基于Maple软件辅助绘制自由基二元共聚曲线的研究

运用数据处理软件(maple)对经典的自由基二元聚合公式进行图形绘制,得到了二元单体之间共聚关系的三组图。一是二元单体的自由基共聚曲线图F1-f1,二是聚合物中单体平均组成(Fp)与投料单体浓度(f1)的关系曲线图,三是聚合物转化率(C)与投料单体(f1)的关系曲线图。通过二组具有代表性的共聚实例,分别是有恒比点的非理想共聚(苯乙烯-丙烯腈共聚物)和非理想非恒比共聚(苯乙烯-乙酸乙烯酯共聚物)展现了绘图步骤和分析了不同竞聚率情况下的聚合物转化过程。     

Matlab在二元共聚物组成曲线绘制中的应用

通过Matlab GUI工具开发出一款专供反复使用且操作简单的绘制共聚物组成曲线的图形用户程序.其开发过程包括图形用户界面的构思、控件的绘制与调整、图形对象属性的设置、M文件的编写和程序调试与运行.该图形用户程序可实现绘图、参数显示、坐标捕捉和曲线风格设置等功能.它的使用在高分子化学教学中收到了良好的效果,通过随机输入...     

乙烯基单体/N-苯基马来酰亚胺共聚物组成预测、控制和优化

采用递推方法成功地预测了乙烯基单体/N-苯基马来酰亚胺(PMI)共聚物组成随转化率的变化.选择共聚单体种类和用量,控制和优化共聚物组成.针对氯乙烯(VC)/PMI/丙烯腈(AN)三元悬浮共聚合特殊体系的聚合特点和工艺,得到该三元体系的单体选择范围.     

高分子染料的合成研究2．乙烯砜型染料与丙烯腈的溶液共聚合

对乙烯机型染料在较高浓度下与丙烯腈溶液共聚合反应合成高分子染料进行了研究．考察了单体组成对聚合转化率、共聚组成和共聚物分子量的影响，合成了共聚组成中染料单体含量为３７％的高分子染料．     

用竞聚率画示意共聚曲线的简便方法

有关高分子化学共聚问题,常需要讨论二元共聚物曲线的类型,即从单体竞聚率r_1和r_2的数值,判别共聚物组成中单体1的克分子分数-F_1与原料混合物中单体1的克分子分数-f_1之间的关系.理论上讲,将r_1,r_2的数值代入共聚方程,可以得到F_1与f_1的函数关系式,然后选定一系列f_1值代入关系式,求出对应的F_1值,再以f_1为横坐标,F_1为纵坐标作图,即得到较精确的F_1～f_1共聚曲线(其精确程度由选取的f_1值     

論合成化学均匀共聚物时添加单体的計算——与史悠彰同志商榷

一、前言分批共聚合时,由于单体竞聚率的不同,在每一个瞬间,共聚物的组成与形成該共聚物的未反应单体混合物的比例是不同的(它们的关系卽所谓共聚方程式)。故一般来说,分批共聚合所得共聚物的化学组成总是不均匀的。因此,与均聚物不同,共聚物除了有分子量不均匀的问题以外,还有化学组成不均匀的问题。化学组成不均匀对共聚物的性能发生不利的影响。例如,丙烯腈共聚物能改进聚丙烯腈的染色能力,但假如此共聚物的化学组成不均匀,则染色力也就不     

借助微机测算三元共聚体系的竞聚率及不同转化率下共聚物的组成

将单纯形调优法与数值积分法相结合，建立了Ａｌｆｒｅｙ－Ｇｏｌｄｆｉｎｇｅｒ微分方程的数学模型，编制了计算机通用程序。应用此程序可以直接根据三元共聚体系的起始组成、任一转化率下共聚物的组成而求出相应单体的竞聚率；反之，也可求算不同转化率下三元共聚体系共聚物的组成。同时，以苯乙烯、丙烯腈、β－溴代苯乙烯所组成的三元共聚体系为例，验证了此程序的有效性     

St/AN乳液共聚合的表观竞聚率和恒比组成

<正> 共聚合中竞聚率的正确测算对于研究共聚物组成与单体配料比及转化率的关系、共聚物组成分布及链段分布和共聚合机理都有重要意义。对于大多数二元自由基共聚体系,聚合方法不同对竞聚率无影响,但对某些聚合体系,如苯乙烯/丙烯腈,不同的聚合方法测得的“竞聚率”会有所不同。一般文献报道,苯乙烯/丙烯腈自由基共聚合,60℃下的竞聚率分别为r_st=0.41±0.08,r_(AN)=0.04±0.04,均系本体聚合的实验结果。为此,     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基共聚

研究了甲基丙烯酸丁酯和苯乙烯两种不同极性单体的原子转移自由基嵌段共聚和无规共聚，得到了实测分子量与理论分子量相近、分子量分布较窄的嵌段共聚物和无规共聚物。聚合过程中分子量和单体转化率成比例增加，多分散性指数变化不大。用＾１Ｈ ＮＭＲ法测定共聚组成，Ｋdisplay status     

