高聚物固体电解质聚氧化乙烯－溴化铜复阻抗谱及介电常数的静水压效应

采用分子量５００万的聚氧化乙烯和无水溴化铜，通过混溶蒸发法制备成高聚物固体电解质Ｐ（ＥＯ）ｎ－ＣｕＢｒ２薄膜，并在０．１～３００ＭＰａ范围不同的流体静水压下详细测量其复平面阻抗谱，分别得到在不同压力下离子电导率和介电常数与测量频率的关系．进一步解谱准确地求出Ｐ（ＥＯ）ｎ－ＣｕＢｒ２（ｎ＝１２、１６）薄膜离子电导率和介电常数的静水压效应，并结合Ｘ－光物相分析，根据离子迁移通道的物理图象和高聚物的极化机构进行了初步的讨论．添加２０％的增塑剂碳酸丙烯酯，较大改进了压力下的导电性．１２０～３００ＭＰａ的离子电导率提高一个数量级     

CuZSM-5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量、反应温度、反应时间及ｎ（ＰｈＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响．     

聚醋酸乙烯酯与铜（Ⅱ）离子的配位反应及其催化作用

以ＥＳＲ、ＵＶ和ＩＲ表征Ｃｕ（２＋）离子与ＰＶＡＣ的配位反应。根据ＣＵＣｌ２·２Ｈ２Ｏ乙醇溶液与ＰＶＡｃ－ＣｕＣｌ２·２Ｈ２Ｏ乙醇溶液的电导率差值随Ｃｕ（２＋）离子摩尔浓度变化的明显转析点得知，１个Ｃｕ（２＋）离子大约能与ＰＶＡｃ４个链节单元配位。证实ＭＭＡ在Ｃｕ（Ⅱ）－ＰＶＡｃ配合物／Ｎａ２ＳＯ３体系的聚合体是无规ＰＭＭＡ，得率为７０％。讨论了ＭＭＡ在Ｃｕ（Ⅱ）－ＰＶＡｃ配合物／Ｎａ２ＳＯ３体系络合催化引发下的游离基反应历程。     

碳基铁—硫醇（硫酚）—格氏试剂体系与芳酰氯反应的研究：…

通过Ｆｅ３（ＣＯ）１２、硫醇（硫酚）和ＥｔＭｇＢｒ所形成的络盐［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ６）》－Ｍｇ＾＋Ｂｒ与氯代芳酰氯的原位反应，合成了通式为（μ－ＲＳ）（μ－ｏ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ６）和（μ－ＲＳ）（μ－ｍ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６（Ｒ＝ｎ－Ｂｕ，ｔ－Ｂｕ，Ｐｈ）的６个新桥芳酰基铁硫配合物，并用Ｃ／Ｈ分析、ＩＲ和＾１ＨＮＭＲ表征了它们的结构。     

β—型过渡元素三取代钨锗杂多配合物的合成,表征和催化活性

报道Ａ－β－Ｍ＇ｘＨｙ－［ＧｅＷＯＭ３（Ｈ２Ｏ）３Ｏ３７］．ｎＨ２Ｏ（Ｍ＝Ｃｒ＾３＾＋，Ｃｏ＾２＾＋，Ｎｉ＾２＾＋，Ｃｕ＾２＾＋；Ｍ＇＝Ｂｕ４Ｎ＾＋，Ｋ＾＋）的立体有择合成法制备及红外和远红外光谱，紫外和可见光谱和循环伏安，磁化率和磁矩，ＸＰＳ，ＥＳＲ以及催化活性等研究结果。     

CuZSM—5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量，反应温度，反应时间及ｎ（ＰｂＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响。     

