碘掺杂的聚二茂铁基席夫碱的合成与性能研究

利用二茂铁甲醛与对、间、邻苯二胺在中性条件下缩合,得到了3种小分子二茂铁基席夫碱,利用Friedel-Crafts反应合成了一类新型的导电聚二茂铁基席夫碱,然后用碘对其进行掺杂,得到了系列电荷转移配合物.聚合物的电导率经碘掺杂后可提高几个数量级,同时均有紫外吸收功能;其中碘掺杂聚对二茂铁基席夫碱配合物的电导率最高,达3.17×10-4S/cm,而碘掺杂聚邻二茂铁基席夫碱配合物的磁增重另外2种配合物的2～3倍.     

席夫碱钼(Ⅵ)配合物催化合成环氧环己烷

以合成的水杨醛缩2-氨甲基吡啶席夫碱钼配合物([MoO_2(L_1)(EtOH)])、邻羟基苯乙酮缩2-氨甲基吡啶席夫碱钼配合物([MoO_2(L_2)(EtOH)])、2-吡啶甲醛缩邻氨基酚席夫碱钼配合物([MoO_2(L_3)(EtOH)])为催化剂,研究了叔丁基过氧化氢(TBHP)作氧化剂时3种配合物在制备环氧环己烷中的催化活性。3种席夫碱配合物中[MoO_2(L_3)(EtOH)]的催化活性最高。详细考察了反应时间、温度、催化剂用量、氧化剂用量对环己烯转化率、环氧产物选择性的影响,筛选出了席夫碱钼催化剂最佳的反应条件:70℃,10 mg[MoO_2(L_3)(EtOH)],n(环己烯)∶n(叔丁基过氧化氢)=1∶2,反应5 h,环己烯的转化率为77.2%,环氧环己烷选择性99%,产率为77.2%。催化剂重复使用性实验表明,该席夫碱配合物具有较高的稳定性。     

二茂铁基席夫碱及盐的合成与导电性能

中性条件下,以二茂铁甲醛和对苯二胺为原料,合成了二茂铁基席夫碱,考查了反应温度和时间对产率的影响,并测得其本征态室温电导率σ＝1.26×10-9 S·cm-1。利用Fe3+、Al3+、Ti3+盐对二茂铁基席夫碱进行了掺杂,探讨了掺杂量和掺杂温度对产物室温电导率的影响,研究了掺杂产物电导率与温度的变化关系,并用红外光谱、紫外光谱和电子探针对产物结构和组成进行了表征。结果表明：经金属盐掺杂后,电导率可提高4～5个数量级, 根据Arrhenius曲线得到了化合物的电活化能在0.09～1.54 eV范围内,表明了它们具有较好的半导体性能。     

聚合长链席夫碱盐的合成与性能

在0℃和弱酸催化下利用乙二醛和乙二胺合成聚合长链席夫碱,再用FeCl3掺杂上述中间产物制得聚合长链席夫碱铁盐。阐述了聚合长链席夫碱的合成机理,分析了合成温度对反应的影响以及掺杂剂用量对产物电导率的影响,并表征产物的结构与组成。当掺杂剂FeCl3的用量达到饱和掺杂率时,该方法制得的聚合长链席夫碱铁盐,其电导率为3.02×10-3S/cm。     

纳米棒状聚苯胺/席夫碱复合材料的制备及其电性能研究

采用种子聚合法制备了纳米棒状聚苯胺/席夫碱复合材料,研究了席夫碱用量、酸的浓度、有机介质对复合材料导电性能的影响。通过红外光谱、紫外光谱和扫描电镜对复合材料的结构及表面形态进行了表征。结果表明,室温下,保持席夫碱质量为15 %,盐酸浓度为2 mol/L,乙二醇介质中,复合物的电导率最高可达到1.201 S/cm,比聚苯胺的电导率(9.21×10^-6 S/cm)提高了6个数量级,同时聚苯胺/席夫碱复合物分散性和耐热性明显改善。     

