茂金属聚乙烯共混体系液液相分离行为

研究了茂金属催化的高密度聚乙烯 (mPEO)和传统工艺生产的低密度聚乙烯 (LDPE)共混体系液 液相分离行为 .用DSC测试了共混体系在两种聚乙烯熔点之间的等温结晶动力学 ,发现共混体系经过 15 0℃培养 ,其等温结晶速率明显增快 .在排除成核作用和共结晶的影响后 ,表明上述结果是由于聚乙烯共混体系在熔融态发生了液 液相分离引起的 .从而为聚乙烯共混体系液 液相分离的存在提供了新证据     

生物分子液-液相分离的物理化学机制

近年来,有关生物分子通过液-液相分离机制进行组织定位、功能调控的研究发展迅速。相分离产生的聚集体在众多细胞活动事件中发挥了关键作用。这些聚集体的生物功能是以相分离的物理化学性质为基础的。本文将从相分离聚集体的基本性质、相图、微观结构,相分离的统计热力学、实验和分子模拟研究等方面阐释相分离物理化学机制研究相关进展。对于生物分子相分离的重要功能体系进行了列举和归纳,收集了相分离研究的模式体系,探讨了生物分子相分离的生物功能同物理化学机制之间的关系,总结了生物分子相分离的调控机制和调控分子的设计方法,并对生物分子相分离物理化学机制研究的未来发展方向进行了展望。     

生物大分子液-液相分离研究方法

生物大分子液-液相分离是一种普遍存在的生物物理现象,是近年来生命科学领域的新兴研究热点。生物大分子通过多价相互作用不断富集,当分子浓度达到溶液中的溶解阈值,就会以液-液相分离的形式从溶液中析出。这一现象与细胞内许多重要的生物学过程(如无膜细胞器的形成等)息息相关。随着相分离相关研究的不断深入,其研究方法也在不断发展与完善。本文从相分离的原理与特点出发,对目前常用的一些相分离研究方法进行了介绍,为后续相分离研究提供方法依据,促进相分离技术和方法的进一步发展。     

温控配体与液／液两相催化

 以作者近年的研究工作为主，对液／液两相催化研究领域取得的进展做一综述．着重介绍了以温控配体为基础的新型液／液两相催化过程温控相转移催化（thermoregulatedphasetransfercatalysis，TRPTC）和温控相分离催化（thermoregulatedphase－separablecatalysis，TPSC）的基本原理及其在高碳烯烃氢甲酰化、芳香硝基化合物的CO选择性还原及烯烃加氢等反应中的应用．基于温控配体在水中的“浊点”特性而提出的温控相转移催化概念，为从根本上解决水／有机两相催化 的适用范围受底物水溶性限制的问题提供了一条新途径．而利用温控配体在某些有机溶剂中存在临界溶解温度（CST）的特性而实现的温控相分离催化，则使在高于临界溶解温度的反应温度时为均相的反应体系，在低温（＜CST）时则分成两相，催化剂自成一相，形成一种具有“均相反应、两相分离”特色的液／液两相催化新体系．     

无相分隔与/或无相分离的流动注射-液液萃取技术的进展

本文对无相分隔与 /或无相分离的流动注射 -液液萃取技术的进展作了回顾与评述。引用文献 32篇     

聚合物共混物的相容性及相分离

综述了聚合物共混物相容性和相分离的研究现状。介绍了聚合物共混物的相容性理论,影响相容性的因素及改善和相容性的方法和表征相容性的手段。聚合物共混物的相分离机理制约着材料的性能,旋节分离和成核－增长相分离分别形成不同的形态结构。旋节分离和成核－增长相分离所对应的动力学过程是不同的,散射光强与相分离时间分别满足指数和幂指数关系。     

