不溶混聚合物共混体系相态反转的研究进展

对不溶混聚合物共混体系相态反转的粘度比模型、弹性比模型、粘弹性比模型和扭矩比模型进行了分析，提出了动态硫化EPDM／PP等热塑性弹性体相态反转的判断方法，认为振动力场对控制不溶混聚合物共混体系的相态反转具有积极作用。     

醇-水-醋酸钠/碘化钾体系汽液平衡

用改进的Othmer汽液平衡釜测定了101．3kPa下盐摩尔分率x3=0.008、0.012、0．02乙醇—水—醋酸钠／碘化钾体系；x3=0.01异丙醇／正丙醇—水—醋酸钠／碘化钾体系，共10组汽液平衡数据，并用Mock模型、Sander模型、Macdo模型和Kikic模型对这10组实验数据分别进行了关联，结果良好，基本上满足工程设计要求。其中，Mock模型明显好于其他三类模型，所需模型参数也较少，Sander模型与Macedo模型精度相仿，但Macedo模型消除了D-H项中的不一致性。     

超临界流体萃取中的相平衡研究

本文综述了超临界流体萃取过程中的相平衡模型及其实验研究的新进展，特别着重介绍了压缩气体模型，膨胀液体模型，经验模型和计算机模拟模型，研究体系包括液体／ＳＣＦ，固体／ＳＣＦ，固体／ＳＣＦ／夹带剂体系。     

Haake混合器中双组分聚合物熔体共混过程的数值模拟研究

采用有限元分析软件POLYFLOW对发生在Haake密闭式混合器中的双组分聚合物熔体共混过程进行了二维等温数值模拟，并进行了实验验证。首先采用仅和流场有关的黏度模型对共混过程进行了数值模拟，模拟结果与实验结果符合较好。进而又考虑了共混体系中组分含量对共混体系黏度的影响，对原来的黏度模型进行了修正，修正后的数值模拟结果和实验结果更接近。通过利用数值模拟的方法进一步获悉了双组分聚合物体系对流混合的规律。     

Haake混合器中双组分聚合物熔体共混过程的数值模拟研究

采用有限元分析软件POLYFLOW对发生在Haake密闭式混合器中的双组分聚合物熔体共混过程进行了二维等温数值模拟，并进行了实验验证。首先采用仅和流场有关的黏度模型对共混过程进行了数值模拟，模拟结果与实验结果符合较好。进而又考虑了共混体系中组分含量对共混体系黏度的影响，对原来的黏度模型进行了修正，修正后的数值模拟结果和实验结果更接近。通过利用数值模拟的方法进一步获悉了双组分聚合物体系对流混合的规律。     

λh方程在混合溶剂中的应用

推导了固体在混合溶剂中的溶解度模型（λｈ方程）。对８９个三元体系和４个五元体系的两参数回归计算表明，该模型具有较好的精度。进而本文提出了一个与混合溶剂组成有关的基于纯溶剂参数的混合规则。根据该规则仅用于个参数回归三元体系就能获得较好的精度，利用三元体系的回归参数预测五元体系的溶解度也获得了令人满意的结果。     

ASOG模型推算溶液表面张力

本文将ＡＳＯＧ基团贡献模型引入Ｂｕｔｌｅｒ方程，使ＡＳＯＧ模型能够推算溶液的表面张力。对９０个二元体系和８个元体系的表面张力作了推算，并与ＵＮＩＦＡＣ推算表面张力的结果作了比较，结果令人满意。     

聚合物-表面活性剂相互作用与溶液表面性质

在查阅了大量文献的基础上，对聚合物／表面活性剂缔合复合体系的结构进行了讨论，总结了不同种类聚合物及表面活性剂缔合复合体系的结构模型，并着重讨论了目前研究较少的聚像体系动态表面张力方面的研究。     