1H-吲哚亚甲基氨基硫脲席夫碱铜（Ⅱ）配合物及其涂层的抗菌性研究

选用具有生物活性的吲哚-3-甲醛与氨基硫脲制备了席夫碱及其铜（Ⅱ）配合物,通过核磁共振氢谱、红外及紫外光谱等手段鉴定了其结构并确认配合物的配位方式。选用金黄色葡萄球菌（S. aureus）与大肠埃希氏菌（E. coli）测试了席夫碱及其铜（Ⅱ）配合物的抗菌性。结果表明：所制备的铜（Ⅱ）配合物对革兰氏阳性与革兰氏阴性菌均具有较好的抗菌效果,对金黄色葡萄球菌（S. aureus）和大肠埃希氏菌（E. coli）的最小抗菌浓度分别为0.40 g/L和0.95 g/L,具备广谱抗菌性。以吲哚甲醛氨基硫脲席夫碱铜（Ⅱ）配合物作为抗菌剂制备的抗菌涂层同样具有良好的抗菌效果,质量分数为5%时就能够杀灭抗菌涂层上黏附的大肠埃希氏菌（E. coli）。通过电镜观察细菌形貌推测吲哚甲醛氨基硫脲席夫碱铜（Ⅱ）配合物可能通过直接作用于细胞膜将其杀灭,具有较优的抗菌性。     

Pd(DD)_2/Hβ上苯酚氧化羰基化反应研究

采用微波辅助浸渍法,以Hβ分子筛为载体,合成了负载型席夫碱钯配合物催化剂Pd(DD)2/Hβ(DD为对羟基苯甲醛缩对氨基苯甲酸配体)。采用1H-NMR、XRD、FT-IR、ICP等方法对Pd(DD)2/Hβ进行结构确认,将该配合物用于催化苯酚氧化羰基化制备碳酸二苯酯反应,考察了助催化剂Cu加入量、助催化剂铜钴锰复合氧化物加入量、反应温度、反应时间对DPC产率和选择性的影响。实验结果表明,在反应条件为:铜加入量0.04 g、铜钴锰复合氧化物加入量0.4 g、反应时间8 h、反应温度110℃时,碳酸二苯酯的收率及选择性分别为36.1%和82.2%。     

希夫碱催化剂催化本体开环聚合制备聚己内酯

以ε-己内酯(ε-CL)为单体,希夫碱类配合物为催化剂,本体开环聚合得到高转化率高黏均摩尔质量的聚己内酯(PCL)。考察了催化剂用量、聚合温度和聚合时间对催化性能的影响。在单体物质的量比为150,聚合时间7 h,聚合温度110℃,所得聚己内酯转化率为98.3%,黏均摩尔质量Mη=3.101×104g/mol。     

咪唑烷-2-亚胺为配体的镍配合物催化的降冰片烯与苯乙烯共聚

为了研究[P, N]型镍催化剂的双重强供电子效应对烯烃与极性单体共聚性能的影响，本文设计合成了两种咪唑烷-2-亚胺为配体的镍配合物Ni1和Ni2,并通过核磁对其表征，研究了该类镍配合物在二氯乙基铝(EtClAl₂)助催化剂的活化下催化降冰片烯均聚及其与苯乙烯的共聚行为。结果表明，以EtClAl₂为助催化剂时，配合物Ni1催化降冰片烯均聚活性高达1.92×10⁷ g/(mol·h)。该体系配合物同样有效催化降冰片烯与苯乙烯共聚，Ni1的聚合活性高达2.14×10⁶ g/(mol·h)。该体系催化剂对降冰片烯与苯乙烯共聚表现出良好的聚合性能，从而为高效镍金属催化剂的开发提供理论依据。     

聚苯胺的合成工艺优化及其性能表征

采用化学氧化聚合法在苯胺/过硫酸铵/HCl的水溶液体系中合成聚苯胺,并对其聚合条件([S2O2-8]/[An]比、HCl浓度变化等)进行了优化,以提高PAn的电导率和产率。通过四探针、傅立叶红外吸收光谱(FTIR)、XRD、CV等测试方法对聚苯胺电导率及掺杂前后结构的变化进行了分析。结果表明,当[S2O2-8]/[An]=1∶1、[HCl]=0.8 mol/L时电导率达到最大值2.13 S/cm,产率为94.37%。聚合物具有一定的结晶性,通过CV曲线可以分析出PAn具有掺杂/脱掺杂的电化学活性。     

Synthesis and Characterization of Some Poly(1,2-Phenylenedithiocarbamate)–Metal Complexes

