3,6-二（3,6-二叔丁基咔唑基）-咔唑的合成研究

以咔唑为主要原料,经烃化、碘代、磺酰化、Ullmann反应和水解反应合成了3,6-二（3,6-二叔丁基咔唑基）-咔唑,五步反应总收率为50.3%,中间体及产品进行了1 HNMR检测。该合成工艺具有路线简单、操作方便、产率高等优点,适合大批量制备。     

3-羟基-1-金刚烷甲酸的合成研究

以1-金刚烷甲酸为原料、硝酸和浓硫酸为氧化剂氧化合成了3-羟基-1-金刚烷甲酸。在优化反应条件下,3-羟基-1-金刚烷甲酸最高收率可达77％。采用红外光谱、核磁共振氢谱、元素分析、熔点测定等方法对产物进行了结构鉴定,并提出了可能的反应机理。     

N-烃基咔唑-3,6-二甲醛的合成

以苄基三正丁基氯化铵为相转移催化剂,苯为溶剂,50%NaOH溶液为缚酸剂,咔唑与卤代烃(RX)在n(咔唑)∶n(RX)=1∶1.2,回流状态下反应3～4 h,制得N-烃基咔唑;氯苯为溶剂,所制备的烃基咔唑与4倍物质的量的新蒸DMF和POCl3反应,合成了标题化合物,通过1HNMR、IR对产物进行了结构表征。     

硅胶催化合成3,6-二溴咔唑

以咔唑、N-溴代丁二酰亚胺(NBS)为原料,硅胶为催化剂,合成3,6-二溴咔唑,考察了反应时间、原料配比、溶剂用量和催化剂用量对反应的影响。正交实验表明,较佳工艺条件为:咔唑、NBS的摩尔比为1∶2,二氯甲烷50 mL,硅胶17 g时,室温下反应12 h,收率达89.25%,熔点为213.5℃。产物结构经TLC、IR进行表征。     

3,6-二溴咔唑的合成工艺改进

3,6-二溴咔唑是重要的医药中间体,本文采用N-溴代丁二酰亚胺法、液溴法和硅胶法三种方法合成了3,6-二溴咔唑,实验结果表明,硅胶法为较佳路线,并通过正交实验得出最优工艺条件为：室温下反应时间为12h,原料咔唑、N-溴代丁二酰亚胺、溶剂二氯甲烷、催化剂硅胶的用量物质的量比为1：2：131：47时,产品平均收率可提高到89．25％。同时,通过单因素实验对原料配比、反应时间、溶剂用量和催化剂用量四种因素对反应的影响进行了研究。     

改性骨架镍催化加氢合成3-氨基-9-乙基咔唑研究

以改性骨架镍为催化剂，对3-硝基-9-乙基咔唑进行低压液相催化加氢合成3-氨基-9-乙基咔唑。研究了催化剂／溶剂体系、温度和氢气压力等因素对加氢反应的影响，并进行了催化剂的循环套用试验和放大试验。     

基于1,3-金刚烷二甲酸Cu配位聚合物的构筑及其性能研究

混合的1,3-金刚烷二甲酸和1,4-二(2-甲基咪唑)丁烷溶解在甲醇溶液中,调节pH至7. 0,然后将该溶液扩散到含有Cu(NO_3)2的水溶液中反应去构筑二维金属有机化合物。此外,我们也做了X-射线粉末衍射、热重等性质的表征,这些性质的测定为该类配合物的研究奠定了一定基础。本论文拟得到的配合物材料是具有生物活性,通过实验结果分析,这些结果可以为新药的研制、筛选提供初步的理论指导和实验依据。     

金刚烷衍生物的合成

以2-金刚烷酮为原料,经还原、氯代,得到2-氯金刚烷,确定金刚烷酮∶硼氢化钠的最佳物质的量比为1∶5,总收率49.3%。以1-金刚烷胺为原料合成了1-异硫氰酸金刚烷酯,确定n(1-金刚烷胺)∶n(二硫化碳)∶n(三乙胺)=1∶2.5∶2,选用氯乙酸钠酯化分解,总收率56.5%。目标化合物结构用核磁和红外光谱进行了表征。     

N-(3-氯苯基)金刚烷甲酰胺的合成

以金刚烷和无水甲酸为原料,在浓硫酸催化下合成1-金刚烷甲酸,再经酰化反应生成目标产物,总收率约为85.3%。第2步最佳的工艺条件为:反应温度130℃,反应时间4 h,1-金刚烷甲酸、间氯苯胺和亚磷酸三苯酯的投料物质的量比为1∶1∶0.6,溶剂用量50 mL。所得化合物结构经1H NMR和IR进行表征。     

