高(85%～93%)的优点. 同时对合成化合物2h的反应历程进行了讨论.     

Non‐isocyanate synthesis and application of telechelic polyurethanes via polycondensation of diurethanes obtained from ethylene carbonate and diamines

Aliphatic polyurethanes could be obtained in high yield via a non‐isocyanate method based on the self‐polycondensation of dihydroxyurethanes obtained by the reaction of diamines and ethylene carbonate. The polycondensation under a N₂ atmosphere yielded [6,2]polyurethane with a M_n value of 5300 in 87% yield. Two‐step polycondensation, consisting of the polycondensation under a N₂ atmosphere followed by that under reduced pressure, was effective to improve the yield and the molecular weight up to 90% and 10,000, respectively. Although the second polycondensation step at 180 °C was accompanied by formation of urea groups, this side reaction was relatively suppressed at 150 °C. The resulting polyurethane having hydroxyl groups at both of the end groups was converted to polyurethane methacrylate via a reaction with glycidyl methacrylate, and the polyurethane methacrylate served as a crosslinker for radical polymerization of methyl acrylate. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Asymmetric synthesis of tetrahydropalmatine via tandem 1,2-addition/cyclization

[Reaction: see text]. The enantioselective synthesis of both enantiomers of tetrahydropalmatine (2) (ee = 98%), a natural alkaloid belonging to the tetrahydroprotoberberine family, is described. The key step of this total synthesis is based on our tandem 1,2-addition/ring-closure methodology employing lithiated methylbenzamide and benzaldehyde SAMP or RAMP hydrazones as substrates. An initial route was investigated for the formation of N- and 3-substituted dihydroisoquinolones starting from 2-substituted benzaldehyde SAMP hydrazones, but although high diastereoselectivity was achieved, only disappointing yields were obtained. In our subsequent synthetic strategy, 2,3-dimethoxy-6-methylbenzamide 6 and 3,4-dimethoxybenzaldehyde SAMP or RAMP hydrazone 19 gave the dihydroisoquinolones 20 in high diastereomeric purity (de > or = 96%) and reasonable yield (54-55%), taking into account the complex functionalities established in one step. Cleavage of the N-N bond of the chiral auxiliary and reduction of the carbonyl group of the amide moiety were performed in the same step, and the resulting tetrahydroisoquinolines 22 (ee = 99%) were N-functionalized by treatment with various electrophiles to investigate the ring closure by Pummerer, Friedel-Crafts, and Pomeranz-Fritsch reactions. The Pummerer cyclization led to the formation of (S)-(-)-2 with slight racemization (ee = 89%), whereas the Friedel-Crafts reaction proved to be unsuccessful. Finally, Pomeranz-Fritsch-type cyclization afforded the desired title compound (R)-(+)-2 in excellent enantioselectivity in 9% overall yield over seven steps and after optimization of the last step (S)-(-)-2 in 17% overall yield.