低分子量结晶性丙交酯/乙交酯与己内酯/乙交酯共聚物热转变温度的组成与分子量依赖性

以1,4-丁二醇为引发剂、辛酸亚锡为催化剂,通过L-丙交酯(LLA)、乙交酯(GA)、ε-己内酯(CL)的开环共聚,制得了低分子量的端羟基结晶性LLA/GA共聚物(PLLGA)和CL/GA共聚物(PCG),分别以FTIR1、H-NMR、GPC、DSC对其微结构和热转变温度进行了表征,重点考察了其热转变温度的组成、分子量依赖性.结果表明,利用辛酸亚锡/二元醇引发开环聚合,通过改变单体配比和单体/引发剂配比,可方便地调控共聚物的组成和分子量;通过改变共聚物的组成和分子量,可在较宽的范围内调节共聚物的热转变温度,并得到了玻璃化温度和熔点与组成、分子量之间定量的经验关系式.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

四环素-铕与卵磷脂的相互作用及卵磷脂的测定

以四环素(TC)-Eu3 作为荧光探针,提出了新的荧光光度法测量卵磷脂(PC)。在pH 5.7的酸度条件下,扫描不同浓度的PC与TC-Eu3 的荧光光谱。通过优化实验条件,得到了测定PC的最佳条件。卵磷脂能使TC-Eu3 位于612 nm处的特征荧光显著增强且增强的荧光强度与PC的量成正比。测量的线性范围为4.0×10-7~1.4×10-5mol/L,检出限为3.9×10-8mol/L。该方法已用于实际样品的测定。     

Synthesis and structure of hydroxyisoxazolidines and derivatives of hydroxylamine and alkenals

The reactions of N-substituted hydroxylamines with alkenals serve as a method for the synthesis of the corresponding 2-substituted 3(5)-hydroxyisoxazolidines. The reaction pathway is determined by the nature of the substituent attached to the nitrogen atom. Ring-chain isomerism has been detected in these newly obtained compoundsTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1276, September, 1987.     

Ni(Ⅱ)和Zn(Ⅱ)的乙基黄原酸盐与吡啶碱配合物的合成及性质的研究

乙基黄原酸基的结构为:(简写为Exan,它是一个双齿配体,能和许多金属离子形成稳定配合物。 本文依据实验结果,对3种Ni(Ⅱ)和2种Zn(Ⅱ)的乙基黄原酸盐混合配合物的性质作一些系统的比较.应用红外光谱讨论这些混合配合物的C—O及C—S键振动频率位移;用热谱讨论它们的热稳定性及失重过程的变化;通过组成分析用电子光谱及磁学方     

红霉素9,11-亚胺醚和乙腈分子加合物的合成和晶体结构

通过控制红霉素A (E)肟的贝克曼重排反应条件合成了一种关键中间体红霉素9,11-亚胺醚, 该化合物可与乙腈形成稳定的分子加合物(摩尔比为1∶1), 未见文献报道. 阐述了该化合物的合成、晶体结构、晶体学数据和结构参数. 该化合物为无色透明晶体, 属单斜晶系, 空间群P2₁. 对该加合物和已知化合物红霉素6,9-亚胺醚晶体结构的对照解析, 有助于对重排反应机理、异构化机理和两异构体还原差异性的分析, 对重排反应和还原反应起到积极的指导作用.     

Sizes of atoms and ions and covalency of bonding in molecules and crystals

A new system of atomic radii for the elements up to barium inclusive is constructed. Values of the radii are chosen so as the dependence between the dissociation energy of diatomic homonuclear molecules and a depth of atom overlapping is monotonous, and the scatter of data is minimal. The depth of overlapping is calculated as a difference between the sum of atomic radii and an experimental interatomic distance. Conclusions are made that: the radii of free atoms and ions are determined by the value of the electron density equal to 0.01 au; they considerably change in molecules and crystals only as a result of the charge transfer from cation to anion; covalent bonding is well described by the overlapping of free atoms (ions), confined by the surface of the given radius, and its energy depends upon the depth of overlapping of valence electron densities of atoms. A method of overlapping atoms is proposed for the approximate estimation of ionic sizes and charges in bound systems.     

Interaction and Stability of Mixed Micelle and Monolayer of Nonionic and Cationic Surfactant Mixtures

Interaction and stability of binary mixtures of cationic surfactants hexadecyltrimethylammonium bromide (HTAB) or hexadecylpyridinium bromide (HPyBr) with nonionic surfactant decanoyl-N-methyl-glucamide (Mega-10) have been studied at different mole fraction of cationic surfactants by using interfacial tension measurements and fluorescence probe techniques. From interfacial tension measurements, the critical micellar concentration and various interfacial thermodynamic parameters have been evaluated. The experimental cmc's were analyzed with the pseudophase separation model, the regular solution theory, and the Maeda's approach. These approaches allowed us to determine the interaction parameter and composition in the mixed state. By using the static quenching method, the mean micellar aggregation numbers of pure and mixed micelles of HTAB + Mega-10 were obtained. It has been observed that the aggregation number of mixed micelles deviates negatively from the ideal behavior. The micropolarity of the micelle was monitored with pyrene fluorescence intensity ratio and found to be increase with the increase of ionic content. The polarization of fluorescence probe Rhodamine B was monitored at different mole fraction of cationic surfactants.     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

Synthesis and characterization of triazenide and triazene complexes of ruthenium and osmium

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.