炭黑对聚氨酯泡沫塑料发泡行为的影响

建立了在聚氨酯导电泡沫塑料反应体系中炭黑的乳化和稳泡作用模型，研究了不同粒径的炭黑和不同的添加量对体系发泡行为的影响，初步探讨了炭黑对微相分离的影响。     

碳纳米管填充复合材料体系的导热模型研究进展

综述了以聚合物为基体的碳纳米管填充复合材料导热模型，分析了复合材料热传导体系中碳纳米管(CNTs)填料的作用机制，归纳了均质模型、非均质模型和随机分散模型等，总结了导热模型常用的数值计算方法。这些模型丰富了导热理论，可以对复合材料导热系数进行初步预测，但在数值上都存在近似或者简化处理，对碳纳米管复合材料预测广谱性较差，若要提高预测准确性，需要更深入探究分子界面处的热阻。     

聚二甲基硅氧烷/溶剂体系气液平衡研究

采用气液色谱法测定了聚二甲基硅氧烷（ＰＤＭＳ）和９种溶剂在５８～１８０℃范围内,７个不同温度下无限稀溶剂活度系数和Ｆｌｏｒｙ－Ｈｕｇｇｉｎｓ相互作用参数。应用ＵＮＩＦＡＣ和ＵＮＩＦＡＣ－ＦＶ模型对ＰＤＭＳ／烃溶剂体系无限稀溶剂活度系数进行了估算。结果表明,ＵＮＩＦＡＣ－ＦＶ模型能较好地预测ＰＤＭＳ／烃溶剂体系无限稀溶剂活度系数。     

An improved prediction result of entropic‐FV model for vapor–liquid equilibria of solvent–polymer systems

In this work, entropic expressions of UNIFAC‐FV and Entropic‐FV models were evaluated by using an extensive database of infinite dilution vapor–liquid equilibrium (VLE) data of athermal systems containing polypropylene, polyethylene, and polyisobutylene. For the infinite dilution athermal systems, performance of the Entropic‐FV model was better than that of the UNIFAC‐FV model. Then, finite concentration VLE data of non‐athermal systems that consisted of 16 polymers and 36 solvents containing a large variety of solvent–polymer systems ranging from nonpolar to polar substances were considered to optimized 46 pairs of group interaction parameters of the Entropic‐FV model. For systems containing polar solvents of three types of solvents studied, revised group interaction parameters gave significant improvements from 17.9 to 13.0% average absolute deviation (AAD) of solvent activities. For overall results, improvements were achieved from 15.1 to 12.4% AAD. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1145–1153, 2005     

UNIFAC and infinite dilution activity coefficients

This paper deals with the possibility of estimating UNIFAC parameters from infinite dilution activity coefficients. Such activity coefficients can be obtained from gas chromatographic measurements (GLC). In some cases the original UNIFAC equations do not represent very well the variations of the activity coefficients with the concentration in the very dilute regions. It is then not possible to estimate reliable parameters from infinite dilution activity coefficients alone. It is shown that a recent modification of the combinatorial part of the UNIFAC equations allows for the estimation of UNIFAC parameters from infinite dilution activity coefficients for alkane—-ketone, alkane—-alcohol, and other mixtures.     

Solvent extraction of aromatics from middle distillates: Equilibria prediction method by group contribution

This work describes a method of calculating liquid-liquid aromatics extraction of a middle distillate. The group contribution models of the ASOG and UNIFAC type are investigated. Four vapour liquid equilibrium (VLE), two solid-liquid equilibrium (SLE), three binary and six ternary liquid-liquid equilibrium (LLE) have been measured. The parameters of the models are based mainly on the data of the systems having 10–20 carbon number. VLE, SLE, and infinite dilution activity coefficient data (17–245°C) have been used for calculating interaction parameters between hydrocarbon groups and LLE data (20–80°C) for interaction parameters of dimethylformamide-hydrocarbon groups. Middle distillate representation is based on mass spectrometric and gas chromatographic analysis and on limited data of middle distillate-DMF liquid-liquid equilibrium. It is shown that the performance of ASOG and UNIFAC models are sufficiently valid in representation of data base and in extraction calculations. Considering the predictive character and the rapidi of its application this method can be useful in the preliminary study of extraction processes.     