甲烷部分氧化制合成气Ⅱ．镍系催化剂的反应性能

主要用第四周期金属元素的氧化物与Ａｌ２Ｏ３的复合氧化物催化剂上甲烷氧化的结果证实了催化剂设计中的预测：（１）催化剂首先应能解离活化甲烷，（２）催化剂要能较快地活化Ｏ２分子．只有同时满足这两个条件，催化剂才可能有较好的甲烷部分氧化活性．第四周期元素中只有镍具有这样的性质．Ｃｕ，Ｍｎ，Ｃｒ，Ｌａ，Ｃａ，Ｚｎ等氧化物的添加可明显提高Ｎｉ－Ａｌ２Ｏ３催化剂的甲烷部分氧化性能，其中Ｃｕ的助催化性能最好．催化剂ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３，ＮｉＯ－ＭｎＯ－Ａｌ２Ｏ３，ＮｉＯ－Ｃｒ２Ｏ３－Ａｌ２Ｏ３的反应活性和选择性顺序，与金属Ｃｕ，Ｍｎ，Ｃｒ上ＣＯ和Ｈ２脱附的顺序是一致的     

稀土铕与2—[（取代苯胺基）羰基]苯甲酸配合物的研究

报道了配合物Ｅｕ（ＸｎＰ）３．３Ｈ２Ｏ「其中Ｘ＝Ｈ，２－Ｃｌ，３－ＯＨ，４－Ｂｒ，３－ＮＯ２，２－ＯＣＨ３，２－ＣＨ３，２，４－二氯；Ｐ＝２－（ＣＯＯ）Ｃ６Ｈ４ＣＯＮＨＣ６Ｈ５－＾－，ｎ＝１，２」的制备，并用元素分析，红外光谱，电子反射光谱，热重分析进行了表征。     

MoO_2Br_2体系催化丁二烯聚合中烯丙基卤素的作用

ＭｏＯ２Ｂｒ２－Ａｌ（ｉ－Ｂｕ）２ＯＰｈＣＨ３（－ｍ）体系催化丁二烯１，２－聚合过程中添加Ｃ３Ｈ５Ｘ（Ｘ＝Ｃｌ、Ｂｒ和Ｉ）对聚合物分子量有较好的调节作用，其中以Ｃ３Ｈ５Ｂｒ的调节作用最强，Ｍｎ从１７．５×１０５降至３．５×１０５，但对催化活性有一定的影响．在测定催化体系的ＵＶ光谱、（１３）Ｃ－ＮＭＲ谱、聚合活性和聚合动力学参数的基础上，讨论了Ｃ３Ｈ５Ｘ在催化体系中的行为．     

双核金属酞菁类化合物催化脱硫机理研究Ⅳ──中心金属离子对MPc－PcM催化活性的影响

实验研究结果表明双核金属酞菁类化合物ＭＰｃ－ＰｃＭ（Ｍ＝Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ）是催化Ｈ＿２Ｓ液相氧化反应的良好催化剂，且其催化活性顺序为Ｃｏ＞Ｎｉ＞Ｖ＞Ｆｅ＞Ｃｕ＞Ｃｒ＞Ｍｎ．采用量子化学理论计算方法（ＩＮＤＯ／Ｓ）分析了其前线分子轨道的构成特征，结果表明这几种ＭＰｃ－ＰｃＭ的ＬＵＭＯ轨道皆为有金属离子参与形成的π轨道，但ＨＯＭＯ轨道间的差异却很大．Ｍ＝Ｃｏ、Ｎｉ、Ｃｕ、Ｃｒ时，其ＨＯＭＯ为π轨道；而Ｍ＝Ｆｅ、Ｍｎ时，其ＨＯＭＯ却为σ轨道．正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下，才导致ＭＰｃ－ＰｃＭ的催化活性顺序并非按中心金属离子价电子层ｄ电子数的递变而呈现出规律性的变化．     

Self-assembled monolayers of an oligo(ethylene oxide) disulfide and its corresponding thiol assembled from water: characterization and protein resistance