Poly(1,2-phenylenedithiocarbamate) (PPDTC) was prepared by the reaction of 2-aminothiophenol with carbon disulfide followed by condensation through the removal of H₂S gas. PPDTC was used as a ligand to prepare four poly(1,2-phenylenedithiocarbamate)–metal complexes of iron(II), cobalt(II), copper(II), and lead(II), by refluxing with the metal salts. The polymer and its metal complexes were investigated by elemental analyses, UV–visible and IR spectroscopy, inherent viscosity, and magnetic susceptibility. The DC electrical conductivity variation with the temperature in the range 298–498 K of PPDTC and its polymeric copper complex was measured. Both polymer and polymer metal complexes showed an increase in electrical conductivity with an increase in temperature: typical semiconductor behavior. The proposed structure of the complexes is (MLX₂·mH₂O) _n .     

Novel Solid Acid Catalyst,Bentonite-Supported Polytrifluoromethanesulfosiloxane for Friedel–Crafts Acylation of Ferrocene

Solid acid catalyst, bentonite-supported polytrifluoromethanesulfosiloxane (B-PTFMSS) has been for the first time prepared and used in the Friedel–Crafts acylation of ferrocene with various acyl chlorides. The catalytic activities were influenced by reaction time, reaction temperature, solvent and loaded amount of B-PTFMSS. It was found that the new catalyst B-PTFMSS possessed the advantages of high activities giving similar yield of aliphatic acyl ferrocene (>70%) as conventional Lewis acid catalyst aluminum chloride and it can be used repeatedly and easily regenerated. B-PTFMSS has also been characterized by IR spectra, pyridine adsorbed IR, specific surface area and XRD.     

Optimization of PVC– PAN‐based polymer electrolytes

The hybrid plasticized polymer electrolyte composed of the blend of poly(vinyl chloride) (PVC) and poly(acrylonitrile) (PAN) as host polymer, propylene carbonate as plasticizer, and LiClO₄ as a salt was studied. An attempt was made to optimize the polymer blend ratio. XRD, Fourier transform infrared, and DSC studies confirm the formation of polymer–salt complex and miscibility of the PVC and PAN. The electrical conductivity and temperature dependence of ionic conductivity of polymer films are also studied and reported here. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

AlCl3-丙三醇络合催化剂催化1-辛烯齐聚工艺

以1-辛烯为原料,A1C13/丙三醇络合物为催化剂,催化1-辛烯齐聚反应,合成α-烯烃。考察了络合催化剂的添加量、反应温度、反应时间、丙三醇与AlCl3的摩尔比对聚α-烯烃(PAO)收率的影响。结果表明,在AlCl3摩尔分数为4%,丙三醇与AlCl3的摩尔比为0.5,反应温度为40℃,反应时间为4 h的条件下,PAO收率达到85.6%,且具有较好的选择性。     

Polymerizations of nitrogen-containing heterophanes by vapor deposition method,transformation to polymeric films bearing a conjugated structure,and their properties

Summary The polymerizations of three nitrogen-containing heterophanes such as [2.2](2,5)pyridinophane (1), [2.2](2,5)pyrazinophane (2) and N, N-dimethyl-[2.2](2,5)pyrrolophane (3) by the vapor deposition method were carried out. Compounds1, 2 and3 gave poly(2,5-pyridinediyl-ethylene), poly(2,5-pyrazinediylethylene), and poly(N-methyl-2,5-pyrrolediyl-ethylene) as tough films, respectively. The transformation of the ethylene unit in the polymer films to the vinylene one by the dehydrogenation reaction using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) failed in the former two polymeric films and succeded to a certain extent in the latter one. The electrical conductivity of a poly(N-methyl-2,5-pyrrolediyl-vinylene) film obtained by the dehydrogenation reaction was measured to be 4×10^-4 S/cm at room temperature and increased up to 1×10^-2 S/cm on doping with iodine.     

