N-甲基-2-[4-二甲基氨基]苯基-3,4-富勒烯基吡咯烷微米片控制合成研究

以富勒烯C60、4-(N,N-二甲基氨基)苯甲醛为原料,通过1,3-偶极环加成反应合成了N-甲基-2-[4-二甲基氨基]苯基-3,4-富勒烯基吡咯烷。首次采用表面活性剂协助自组装的方法制得C60衍生物的微米片结构。结果表明,N-甲基-2-[4-二甲基氨基]苯基-3,4-富勒烯基吡咯烷结晶态形貌为片状结构,形貌和晶体结构受溶剂种类、溶液浓度、醇与溶剂体积配合比、表面活性剂浓度的影响。当甲苯为溶剂,溶液浓度为1.0mg/mL,异丙醇与甲苯体积配合比为3∶1,表面活性剂十六烷基三甲基溴化铵(CTAB)浓度为5.0mmol/L时,N-甲基-2-[4-二甲基氨基]苯基-3,4-富勒烯基吡咯烷结晶态形貌为宽度约3μm、厚度约50nm规则的正方形片状结构。     

一种笼形超分子主体化合物Cryptophane E的合成与表征

以香草醛为原料,在乙醇介质中与1,3-二溴丙烷反应生成1,3-二(4-甲酰-2-甲氧基苯氧基)丙烷,然后在甲醇介质中进行硼氢化还原,最后在甲酸介质中聚合,合成笼形超分子主体化合物Cryptophane E.采用核磁共振谱(1H NMR、13C NMR)、质谱(MS)、紫外光谱(UV)荧光光谱、红外光谱、元素分析等测试技术对Cryptophane E进行表征,重点考察反应温度、时间及原料配比等因素对合成产率的影响,获得最佳反应条件,并深入探讨了合成机理.     

N-甲基-2-(3-羟基苯基)[60]富勒烯吡咯烷衍生物的合成研究

利用1,3-偶极环加成反应,合成分离得到了一种C60吡咯烷衍生物:N-基-2-(3-羟基苯基)[60]富勒烯吡咯烷,通过单因素方法,探讨了反应条件对产物产率的影响,并得到了最佳工艺条件:反应物摩尔比(C60:3-羟基苯甲醛:N-甲基甘氨酸)为1:2:4,反应温度90℃,反应时间2h,产物的产率可达82%(以消耗的C60计).同时用Uv-Vis、FT-IR、1H-NMR、MS等测试手段表征了产物的结构.     

N-甲基-2-(4-羟基苯基)[60]富勒烯吡咯烷衍生物的合成研究

利用肌氨酸和对羟基苯甲醛所形成的亚胺叶立德与C60发生 1,3-偶极环加成反应,合成了一种新型含羟基C60吡咯烷衍生物:N-甲基-2-(4-羟基苯基)[60]富勒烯吡咯烷.通过UV-vis、1H-NMR、MS、FT-IR确定了产物的结构.探讨了反应条件对产物产率的影响,得到了最佳工艺条件:反应物摩尔比为1:2:6,温度为90℃,反应时间为5h,此时产物的产率可达到87%(以消耗的C60计).     

2种富勒烯吡咯烷中间体的合成

利用亚胺叶立德的1,3-偶极环加成法合成了2种带活性基团的富勒烯吡咯烷中间体,即氨基乙基富勒烯吡咯烷和N取代3,4-富勒烯吡咯烷.经基质辅助激光解吸电离飞行时间质谱仪、傅里叶变红外光谱仪和紫外可见光分光光度计表征可知,它们是2种富勒烯吡咯烷中间体.这2种中间体含活性基团,可用于合成更多的富勒烯衍生物,因此在富勒烯化学领域具有广阔的应用前景.     

一种新型螺环酚醛树脂的制备及性能研究

以氮甲基苯胺和苯丙炔酸为原料合成了底物N-甲基-N-苯基-3-丙炔酰胺,叔丁基过氧化氢(TBHP)作氧化剂,三溴化铁作催化剂,通过串联反应发生分子内环化反应生成3-溴-螺[4,5]-三烯酮,进一步与低模量酚醛树脂反应生成螺环酚醛树脂。实验探讨并优化了影响合成反应的因素,对合成的螺环酚醛树脂进行了表征和性能测试,结果令人满意。     