Self-assembled monolayers (SAMs) of the disulfide [S(CH2CH2O)6CH3]2 ([S(EO)6]2) on Au from 95% ethanol and from 100% water are described. Spectroscopic ellipsometry and reflection-absorption infrared spectroscopy indicate that the [S(EO)6]2 films are similar to the disordered films of HS(CH2CH2O)6CH3 ((EO)6) and HS(CH2)3O(CH2CH2O)5CH3 (C3EO5) at their protein adsorption minima. The [S(EO)6]2 SAMs exhibit constant film thickness (d) of 1.2 +/- 0.2 nm over long immersion times (up to 20 days) and do not attain the highly ordered, 7/2 helical structure of the (EO)6 and C3EO5 SAMs (d = 2.0 nm). Exposure of these self-limiting [S(EO)6]2 SAMs to bovine serum albumin show high resistance to protein adsorption.     

交联PEO嵌段共聚物固体电解质的制备及导电性研究

利用低分子聚乙二醇 (PEG ,Mn=6 0 0 )与CH2 Cl2 在碱性条件下通过Williamson反应生成氧亚甲基连接的聚氧化乙烯嵌段聚合物 .1 H NMR表明 ,其分子平均组成以 [CH2 O(CH2 CH2 O) 1 3]为重复单元结构 .适量的2 ,4 二异氰酸甲苯酯 (TDI)与聚合物 锂盐电解质形成交联网络结构 ,具有较好的成膜性能、力学性能与热稳定性能 .在测试温度范围内 ,电导率与温度的关系很好的符合Arrhenius关系式 (σ =Ae-Ea RT) .锂盐浓度不同 ,Arrhenius曲线有一个或两个活化能 (Ea)值出现 .该聚合物掺混LiN(CF3SO2 ) 2 形成的固体电解质具有良好的导电性 ,在EO Li =2 5∶1(摩尔比 )时 ,室温下σ =1 12× 10 - 5S cm ,分解电压可达 5 0V .     

PREPARATION OF STAR NETWORK PEG-BASED GEL POLYMER ELECTROLYTES FOR ELECTROCHROMIC DEVICES

An amorphous,colorless,and highly transparent star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized from the poly(ethylene glycol)(PEG),pentaerythritol,and dichloromethane by Williamson reaction.FTIR and ~1H-NMR measurement demonstrated that the polymer repeating units were C[CH_2-OCH_2O-(CH_2CH_2O)_m-CH_2O-(CH_2CH_2O)_n-CH_2O]_4.The polymer host held well mechanical properties for pentaerythritol cross-linking.The gel polymer electrolytes based on Lithium...     

二氧化碳-环氧乙烷-氧化环己烯三元共聚物的制备与性能

采用稀土三元催化剂实现了二氧化碳、氧化环己烯与环氧乙烷的三元共聚,当环氧乙烷和氧化环己烯等摩尔投料时催化活性达到690 g/(mol Zn h),所得三元共聚物的数均分子量达到7.9×104,远程异核多量子相关核磁谱证明所得共聚物主要是无规三元共聚物,其中环氧乙烷-二氧化碳结构单元与氧化环己烯-二氧化碳结构单元相连的全交替结构占26.9%.二氧化碳-氧化环己烯共聚物的脆性导致其熔体加工十分困难,引入环氧乙烷为第三单体进行三元共聚,实现了二氧化碳-氧化环己烯共聚物的增韧,解决了其熔体加工难题,而且改变环氧单体比率能够调节三元共聚物的耐温性能和力学性能,当环氧乙烷与氧化环己烯等摩尔投料时,所得三元共聚物在20℃下的杨氏模量达到(900±17)MPa,拉伸强度为(38±2)MPa,断裂伸长率为(26.3±9.2)%.     

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.     