N-乙基-3-咔唑丙烯酸的合成及性质研究

用N-乙基咔唑合成N-乙基-3-咔唑甲醛,在吡啶介质中以六氢吡啶为缩合剂,通过N-乙基-3-咔唑甲醛与丙二酸的Knoevenagel缩合反应合成N-乙基-3-咔唑丙烯酸,并对影响产率的因素进行了研究。结果表明,当n(N-乙基-3-咔唑甲醛)∶n(丙二酸)∶n(吡啶)∶n(六氢吡啶)=1.0000∶3.0000∶2.0000∶0.0015时,在105℃下反应2h,N-乙基-3-咔唑丙烯酸的产率为85%,纯度为99.45%。     

Synthesis and properties of poly(3,9-carbazole) and low-molar-mass glass-forming carbazole compounds

The novel π-conjugated polymer poly(3,9-carbazole) was prepared by Ullmann polycondensation reaction of 3-iodo-9H-carbazole. The polymer has a number-average molecular weight of ca. 2400 with a molecular weight distribution of 2.15. The dimer model compound and the carbazole trimer 3,6-di(carbazolyl)alkylcarbazole have been synthesized by stepwise reactions. All these compounds have been found to form glasses with glass transition temperatures in the range 35-157 °C as characterized by differential scanning calorimetry. The ionization potentials of these compounds range from 5.45 to 5.97 as determined by the electron photoemission method. Time of flight experiment showed that hole drift mobilities of the low-molar-mass glasses were in the range 10⁻⁵-10⁻³ cm² V⁻¹ s⁻¹.     

Synthesis and properties of novel conducting polyaniline copolymers

A novel copolymer based on aniline and N‐β‐cyanoethylaniline was chemically prepared and characterized by a number of techniques including UV–vis, FTIR, ESR, XRD, and TGA. According to the systematic studies on the physical properties, it was found that the copolymers had excellent solubility in common organic solvents especially in DMF and pyridine, while the conductivity and yield decreased as the content of cyanoethyl group increased in the system. Moreover, an increase in the feed ratio of N‐β‐cyanoethylaniline induced a blue‐shift of the absorption bands in the UV–vis and IR region and significant line broadening of ESR signals together with a reduction in spin density. The XRD patterns of the copolymers lost the characteristic diffraction peaks of emeraldine salt as the ratio of cyanoethyl group increased. The thermal stability of the copolymer was increased with increasing the feed molar ratio of N‐β‐cyanoethylaniline. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 140–147, 2007     

Synthesis and properties of styrene–butylacrylate emulsion copolymers modified by silane compounds

Styrene (St)/butyl acrylate (BA) copolymers were prepared by adding triethoxyvinylsilane (TEVS), trimethoxyvinylsilane (TMVS), and triphenylvinylsilane (TPVS), each one through emulsion copolymerization. The polymerization was performed with methacrylic acid and auxiliary agents at 80°C in the presence of potassium peroxodisulfate as the initiator. Nonylphenol ethylene oxide‐40 units (NP‐40) and sodium lauryl sulfoacetate were used as nonionic and anionic emulsifiers, respectively. The resulting copolymers were characterized by using Fourier transform infrared spectroscopy. Thermal properties of the copolymers were studied by using thermogravimetric analysis and differential scanning calorimetry. The morphology of copolymers was also investigated by optical microscopy, and then the effects of silicone kinds and concentrations on the properties of the St/BA emulsion copolymers were discussed. The obtained copolymers have high solid content (50 %) and can be used in emulsion paints as a binder. The comparison of three different vinyl silanes indicates that the TEVS influences on the copolymer properties more than the others. The calculations of monomer conversion and monomer conversion versus time histories indicate that by increasing the silicone concentration, the polymerization rate decreases. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

3,6-二苯甲酰苊的合成与表征

为制备新型精细化工和功能高分子中间体,研究了在高活性Lewis酸无水AlCl3催化下,苊与苯甲酰氯的Friedel-Crafts酰基化反应,GC/MS分析发现生成了3,6-二苯甲酰苊;用GC法考察了各种反应条件对3,6-二苯甲酰苊收率的影响,结果表明,在以1 mmol苊为基准,苯甲酰氯8mmol,AlCl38 mmol,溶剂为CCl4(15 mL),反应温度45℃,反应时间10 h的条件下,3,6-二苯甲酰苊的收率可达到84.2%,选择性达89.9%。通过萃取、重结晶等方法得到3,6-二苯甲酰苊的纯品。通过FT IR、GC/MS和1H NMR等分析测试手段鉴定了其结构。     

3,6-二氯吡啶甲酸合成方法进展

3,6-二氯吡啶甲酸是一种高活性、低毒的农药,主要用作除草剂、杀虫剂和植物生长调节剂.综述了3,6-二氯吡啶甲酸的合成方法并重点介绍了电化学还原脱氯法.水解法反应选择性较高,但原料成本太高,难以实现工业化;肼还原脱氯-水解法和肼还原脱氯法原料制备较为方便,设备比较简单,反应收率可达70％～80％,但反应中需使用剧毒的氰...     