螺环原碳酸酯预聚物的合成及其与环氧树脂的共聚研究

利用正癸醛与甲醇之间的坎尼扎罗反应，合成新的三元醇：2-辛基-2-羟甲基丙二醇，进而合成新的螺环化合物：3，9-二羟甲基-3’，9’一二辛基-1，5，7，11一四氧杂螺环［5，5］十一烷．通过红外光谱、核磁共振且语和元素分析表征了它的结构，在三氯化硼单已胶络合物的催化作用下，该化合物能够进行阳离子双开环聚合反应．用膨胀计法跟踪测试了在聚合反应过程中它的体积膨胀率约为2．8％．合成了它与MDI反应生成的预聚物，研究了该预聚物与环氧树脂共聚固化反应，对共聚过程中的反应历程进行初步探讨，并测试了其改性效应．     

新型螺环化合物的合成及膨胀性能研究

首先将甲醛和丁醛在碱性催化剂的条件下,反应生成2,2-二羟甲基丁醛(DMB),其次将DMB与DOPO反应生成DOPO三元醇,最后用DOPO三元醇与二正丁基氧化锡反应生成新型的螺环化合物,并通过FT-IR和NMR对中间体和最终产物进行结构表征,结果表明成功制备了中间体和最终产物。同时还考察了螺环化合物开环聚合过程中体积膨胀率以及对环氧树脂体积膨胀率的变化,实验结果表明,开环聚合过程体积膨胀率为3.46%,当螺环化合物的添加量为20%时,环氧树脂的体积膨胀率为2.67%。     

新型磷氮硅复合阻燃剂的制备及对ABS树脂的阻燃性能提高研究

以提高ABS树脂阻燃性能为目标,通过三步合成路线,以季戊四醇和三氯氧磷为原料制备螺环磷酸酯二酰氯(SPDPC)为基础,利用二苯基硅二醇和带氨基的KH602反应合成聚硅氧烷来引入硅、氮元素,制得同时含有磷(P)、氮(N)、硅(Si)3种元素的新型阻燃剂PAS,通过FT-IR和31P-NMR分析反应中间体及产物的结构,表明成功合成出了目标化合物;PAS添加到ABS树脂中可明显提高树脂的阻燃性能;PAS添加量为30%(wt)时,其中磷含量为4.47%、氮含量为1.03%和硅含量为4.10%时氧指数达到最高为27.0%。     

含磷螺环原碳酸酯的制备与性能

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和2,2-二羟甲基丁醛(DMB)为原料,合成了DOPO基三元醇(DTHA),再与原碳酸四乙酯(TEOC)发生酯交换反应合成出一种含磷螺环原碳酸酯(SOC)。利用红外光谱、核磁分析和元素分析对合成产物的结构进行了表征。将SOC在三氟化硼乙胺络合物的催化作用下进行阳离子开环聚合,用膨胀计法跟踪测定其膨胀率,对其开环聚合机理进行探讨,并对SOC开环聚合产物的本征阻燃性能进行研究。结果表明,该螺环化合物在160℃进行开环聚合时,体积膨胀率可达5.21%;其开环聚合产物的极限氧指数(LOI)在30%以上,并可通过UL-94 V-0级试验。     

联苯型三芳胺空穴传输材料的新合成工艺研究

三芳胺是一种优良的空穴传输材料,在有机电致发光和有机光导领域有着重要应用.目前的合成方法是在氯化亚铜和邻菲哆啉的催化下,以4,4'-二-碘联苯和二芳基胺反应制备.研究了以4,4'-二溴联苯与二苯胺为原料,研究了在醋酸钯、三叔丁基膦的催化作用下合成N,N,N’,N’-四苯基-1,1'-联苯-4,4’-二胺(TPD)的反应.考察了原料配比、反应时间、催化剂用量以及反应温度对产品收率的影响,得到优化工艺条件为二苯胺与4,4 '-二溴联苯的摩尔比为2.5∶1,醋酸钯用量为0.05mmol,在145℃回流反应6h,产品收率为78.89％.在此条件下,用4,4’-二溴联苯分别与3-甲基二苯胺、4-甲基二苯胺反应合成了N,N'N'-二苯基-N,N '-二(3-甲基苯基)-1,1'-联苯-4,4’-二胺(m-TPD)、N,N’-二苯基-N,N’-二(4-甲基苯基)-1,1’-联苯-4,4’-二胺(p-TPD),产品收率分别为75.59％和69.96％.通过比较,新工艺有效地降低了工艺物料平衡图(PFD)类空穴传输材料的合成成本.     