Mixed protonic-electronic conduction and dielectric response in layered vanadyl phosphate nanocomposites

The layered vanadyl phosphate, VOPO(4)2H(2)O, is employed to prepare nanosized conducting polypyrrole by redox intercalation method. Transport and dielectric properties of various compositions have been investigated by impedance technique over a temperature range of 300-120 K. Grain boundary conductivity is larger than the bulk conductivity. The conductivity reveals a discontinuity at about 212-235 K. The conductivity is predominantly ionic at high temperature and electronic at low temperature. The dielectric spectra reveal a peak in the frequency range up to 2 MHz for higher concentration of intercalated polypyrrole. The activation energy of conductivity relaxation is different from that of total conductivity derived from the impedance plot.     

Electrical and optical characterization of PMMA doped with Y0.0025Si0.025Ba0.9725 (Ti(0.9)Sn0.1)O3 ceramic

<正>Poly(methylmetacrylate)(PMMA)/Y_(0.0025)Si_(0.025)Ba_(0.9725)(Ti_((0.9))Sn_(0.1))O_3(YBTS) composites were prepared at different weight ratios of YBTS(0 wt%,5 wt%,10 wt%and 20 wt%YBTS) in order to investigate effect of YBTS additions on the electrical and optical properties of PMMA host.The electrical properties(impedance,dielectric constant dielectric loss and AC conductivity) were studied in the frequency range 10 kHz-1 MHz and in temperature range 20-90℃.Upon increasing the contents of YBTS ceramic,we observed a reduction in the impedance and an increase in the dielectric constant,dielectric loss and AC conductivity of PMMA host.We also found that the relaxation process at high YBTS contents was due to relaxation in the ionic conductivity.The absorption coefficient(α) has been determined in the wavelength range 230-800 nm at room temperature for all YBTS-PMMA composites.Moreover,the addition of YBTS ceramic highly enhances the UV absorption of PMMA host especially below 300 nm.Addition of 20 wt%YBTS ceramic to PMMA host decreases the optical energy gap from 5 eV to 3.41 eV.Correlations between electrical,optical and SEM results are reported.     

梳状高分子固体电解质的离子导电性研究

深入研究了交替马来酸酐共聚物多缩乙二醇酯（ＣＰ３５０）两种锂盐络合物ＣＰ３５０／ＬｉＡｓＦ＿６和ＣＰ３５０／ＬｉＰＦ＿６的离子传导性能,给出了与复阻抗谱相对应的等效电路．离子电导率随［Ｌｉ］／［ＥＯ］的变化而出现一极大值,室温下,两体系电导率极大值分别为１．３８×１０（－４）,８．３２×１０（－５）Ｓ／ｃｍ．电导率随温度升高而增加．导电行为呈非－Ａｒｒｈｅｎｉｕｓ特征．阴阳离子半径之和（ｒ＿ｃ＋ｒ＿ａ）愈大,离子电导率愈高．     

超支化聚氨酯固体电解质导电性能的光谱学研究

用超支化聚氨酯 +线性聚氨酯作为基体 ,LiClO4作为离子源制得聚合物固体电解质 .用Raman光谱 ,FTIR光谱等光谱学方法研究了聚合物电解质中盐离子和聚合物基团之间的相互作用 .研究表明超支化聚氨酯对盐有较好的溶解作用 .研究还表明超支化聚氨酯加入有利于提高体系的电导率     

Dielectric study of hot-pressed nanocomposite polymer electrolytes

Ion-conducting nanocomposite polymer electrolyte films based on poly(ethylene oxide)-NaPO₃ 3: 1 with up to 15 wt % of SiO₂ have been prepared using recently developed hot-press technique instead of conventional solution cast method. With 7 wt % of SiO₂, the film conductivity has been enhanced by an order of magnitude. The materials have been characterized by Fourier transform infrared spectrometry and thermogravimetric analysis. For the composition with the highest conductivity, the temperature dependences of ionic mobility, mobile ions concentration, ionic transference number, and ionic drift velocity have been determined. Dielectric constant and dielectric loss have been measured. The conductivity enhancement has been discussed on the basis of existing theories of dielectrics.