二乙基二茂铁合成工艺的研究

以三氯化铝为催化剂,溴乙烷为烷基化剂,利用二茂铁的Friedel-crafts反应合成出了二乙基二茂铁,探讨了反应温度、物料摩尔比、反应时间、催化剂用量及投料方式对反应的影响,确定了适宜合成工艺:二茂铁、溴乙烷和无水三氯化铝的摩尔比为1∶2.2∶(1.88~1)∶2.2∶2.0,反应温度45℃,反应6.5 h,通过元素分析、红外谱图对产物进行了表征,产率达72%。     

Synthesis of vinylferrocene and the ligand-exchange reaction between its copolymer and carbon nanotubes

To improve the dispersibility of carbon nanotubes (CNTs), poly(vinylferrocene-co-styrene) (poly (Vf-co-St)), was grafted onto the surface of CNTs by a ligand-exchange reaction. Poly(Vf-co-St) was obtained by a radical copolymerization reaction using styrene and vinylferrocene as the monomers. The vinylferrocene was synthesized from ferrocene via a Friedel-Crafts acylation. The molecular weight, molecular weight distribution, and amount of Vf in the poly(Vf-co-St) were 1.32 × 10⁴, 1.69 and 17.6% respectively. The degree of grafting of the copolymer onto the CNTs surface was calculated from thermogravimetric analysis and varied from 27.1% to 79.7%. The addition of the poly(Vf-co-St) greatly promoted the dispersibility of the modified CNTs in anhydrous alcohol. The electrical conductivity of composites prepared from the polymer-grafted CNTs and copolymer (acrylonitrile, 1,3-butadiene and styrene, ABS) strongly depended on the degree of grafting. These results show that the amount of polymer grafted onto the surface of CNTs can be controlled and that the electrical properties of composites prepared with these grafted polymers can be tuned.     

线性高分子聚苯硫醚的合成及溶助剂循环利用的研究

采用均匀设计法研究合成线性高分子聚苯硫醚(PPS)树脂。研究了反应温度、反应时间、原料配比、溶剂用量以及助剂用量等因素对产品得率的影响。实验数据经过多元逐步回归分析,找出其最佳工艺条件:前期反应温度为210.9℃,反应时间为2.8 h;后期反应温度为270℃,反应时间为2.5 h,n(Na2S.9H2O)∶n(对二氯苯)=1.1∶1,V(N-甲基吡咯烷酮)∶n(对二氯苯)=550 mL∶1 mol,m(助剂)∶n(对二氯苯)=20 g∶1 mol。按照此反应条件下反应得到线性高分子聚苯硫醚树脂,其重均相对分子质量接近60 000,平均收率在93.7%以上。不需繁琐的回收工艺,即同时实现了助剂和溶剂的可循环利用,多次循环利用后产品的收率仍高于91.2%。并用热分析、红外分析、元素分析对产品进行了表征。     

Synthesis and characterization of a novel biodegradable polymer poly(lactic acid–glycolic acid‐4‐hydroxyproline)

The effect of certain preparative variables, such as the composition of the feeds, the reaction time, catalyst concentration, degrees Centigrade (°C), and the reaction temperature on the properties of prepared polymer poly(lactic acid–glycolic acid‐4‐hydroxyproline) (PLGA‐Hpr), was investigated via direct melt polymerization with stannous chloride as a catalyst activated by a proton acid. The new polymer had pendant amine functional groups along the polymer backbone chain. The results with regard to the inherent viscosity and yield of PLGA‐Hpr are discussed in relation to a recently proposed polymerization mechanism. The content of lactic acid, glycolic acid, and 4‐hydroxyproline (Hpr) in the copolymer was found to affect the surface and bulk hydrophilicity of various PLGA‐Hpr copolymers. The inherent viscosity of the copolymer and the yield of the reaction depended on the reaction temperature and varied with the reaction time. The higher the 4‐hydroxyproline content of the feedzaq, the lower the inherent viscosity of the copolymer and the yield of the reaction. When the glycolic acid content was more than 70% or the content of HPr was more than 10%, the polymer changed from hemicrystalline to amorphous. The in vitro degradation rate of the PLGA‐HPr copolymers is dependent on the feed ratios of lactic acid and glycolic acid in the polymer chain. Lactic acid‐rich polymers are more hydrophobic; subsequently they degrade more slowly. The structure of this polymer was verified by infrared (IR) spectroscopy, proton nuclear magnetic resonance (¹H‐NMR) spectroscopy, X‐ray diffractometry (XRD), and differential scanning calorimetry (DSC). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3585–3590, 2007