凝固-漂浮分散液液微萃取富集分光光度法测定水中亚硝酸根

研究了凝固-漂浮分散液液微萃取（SFO-DLLME）-分光光度法测定水样中痕量亚硝酸根的方法。以1-十二醇为萃取剂,乙醇为分散剂进行分散液液微萃取,离心后通过冷冻凝固操作使漂浮的萃取剂和水相分离。最佳实验条件下,方法的线性范围为2.0-280μg/L（r=0.999 9）,检出限为0.34μg/L。方法已成功应用于环境水样分析,相对标准偏差在2.4%-3.3%,加标回收率在98.2%-102.4%。     

液/液界面电分析化学研究进展

本文对液/液界面电分析化学近年来的进展进行了综述,特别是结合我们自己的工作,对探讨液/液界面微观结构和构筑新型液/液界面方面的进展进行了重点介绍.目前通过理论模拟和各种实验技术的应用,液/液界面微观结构已初具轮廓;可供选择的有机相也得到了一定的拓展.这些进展为该领域今后的发展打下了基础并指明了方向.     

双液系气－液平衡相图绘制中有关问题的探讨

本文以物理化学实验“苯－乙醇气液平衡相图绘制”为研究对象，对其混合液的浓度调整以期达到再利用进行了探讨，提出了调整方法，进行了实验验证，取得了理想的效果。     

液膜富集分光光度法测定水中痕量铬（Ⅵ）

本文研究了分离，富集Ｃｒ（Ⅵ）的最佳液膜组成和实验条件，确立了兰１１３Ｂ－ＴＯＡ－煤油－液体石蜡－ＮａＯＨ液膜体系。用本法富集，测定工业废水中的Ｃｒ（Ⅵ），富集倍数达７５，相对标准偏差为１．１％，回收率９９％以上。     

高强超韧高密度聚乙烯/聚丙烯共混物性能与微相分离结构的研究

在常规注射过程中 ,难以获得超高性能的共混体系注射制件 ,已有的研究表明 ,采用高剪切注射 ,可以抬高共混体系的最低临界相容温度曲线 (LCST)的位置 ,增加相容性 .当熔体进入模具后 ,冷却的同时相容性下降 ,开始相分离 ,相分离程度发展到某一程度即可获得高性能的制件 .对于高密度聚乙烯 (HDPE)、聚丙烯 (PP)两组分均为结晶型聚合物的共混体系 ,由于其相形态与结晶形态相互制约、竞争 ,微相分离程度难以控制 ,因此对其液 液相形态与结晶过程的控制是获得共混物最终形态与性能的关键 .采用振动保压注射成型技术不仅对HDPE、PP各自力学性能有明显的自增强作用 ,而且对HDPE/PP共混体系的力学性能也有十分明显的改善 .DSC、WAXD、SEM结果表明共混体系拉伸强度的提高主要取决于试样中串晶数量和大分子链的定向程度 ,而冲击强度则主要取决于两组分微观的相分离程度 .研究结果表明 ,HDPE/PP含量为 92 / 8的试样拉伸强度为 97 1MPa,80 / 2 0试样的缺口冲击强度为 4 5 5kJ/m2 ,较静态试样分别提高 4 3倍和 9 5倍 .采用振动填充注射技术针对某一组分可以获得高强度、高韧性的共混制件 .     

壳核结构增韧剂对热塑性共聚酯/聚乙烯辛烯弹性体共混体系增容与增韧的影响

研究了马来酸酐接枝的聚乙烯辛烯弹性体 /半结晶性塑料共混物 (TPEg)对热塑性共聚聚酯(PETG) /聚乙烯辛烯弹性体 (TPE)共混体系增容增韧作用的影响 .马来酸酐接枝物显著地改善了PETG与TPE之间的相容性 ,导致TPE分散相颗粒细化 ,并促使分散相颗粒面间距等于甚至小于实现脆韧转变所需的临界面间距 .在固定PETG基体含量为 85wt %的前提下 ,当TPEg在 15 %分散相中的含量由 2 0 %增加到30 %时 ,即TPEg在共混体系中的含量由 3 %增加到 4 5 %时 ,共混体系出现了由脆性到韧性的转变 ,冲击强度急剧升高     