UNIFAC基团贡献法预测烃类在N-甲酰吗啉中的相平衡数据

用ＵＮＩＦＡＣ基团贡献法预测了苯及烷烃在Ｎ甲酰吗啉溶剂中的无限稀释活度系数及苯ＮＦＭ的二元汽液平衡数据。为提高预测精度，对ＵＮＩＦＡＣ的交互作用参数进行了改进。     

Modeling Infinite Dilution Activity Coefficients of Environmental Pollutants in Water Using Conformal Solution Theory

Abstract

The fate of organic pollutants in the environment and in wastewater treatment processes is commonly modeled using a Henry's law constant approach. By definition, Henry's law constant is the product of a compound's vapor pressure and infinite dilution activity coefficient. For many organic compounds in water solution, the infinite dilution activity coefficients are very large and are not adequately modeled by conventional methods such as UNIFAC. In this work, infinite dilution activity coefficients were determined for phenol, pyridine, aniline, p-toluidine, and o-toluidine in water by differential ebulliometry. An equation rigorously derived from conformal solution theory and van der Waals one-fluid mixing rules was used to model the temperature dependency of the infinite dilution activity coefficients. No corrections other than the introduction of two adjustable parameters were incorporated into the model to account for the strong interactions between molecules. Relationships derived from corresponding states theory were used to relate molecular parameters for size and energy interaction to the critical properties. Arithmetic mean combining rules and geometric mean combining rules were used to calculate size and interaction parameters, respectively.     

色谱测UNIFAC参数的方法研究

UNTFAC参数通常从汽液平衡数据回归得出.鉴于汽液平衡实验繁琐且不经济,而气液色谱实验简单、迅速、经济、可靠,近年来巳用于测UNIFAC参数,其中又有两种方法:一种用单体系无限稀释活度系数γ~∞,加上单参数Flory-Huggins方程回归;另一种由几个体系的γ~∞联立回归.前者仅适用于分子大小悬殊的体系,后者则相对来说精度较差、工作量较大.本工作采用了单体系γ~∞与无限稀释条件下活度系数-组成曲线斜率结合回归(简称斜率法).斜率测定用Valentin-Guiochon公式.比较了三种方法,工作表明:多γ~∞法一般较差,斜率法结果较为满意.分析了UNIFAC参数对γ~∞及((?)γ)/(?)x)_x=0的灵敏度,发现γ~∞的影响比((?)γ/(?)x)_x=0大.用极大似然法讨论了参数估计与置信区间.     

计算活度系数的UNIFAC基团贡献法(Ⅱ)

本文综述了近年来UNIFAC基团贡献法在计算汽液平衡、超额焓、无限稀释活度系数等方面的进展情况以及对UNIFAC基团贡献法的修正,并提供了有关的UNIFAC参数表。这是本文的第二部分。     

计算活度系数的UNIFAC基团贡献法(Ⅰ)

本文综述了近年来UNIFAC基团贡献法在计算汽液平衡、超额焓、无限稀释活度系数等方面的进展情况以及对UNIFAC基团贡献法的修正,并提供了有关的UNIFAC参数表。这是本文的第一部分。     

合成硝基麝香三元体系的固液平衡

通过试验测定了合成硝基麝香二元体系的固液平衡数据,回归并修正了UNIFAC模型的相互作用参数,使UNIFAC模型具有更高的预测功能;为了评价修正后的UNIFAC模型对合成硝基麝香三元体系的预测功能,利用试验测定的溶解度数据和修正后的UNIFAC模型计算值进行了比较,结果表明相互作用参数的修正是理想的.