端羟丁腈聚氨酯/聚甲基丙烯酸甲酯互穿网络高聚物的T_g和形态研究——Ⅰ.组分比和交联程度的影响

用同步法合成了端羟丁腈聚氨酯/聚甲基丙烯酸甲酯互穿网络高聚物[PU(HTBN)/PMMA-IPN]。用动态力学方法和透射电镜研究了它们的T_(?)转变行为和形态。理论计算和实验结果表明,样品具有两个明显相互分离但又各自连续的相结构,呈现出分属于组分聚合物的两个Tg转变(Tg_1,Tg_2)。在全IPN中,PMMA相区的尺寸(1000—2000?),比在接枝共聚物(3000—6000?)和半IPN(—3000?)中的明显变小。适当的交联程度可使相区进一步变小,变均匀,相连续性增加。这是网络互穿造成的“强迫互容”所致。部分丁腈羟(HTBN)分子同PMMA的反应,使一些样品出现了Tg_2升高的现象。     

IONIC CONDUCTIVITY OF EPOXY NETWORK/POLYETHYLENE GLYCOL- LITHIUM PERCHLORATE COMPLEX IPN SYSTEM

In an attempt to prepare a polymeric solid electrolyte with both high ionic conductivity at ambient temperature and adequate mechanical strength, an ionic conducting IPN composed of bisphenol A epoxy resin/polyethylene glycol containing LiClO_4 was synthesized. The dependence of conductivity was investigated as a function of salt content, composition and temperature. It has been revealed that a maximum of conductivity appeared when EO/Li=25, where EO denotes the—(CH_2CH_2O)-unit in polyethylene glycol, and that the temperature dependence of conductivity followed VTF equation, suggesting that the motion of ionic carriers resulted from the segmental motion of the polymer. When glycerol epoxy resin was used instead of bisphenol A epoxy, the ambient temperature (25℃) conductivity could somewhat further be raised up to 3×10~(-5) S/cm.     

SYNTHESIS AND NMR CHARACTERIZATION OF PRECURSORS OF EPOXY NETWORK AS POLYMER HOST FOR SOLID ELECTROLYTE

To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether of polyethylene glycols as precursors of the system were synthesized by a two-step process. The presumed structure of the product was characterized, by ~(13)C, ~1H NMR and IR spectroscopy. It was found that a side-reaction occurred between the secondary hydroxyl group of PEG-chlorohydrin and epichlorohydrin in some degree, resulting in a by- product containing—CH_2Cl side group. By selecting a characteristic signal, which is undistorted by the increase in the length of CH_2 CH_2—O segment, a ~1H NMR approach of determining the equivalent epoxy weight (EEW) was proposed. The method is valid to specimens even though the EEW is as high as 2,000. The examination of the specimens by DSC showed that epoxidation greatly depressed the crystallinity of the PEG's, whereas the T_g was raised.     

环氧树脂潜伏性固化促进剂的研究

对环氧树脂/桐油酸酐/乙酰丙酮钕体系的热固化反应进行了研究。用DSC、TBA和固化仪等手段测定了凝胶化时间和表观反应活化能,计算了反应动力学参数。结果表明,乙酰丙酮钕对体系的固化具有潜伏性促进作用。     

VISCOELASTICITY AND IONIC CONDUCTIVITY OF TWO-COMPONENT EPOXY NETWORK CONTAINING LITHIUM PERCHLORATE*

Polymeric solid electrolyte system composed of triglycidyl ether of glycerol (TGEG), diglycidyl ether of polyethylene glycol (DGEPEG)and LiClO_4 salt were synthesized. In this" system the electrolyte has a pecularity that not merely can the LiClO_4 provide ionic carriers, but also catalyze the crosslinking reaction without adding an usual curing agent. The effect of salt content and degree of crosslinking on the viscoelasticity and ionic conductivity were studied. Both WLF and VTF equations were used to treat the experimental data in order to elucidate the mechanism of ionic conduction. It was found that the ionic conductivity of the system is carded out through the segmental motion mechanism. However, the data must be treated with care. For example, in evaluating WLF parameters, the contribution concerned with ionic carrier generation with temperature to the conductivity must be differentiated from that concerned with segmental motion. Besides, the temperature range suitable to WLF equation must also be considered. For VTF equation, it might be inapplicable ff the temperature is too low and close to the glass transition temperature of the specimen. Further study is needed in order to have a quantitative information on the limitation of these equations.     