壳核结构增韧剂对热塑性共聚酯／聚乙烯辛烯弹性体共混体系增容与增 …

研究了马来酸酐接枝的聚乙烯辛烯弹性体／半结晶性塑料共混物（ＴＰＥｇ）对热塑性共聚聚酯（ＰＥＴＧ）／聚乙烯辛烯弹性体（ＴＰＥ）共混体系增容增韧作用的影响。马来酸酐接枝物显著地改善了ＰＥＴＧ与ＴＰＥ之间的相容性,导致ＴＰＥ分散相颗粒细化,并促使分散相颗粒面间距等于甚至小于实现脆韧转变所需的临界面间距。在固定ＰＥＴＧ基体含量为８５ｗｔ％的前提下,当ＴＰＥｇ在１５％分散相中的含量由２０％增加到３０％时,即     

Phase behavior of polymer/diluent/diluent mixtures and their application to control microporous membrane structure

Rechargeable battery separators containing controlled pores were fabricated via the thermally-induced phase separation (TIPS) process. Based on the idea that pores could be manipulated by controlling the liquid–liquid phase separation temperature in the TIPS process, phase boundaries of the polymer–diluent systems were controlled by using diluent mixtures. Phase behaviors of the polymer/diluent/diluent ternary blends consisting of polyethylene (PE) as polymer, and soybean oil (SBO) and dioctyl phthalate (DOP) as diluents were explored. PE/SBO and PE/DOP binary blends, and PE/SOB/DOP ternary blends exhibited typical upper critical solution temperature (UCST) type phase behaviors, and the phase separation temperatures of the PE/SBO blends were higher than those of the PE/DOP blends. When the mixing ratio of the polymer and diluent-mixture was fixed, the phase separation temperature of the PE/SBO/DOP blend initially increased with increasing SBO content in the diluent-mixture passing through a maximum centered at about 80 wt% SBO and decreased beyond this point. Furthermore, the phase separation temperature of the PE/diluent-mixture blend was always higher than that of the PE/SBO blend when the diluent-mixture contained more than or equal to 50 wt% SBO. To understand the observed phase behavior of the blends, thermodynamic analyses based on the lattice-fluid theory were performed. Larger pore membranes were fabricated from the blend when higher phase separation temperatures of the blend were exhibited.     

Sensitive phase separation behavior of ultra-high molecular weight polyethylene in polybutene

Thermally induced phase separation (TIPS) has prompted a great deal of interest, especially as an effective approach to fabricate ultra-high molecular weight polyethylene (UHMWPE) microporous membranes. However, the existing utilized diluents for the TIPS process of UHMWPE suffer from environmental and health issues. Herein, we utilized low molecular weight polybutene (PB) bearing similar structure with liquid paraffin (LP) but inferior miscibility with UHMWPE relative to UHMWPE/LP blend, as a diluent for the TIPS process of UHMWPE. The phase separation behavior of UHMWPE/PB blends were investigated by the combination of rheological measurements, optical microscopy as well as differential scanning calorimeter (DSC). The results suggest that PB is fully miscible with UHMWPE at elevated temperature, but yielding a more sensitive phase separation behavior in respect to LP in TIPS process, because PB has weaker interaction with UHMWPE. The Jeziorny method analysis indicates that the crystallization mechanism of UHMWPE/LP blends is in line with that of UHMWPE/PB blends, which includes nucleation and growth as well as their dynamic competition. Moreover, compared to those of UHMWPE/LP blends, UHMWPE/PB blends display higher TIPS temperature and faster TIPS rate along with faster overall crystallization rate, further demonstrating that PB can accelerate phase separation rates and enhance the efficiency of TIPS process.     