Synthesis and properties of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups for proton‐exchange membrane materials

A series of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups were synthesized via a nucleophilic aromatic substitution reaction from phenolphthalein, hydroquinone sulfonic acid potassium salt, and 2,6‐difluorobenzonitrile in N‐methyl pyrrolidone (NMP) with K₂CO₃ as a catalyst. The synthesized copolymers had good solubility in common polar organic solvents and could be easily processed into membranes from solutions of dimethyl sulfoxide, NMP, N,N′‐dimethyl acetylamide, and dimethylformamide. Typical membranes in acid form were gained, and the chemical structures of these membranes were characterized by Fourier transform infrared analysis. The thermal properties, fluorescence properties, water uptake, ion‐exchange capacity, and proton conductivities of these copolymers were also investigated. The results indicate that they had high glass‐transition temperatures in the range 151–187°C and good thermal stability, with the 10 wt% loss temperatures ranging from 330 to 351°C under nitrogen. The copolymers showed characteristic unimodal ultraviolet–visible (UV–vis) absorption and fluorescence emission, and the UV–vis absorption, fluorescence excitation, and emission peaks of the copolymers were obvious. Moreover, the copolymer membranes showed good water uptake and proton conductivities at room temperature and 55% relative humidity because of the introduction of both sulfonic acid groups and carboxyl groups into the copolymers, whose contents were in ranges 18.45–67.86 and 3.4 × 10^?4 to 3.0 × 10^?3 s/cm, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40213.     

Synthesis and properties of boron-containing soybean oil based thermosetting copolymers

The first example of boron-containing soybean oil based copolymers was prepared from soybean oil, styrene, divinylbenzene and 4-vinylphenyl boronic acid by cationic polymerization using boron trifluoride etherate as initiator. Soxhlet extraction and NMR spectroscopy indicate that the copolymers consist of a crosslinked network plasticized with varying amounts of oligomers and unreacted oil. The thermal degradation mechanism was studied and the thermal, dynamomechanical and flame retardant properties of these materials were examined. Thermosets with glass transition temperatures ranging from 43 to 60 °C, which are thermally stable below 350 °C and with LOI values from 23.7 to 25.6 were obtained. The LOI tests indicate that the flame retardant properties of vegetable oil can be improved by adding boron covalently bonded to the polymer.     

2-羟基-3，6-二氯苯甲酸的合成工艺研究

以2,5-二氯苯酚为原料,经成盐脱水、羧化、酸析合成了2-羟基-3,6-二氯苯甲酸,应用新型羧化催化剂,使羧化收率从原来的65%上升到87%,总收率达86%以上。     

Synthesis and properties of ethylene‐substituted styrene copolymers

The copolymerization of ethylene and substituted styrenes [RSt's; p‐methylstyrene (MSt), p‐tert‐butylstyrene (BSt), 2‐vinylnaphthalene (VN), and p‐(tert‐butyldimethylsilyloxy)styrene (BMSiOSt)] were investigated with dimethylsilylene(tetramethylcyclopentadienyl)(N‐tert‐butyl)titanium dichloride to yield the corresponding ethylene–RSt copolymers. The substituent on the styrene (St) monomers did not affect the monomer reactivity ratio. The effect of the substituent structure of RSt on the thermal and mechanical properties was studied with differential scanning calorimetry, dynamic mechanical thermal spectroscopy, and elongation testing. The glass‐transition temperature (T_g) of the copolymers increased with increasing RSt content, and the order of T_g was as follows: BSt > VN > MSt = St. A copolymer with p‐hydroxystyrene (HOSt) was successively synthesized by means of deprotection of the copolymer with BMSiOSt. The copolymer showed a much higher T_g than the other copolymers because of the hydrogen connection of its OH groups. The mechanical properties of the copolymer in the glass state, at a lower temperature than T_g, were almost independent of the nature of the RSt. The substituent of the St monomers affected the pattern of the stress–strain curve in the elongation testing in the amorphous state. An improvement in the shape memory effect was observed in poly(ethylene‐co‐BSt). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of thiophene functionalized polystyrene copolymers and their electrochemical properties

Thiophene functionalized polystyrene samples (TFPS) were synthesized by atom transfer radical polymerization (ATRP) of styrene, followed by Suzuki coupling with 3‐thiophene (Th) boronic acid. Conducting graft polymer of TFPS with thiophene was achieved at 1.5 V in tetrabutylammonium tetrafluoroborate/dichloromethane (TBAFB/DM) by electrochemical methods. Spectroelectrochemical analysis of the resulting copolymers [P(TFPS‐co‐Th)] reflected electronic transitions at 449, 721 and 880 nm, revealing π ? π* transition, polaron and bipolaron band formation, respectively. We also successfully established the utilization of dual type complementary colored polymer electrochromic devices using P(TFPS‐co‐Th)/poly(3,4‐ethylenedioxythiophene (PEDOT) in sandwich configuration. The switching ability, stability and optical memory of the electrochromic device were investigated by UV–visible spectrophotometry and cyclic voltammetry. Device switches between brown and blue color with a switching time of 1.3 s were prepared with optical contrast (%ΔT) of 25 %. Copyright © 2005 Society of Chemical Industry