电解氟化制备全氟羧酸及其衍生物

一、引言目前,在合成氟有机化合物的手段中,电化学氟化是新近发展起来的一个较为方便而又安全的方法,而且可以广泛应用于各类有机化合物。这个方法的实质在于,电解有机化合物的无水氟化氢溶液或悬浮液,使有机物氟化,而在阴极析出氢气。最早应用此一方法的是席孟斯(Simons),自从他的工作于1949年发表以后,电氟化过程引起了广泛的兴趣,并且得到愈来愈多的应用。     

高分子固体电解质研究的进展

高分子固体电解质是近年来开发的可用于全固态电池等方面的新型材料,它具有优良的成膜性和粘弹性等一般无机固体电解质所不具备的特点。但由于室温电导率很低,应用受到限制。为了改进这一点,已进行了许多研究,并取得了不少进展。目前改性聚氧乙烯(PEO)的室温电导率可达10~(-4)S·cm~(-1)。本文主要讨论提高高分子固体电解质性能的途径,其中大部分是关于PEO的化学和物理改性,例如共聚、共混和交联等,同时也介绍了非聚醚、非氧型及自电离聚合物,并对今后的发展前景作了简要探讨,     

用硷法分解独居石的研究

用热液球磨分解法进行分解国产独居石的研究,在独居石矿砂(不必粉碎)与氢氧化钠的比例1:1,硷液浓度为50％,反应温度为160±2℃,反应时间为6小间的条件下,矿砂的分解率在95％以上。文中列出了常压分解,压热分解等分解独居石的方法的较好操作条件,也将热液球磨分解法、常压分解法和压热分解法进行了比较,认为热液球磨分解法是其中较好的方法。     

MECHANICAL RELAXATION TIME OF A TWO-COMPONENT EPOXY NETWORKLiClO_4 POLYMER ELECTROLYTE

The mechanical relaxation time of a two-component epoxy network-LiClO_4 system as a polymer electrolyte was investigated. The network is composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG), wherein LiCIO_4 was incorporated and acts as both the ionic carrier and the curing catalyst. As the relaxation time is informative to the segmental mobility, which is known to be essential for ionic conductivity, the average relaxation times of the specimens were determined through master curve construction. Experimental results showed that the salt concentration, molecular weight of PEG in DGEPEG and DGEPEG/TGEG ratio have profound effect on the relaxation time of the specimen. Among these factors , the former reinforces the network chains, leading to lengthen the relaxation time, whereas the latter two are in favour of the chain flexibility and show an opposite effect. The findings was rationalized in terms of the free volume concept.     

环氧树脂/聚氧化乙烯共混物及其与硫氰化钠络合物的结构研究(Ⅰ)

对不同分子量聚氧乙烯(PEO)以不同比例与双酚A二缩水甘油醚型环氧树脂(ER)制得的交联共混物ER/PEO,以及再与NaSCN络合后的产物用WAXD,SAXS,DSC和SEM等方法进行了研究,结果表明:随着ER含量的增加,ER/PEO共混物由晶态转为非晶态。ER/PEO属单斜晶系;与NaSCN络合后,体系结晶性变差。ER/PEO-NaSCN属三斜晶系,其长周期比相应ER/PEO交联共混物的长周期值大。EP的加入使非晶层增厚,结晶片层变薄,长周期值增加。