新型手性近晶C相液晶共聚酯的设计与合成

以对苯二甲酰氯 ,2 ,5 二 [4 ((s) 2 甲基丁氧基 )苯甲酰氧基 ]对苯二酚和乙二醇、一缩乙二醇、二缩三乙二醇、三缩四乙二醇和聚乙二醇为单体 ,采用低温溶液缩聚方法 ,合成了一系列新的手性近晶C相串型液晶共聚酯 .共聚酯通过GPC、DSC、TG、WAXD、偏光显微镜和旋光仪等方法表征 .发现所有的共聚酯加热至各自的熔点以上都能形成液晶态 ,在液晶态可以观察到近晶相的焦锥织构 ,所有的手性化合物和共聚酯都有较高的旋光性 .通过变温X 射线衍射研究结合偏光显微镜观察和旋光分析证明它们为手性近晶C相 .所有共聚酯的熔融温度 (Tm)和各向同性温度 (Ti)随共聚酯中不同柔性链段长度的增加逐渐降低 ,液晶态温度范围变宽     

Probing Liquid-Liquid Phase Separation of a Polyethylene Blend with Thermal Analysis

Summary: A series of polyethylene (PE) blends consisting of a high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with a butene-chain branch density of 77/1000 carbon was prepared at different concentrations. The LLDPE only crystallized below 50 °C, therefore, above 80 °C and below the melting temperature of HDPE, only HDPE crystallized in the PE blends. A specifically designed multi-step experimental procedure based on thermal analysis technique was utilized to monitor the liquid–liquid phase separation (LLPS) of this set of PE blends. The main step was first to quench the system from the homogeneous temperatures and isothermally anneal them at a prescribed temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from LLPS, and then cool the system at constant rate to record the non-isothermal crystallization. The crystallization peak temperature (T_p) was used to character the crystallization rate. Because LLPS results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the LLPS for the system indicated by increased T_p. The result showed that the LLPS boundary of the blend measured by this method was close to that obtained by phase contrast optical microscopy method. Therefore, we considered that the thermal analysis technique based on the non-isothermal crystallization could be effective to investigate the LLPS of PE blends.     

PPO/SEBS-g-MAH共混体系的形态结构与冲击性能

从亚微相态和冲击性能出发 ,对比了采用熔融挤出法制备的PPO/SEBS和PPO/SEBS g MAH两种共混物 .结果表明 ,在本文所研究的弹性体用量范围内 ,PPO/SEBS为“海 岛”型结构 ,而PPO/SEBS g MAH呈现网状结构 ;PPO/SEBS体系无脆韧转变现象 ,PPO/SEBS g MAH体系则在弹性体用量为 10 %～ 15 %时出现明显的脆韧转变 ,缺口冲击强度达到 95 0J/m ,这种超韧现象源于其网状结构的形成 .文中进一步用DSC和毛细管流变仪对共混体系的热性能和流变性能进行了测试 ,探讨了PPO/SEBS g MAH共混物网状结构的形成原因     

Scanning electron microscopy methods for studying interfacial interaction in polymer blends

The scanning electron microscopy method in combination with the selective etching technique for polymer blends have been used to evaluate interfacial interaction in natural rubber and low density polyethylene blends. The morphology of the polymer blends, studied under externally applied strain, has been investigated to understand the role of interface adhesion between natural rubber and polyethylene phases, for two separate crosslinking systems, i.e. sulphur and peroxide.

Externally induced strain which facilitates phase separation in sulphur cured blends by initiating cracks at the interface; peroxide curing prevents separating out of the polyethylene phase from the natural rubber matrix. In the latter case, induced stress is distributed predominantly by developing fine flaw paths in the rubber matrix.

The method which has been developed for natural rubber and polyethylene blend systems may be used to evaluate the degree of interfacial adhesion between the dispersed phase and the dispersion medium for other kinds of polymer-polymer, polymer-filler as well as polymer-fibre composites.