A novel slurry sampling analysis of lead in different water samples by electrothermal atomic absorption spectrometry after coprecipitated with cobalt/pyrrolidine dithiocarbamate complex

A preconcentration/separation technique based on the coprecipitation of lead with cobalt/pyrrolidine dithiocarbamate complex (Co(PDC)(2)) and subsequently its direct slurry sampling determination by electrothermal atomic absorption spectrometry (AAS) was described. For this purpose, at first, lead was coprecipitated with cobalt/pyrrolidine dithiocarbamate complex formed using ammonium pyrrolidine dithiocarbamate (APDC) as a chelating agent and cobalt as a carrier element. The supernatant was then separated and the slurry of the precipitate prepared in Triton X-100 was directly analyzed by electrothermal atomic absorption spectrometry with respect to lead concentration. The effects of experimental conditions on coprecipitation of lead with gathering precipitate as well as homogeneity and stability of the slurry were investigated. After the optimization of experimental parameters, a 100-fold enrichment of the analyte with quantitative recovery (>90%) and high precision (<10% R.S.D.) were obtained. By using the proposed technique, the lead concentrations in heavy matrices of Certified Sea-water and wastewater samples could be practically and rapidly determined in the range of 95% confidence level. The detection limit of the described method for lead using sample-matching blanks was 1.5ng/L (3sigma, N=10).     

Synthesis and evaluation of polymer-based zwitterionic stationary phases for separation of ionic species

Three different zwitterionic functional stationary phases for chromatography were synthesized on the basis of 2-hydroxyethyl methacrylate (HEMA) polymeric particles. Two synthesis routes, producing materials designated S300-ECH-DMA-PS or S300-TC-DMA-PS, involved activation of the hydroxyl groups of the HEMA material with epichlorohydrin or thionyl chloride, respectively, followed by dimethylamination and quaternizing 3-sulfopropylation with 1,3-propane sultone. The third route was accomplished by attaching methacrylate moieties to the HEMA through a reaction with methacrylic anhydride, followed by graft photopolymerization of the zwitterionic monomer 3-[N,N-dimethyl-N-(methacryloyloxyethyl)ammonium] propanesulfonate, initiated by benzoin methyl ether under 365-nm light. According to elemental analyses, both the S300-ECH-DMA-PS and S300-TC-DMA-PS materials appeared to have overall charge stoichometries close to unity, whereas the grafted material, S300-MAA-SPE, seemed to carry an excess of anion exchange sites in addition to the zwitterionic groups. Yet all three zwitterionic stationary phases were capable of separating inorganic anions and cations simultaneously and independently using aqueous solutions of perchloric acid or perchlorate salts as eluent, albeit with markedly different selectivities. On the S300-TC-DMA-PS and S300-MAA-SPE materials, the retention times increased for cations and decreased for anions with increasing eluent concentration, whereas with the S300-ECH-DMA-PS material, the retention times of both anions and cations decreased with increasing eluent concentration. These results demonstrate the importance of choosing appropriate synthesis conditions in order to prepare covalently bonded zwitterionic separation materials with an acceptable charge balance.     

含氮化合物的等离子共聚研究

报道了含氮化合物如吡咯（Ｐyr)、吡啶（Ｐd)、四氢吡咯（Ｐyd)和六氢吡啶（Ｐpd)等离子（Plasma)聚合研究结果,它们具有相对不同的聚合行为。同时不研究了催化剂Ｉ２对Ｐlasma聚合的加速作用,可使吡咯Ｐlasma聚合速率提高４０％－６０％。     

Click Chemistry: Versatility and Control in the Hands of Materials Scientists

The increasing need for materials with tightly controlled structures will continue to fuel the induction of synthetic organic concepts into materials science. One powerful example is the embracement of “click chemistry” by the materials science community. Because of their high selectivity, near‐perfect reliability, high yields, and exceptional tolerance towards a wide range of functional groups and reaction conditions click reactions have recently attracted increased attention, specifically for use in polymer synthesis as well as for the modification of surfaces and nanometer‐ and mesoscale structures. As outlined in this Review article, click chemistry, such as the Cu^I‐catalyzed Huisgen 1,3‐dipolar cycloaddition and the Diels–Alder reaction, presents a synthetic concept that lends itself superbly to the controlled preparation of multifunctional materials.     

含联炔多炔丙基化合物的合成及聚三唑树脂的制备EI北大核心CSCD

采用相转移催化法合成了含联炔多炔丙基的单体N,N,N’,N’-四炔丙基-1,4-双(3-氨基苯)-丁二炔(TPBAPB),通过红外、核磁、元素分析等方法表征了TPBAPB的结构。以TPBAPB与4,4’-联苯二苄叠氮(BAMBP)热聚合条件下的1,3-偶极环加成反应制备了一种新型的聚三唑树脂(H-PTA),利用红外和差示扫描量热法研究了树脂的固化行为,并通过动态力学分析和热失重分析考察了炔基与叠氮基不同摩尔比对树脂热性能的影响。结果表明,树脂具有良好的加工性能,能在较低的温度下进行固化(80℃左右),当炔基与叠氮基的摩尔比为1.2∶1.0时,固化后的树脂具有最佳的热性能,玻璃化转变温度(Tg)达到298℃,在氮气中5%的热失重温度(Td5)达到363℃。     

