聚甲基丙烯酸甲酯接枝聚氧乙烯两亲接枝共聚物的合成研究

采用大分子单体法合成了结构明确,规整性好的两亲接枝共聚物－聚甲基丙烯到甲酯接枝聚氧乙烯（ＰＭＭＡ－ｇ－ＰＲＯ）并以ＩＲ,ＮＭＲ和ＧＰＣ方法表征了两亲接枝共聚物,通过定性和定量测试,结果证明两亲接支共聚物具有预期的结构,两亲共聚物的结构,分子量与大分子单体的结构,分子量密切相关。     

碳酸二甲酯生产技术发展趋势

碳酸二甲酯(Dimethyl carbonate以下简称DMC)作为21世纪的重要化工产品,目前正受到世界各国越来越多的重视。众所周知,硫酸二甲酯(DMS)、光气(COCl_2)两种有机化工产品系重要的甲基化和羰基化试剂,在农药、医药、聚氨酯、有机化工等行业有广泛的用途。但这两种产品均系剧毒品,随着人类环保意识的加强,急需开发一种新的低毒或无毒代用品,碳酸二甲酯应运而生。碳酸二甲酯于1992年在欧洲通过非毒性化学品的注册登记,作为一种无毒的化学品,同时又因特殊的化学结构而具有优良的反应活性,DMC正在许多领域有望全面替代剧毒的光气、硫酸二甲酯等,从而成为未来世界化学合成的新基块。 DMC生产方法可分为三大类:即光气法、酯交换法和羰基合成法。光气法又可分为光气甲醇法和光气醇钠法。羰基合成法又可分为液相氧化羰基化法和气相氧化羰基化法。 1.光气甲醇法 该法是古老而经典的合成法,首先由光气与甲醇合成氯甲酸甲酯,氯甲酸甲酯进而与甲醇反应得DMC。此法可工业规模生产DMC,但存在工艺复杂,操作周期长,原料(光气)剧毒,副产HCl腐蚀严重,污染环境,安全性差等问题,不宜推广。     

Salen-AlCl/n-Bu4NBr体系在催化酯交换中协同效应研究

碳酸二甲酯是一种有多种用途的环境友好化学品,主要由甲醇氧化羰基化法(非光气法)和甲醇光气法(光气法)合成,这两种方法都使用了剧毒或有毒的光气和一氧化碳.而酯交换法是一种可以在温和条件下合成碳酸二甲酯的方法.为此研究了Sa len-A l配合物体系催化碳酸乙烯酯与甲醇酯交换反应生成碳酸二甲酯的行为.证明了Sa len-A l配合物体系不仅是环氧烷烃与二氧化碳合成碳酸乙烯酯的优良催化剂,而且也能很好地催化后续酯交换反应.发现最佳催化剂是Sa len-A lC l/n-Bu4NB r,它们间存在协同效应.测得最佳反应条件是温度120℃、反应时间2 h、n(M eOH)∶n(PC)=8∶1、催化剂摩尔分数为0.4%.     

技术转让

天津大学成果集锦联系人:舒歌群电话:022-27405564地址:天津市南开区卫津路92号邮编:300072J201448光学级聚碳酸酯非光气法生产技术天津大学研究开发的酯交换法聚碳酸酯生产工艺是用碳酸二苯酯与双酚A在催化剂作用下直接进行酯交换反应,直接造粒得到聚碳酸酯产品。该法优点是不使用剧毒的光气和溶剂二氯甲烷,无脱溶剂和水洗脱盐工序,流程简单,大大降低了对环境的污染程度,已成为当今PC产业发展的方向。目前我国光学级聚碳酸酯全部依赖进口,若按今后年均增长10%的保守估计计算,预计到2005年我国聚碳酸酯需求量将接近17万t,其中光盘级PC需…     

加压一步法合成碳酸乙烯酯

碳酸乙烯酯的合成方法主要有光气法、氯醇法、酯交换法和加压法.加压法是目前国外普遍采用的工业化合成方法,具有工艺流程短、收率高、选择性好、产品质量优、无环境污染等特点.     

酯交换法合成碳酸二苯酯

碳酸二苯酯(DPC)是一种重要的精细化工中间体,主要用于合成许多有机化合物和高分子材料。目前,合成碳酸二苯酯方法有光气法、氧化羰基化法和酯交换法。酯交换法合成DPC主要是通过苯酚与碳酸二甲酯(DMC)反应合成,在100～200℃常压或加压的条件下进行,反应设备简单、毒性和腐蚀性小,产率较高,是一种绿色合成方法。     

GPC法测定聚酯型高分子表面活性剂的分子量及其分布

本文采用ＧＰＣ法，测定了不同工艺条件下合成的聚酯型高分子表面活性剂的分子量及其分布，从而为确定最佳工艺条件提供了依据。     

甲壳胺对甲基丙烯酸溶液聚合的“模板”效应

研究甲壳胺（ＣＴＳ）对甲基丙烯酸（ＭＡＡ）水溶液聚合的影响，探讨在不同ＭＡＡ／－ＮＨ２摩尔比的水溶液中ＭＡＡ聚合形成聚合物的分子量和结构规整性，结果表明ＣＴＳ对ＭＡＡ聚合物的结构规整性有影响，即具有一定的“模板”效应。     

含磷聚碳酸酯的合成及催化剂对产物性能的影响

以双酚A(BPA)、碳酸二苯酯(DPC)和亚磷酸三苯酯为原料,分别以氢氧化锂(Li OH)和乙酸锂(Li-Ac)为催化剂,通过熔融酯交换法合成得到含磷聚碳酸酯。分别通过红外光谱仪、凝胶渗透色谱仪、示差扫描量热仪和热重分析仪对所得产物结构、分子量及分子量分布、玻璃化温度和热稳定性进行了表征和测定。结果表明,反应5.5 h,Li OH催化体系所得产物数均分子量为8 700 g/mol,分子量分布系数为4.27,玻璃化温度为115.09℃,700℃时残炭率为25.51%;Li Ac催化体系所得产物数均分子量为8 000 g/mol,分子量分布系数为9.36,玻璃化温度为109.91℃,700℃时残炭率为24.11%。     

甲苯二异氰酸酯主要生产工艺对比

甲苯二异氰酸酯（TDI）是工业上重要的有机体,是聚氨酯生产的重要原料。TDI是有名的投资成本高,技术难度大,生产操作困难的化工产品。目前的TDI合成方法包括光气法和非光气放法。其中非光气法又包括所羧基化法、碳酸二甲酯法等。本文从工艺流程、生产设备,操作条件、生产现状、发展前景等方面对光气法、羧基化法、碳酸二甲酯法三种主要合成方法进行对比,并对TDI合成工艺做出展望。     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the     

An affordable accurate evaluation of the binding conformations predicted by molecular docking studies in bio-system

Franck-Condon factors bridge the gap between theoretical modeling and experimental observations for molecular electronic spectroscopy and electron transfer.Under the displaced harmonic oscillator approximation,multidimensional Franck-Condon factors are decomposed into a product of many one-dimensional(1D)Franck-Condon(FC)factors,and each 1D-FC factor is associated with one Huang-Rhys factor that determines the leading contribution of     

Call for Papers

<正>"The Journal of Shanghai Normal University:Mathematics"is published by Shanghai Normal University as regular issues of The Journal of Shanghai Normal University each year from 2014 in English.The editors-in-chief of the issues are professors Yuhao Cong and Maoan Han.The Journal of Shanghai Normal University was started in 1958 with     

Journal of Donghua University ( English Edition) Contents of Volume 31

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