Electrogenerated chemiluminescence derivatization reagents for carboxylic acids and amines in high-performance liquid chromatography using tris(2,2'-bipyridine)ruthenium(II)

2-(2-Aminoethyl)-1-methylpyrrolidine and N-(3-aminopropyl)pyrrolidine (NAPP) were found to be selective and sensitive derivatization reagents for carboxylic acid by high-performance liquid chromatography (HPLC) with electrogenerated chemiluminescence detection using tris(2,2'-bipyridine)ruthenium(II). Free fatty acids and ibuprofen were used as model compounds of carboxylic acids, and the derivatization conditions were optimized with myristic acid as a representative of free fatty acids. All the fatty acids tested were reacted with NAPP to produce highly sensitive derivatives under the mild reaction conditions of room temperature for 30 min in acetonitrile containing 2-bromo-1-ethylpyridinium tetrafluoroborate and 9-methyl-3,4-dihydro-2H-pyrido[1,2-a]pyrimidin-2-one. The chemiluminescence intensities were similar for all fatty acids. The derivatives obtained from 10 free fatty acids were completely separated by reversed-phase chromatography under isocratic elution conditions. The on-column detection limits (signal-to-noise ratio of 3) with proposed HPLC separation and chemiluminescence detection were 70 and 45 fmol for myristic acid and ibuprofen, respectively. The free fatty acids in human plasma were successfully determined using the present method. Histamine, a model compound of primary amines, was also determined after precolumn derivatization with 3-(diethylamino)propionic acid at room temperature for 60 min in acetonitrile containing N,N'-dicyclohexylcarbodiimide and 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine with the detection limit of 70 fmol.     

Self-assembly of one-side-functionalized graphene nanosheets in bilayered superstructures for drug delivery

In this article, we describe the one-side functionalization of graphene nanosheets with hydrophilic catechol-bearing pyrrolidine rings. For this purpose, we used, for the first time, a solvothermal alternative of 1,3 dipolar cycloaddition of azomethine ylide. To achieve asymmetrical reaction, graphene nanosheets were initially and during reaction deposited on glass substrate. The result of one-side functionalization of graphene was the formation of amphiphilic few-layered graphene nanosheets. The modified side becomes hydrophilic due to the attachment of catechols, while the nonmodified side remains hydrophobic. In the literature, there are limited examples of functionalized graphene with different sides, the so-called Janus-type graphenes. These amphiphilic graphene nanosheets dispersed in water were self-organized in bilayer superstructures, with hydrophilic outer surface and hydrophobic internal space. The later can host hydrophobic molecules such as anticancer drugs and could be used in drug delivery systems. As an example, camptothecin, a drug practically insoluble in water, was used here to show that it can be transferred to water phase using graphene as transporter.     

N80钢在川西某气井常温常压和高温高压下的腐蚀行为

管道钢在高温高压环境中的热力学条件和腐蚀动力学过程不同,因而其腐蚀规律及机理与常温常压下有很大不同.利用电化学方法研究了N80管道钢在川西某气井含饱和CO2的腐蚀介质中于常温常压和高温高压环境下的极化曲线和交流阻抗特征,通过对比发现:2种环境下的阳极反应机理相同而阴极反应机理不完全一样;高温高压条件下N80钢的腐蚀速率...     

Evaluation of 1,3-butadiene dimerization and secondary reactions in the presence and absence of oxygen

Thermal stability evaluation of exothermic chemical reactions is of great importance to the safer design and operation of chemical processes. Dominant reaction stoichiometries and their thermochemistry parameters are key elements in the evaluation process. Identification of significant reaction pathways under possible process conditions will lead to an understanding of the overall thermodynamic and kinetic behavior. The kinetics of 1,3-butadiene (BD) is an excellent example of conjugated dienes that undergo addition reactions. At elevated temperatures, 1,3-butadiene monomers can dimerize exothermally, and as temperature increases, secondary exothermic reactions will take place. The very high temperature and pressure rates that these reactions can attain may lead to a reaction runaway or even a thermal explosion. BD is a vapor at ambient conditions, usually stored as a pressurized liquid, and is a carcinogen, so the experimental evaluation is potentially difficult and hazardous. In this paper, the thermal stability of BD is evaluated. Dimerization and other secondary reactions are investigated by experimental thermal analysis using an automatic pressure adiabatic calorimeter (APTAC), by theoretical computational quantum chemistry methods, and empirical thermodynamic-energy correlations. A theoretical approach is conducted to predict some of the BD reaction behavior. Results are compared to other literature data obtained using different experimental methods.