新型七员环缩醛(酮)的催化合成研究

研究了在HMCM-22沸石分子筛催化下,1,4-丁二醇与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正辛醛、苯甲醛等10余种醛(酮)的缩合反应合成新型七员环缩醛。系统考察了反应时间、醛(酮)与醇的配比、HMCM-22沸石的用量及催化剂重复使用等因素对反应的影响,优化了反应条件。结果表明,当醛(酮)与1,4-丁二醇物质的量比为1∶1.5,催化剂用量为5 g/1 mol醛(酮),反应2 h,转化率一般可达95%以上,选择性一般可达95%以上。证明HMCM-22沸石分子筛对该缩合反应有较好的催化活性和选择性。     

环缩酮类香料催化合成

采用氟磺酸树脂作催化剂,乙酰乙酸乙酯、环己酮分别与乙二醇、１,２－丙二醇进行催化缩合,合成了具有新鲜苹果香和花木一薄荷香的两类环缩酮香料。试验结果表明,此固体催化剂不仅活性高,而且后处理简便,不污染环境;其缩合的最佳温度均为９５℃。     

Insoluble Lignin Models (V): Preparation and Alkaline Condensation Reactions of a Polymer-Bound Quinone Methide

A lignin model, capable of forming a quinone methide in alkali, was bound to polystyrene and heated in alkali with 2,6-dimethoxyphenol. The polymer-supported phenol did not react with the soluble phenol under a variety of conditions, while an analogous non-bound phenol rapidly reacted with 2,6-dimethoxyphenolate ion, giving a condensation dimer in good yield. Condensation in the two-phased system appeared to be inhibited primarily by steric factors involving the supporting polystyrene resin.     

单质碘催化合成缩醛（酮）

以单质碘为催化剂,对以乙酰乙酸乙酯、环己酮、丁酮、苯甲醛和正丁醛与二元醇(乙二醇,1,2-丙二醇)为原料合成了2-甲基-2-乙氧羰甲基-1,3-二氧环戊烷、2,4-二甲基-2-乙氧羰甲基-1,3-二氧环戊烷、环己酮乙二醇缩酮、环己酮1,2-丙二醇缩酮、丁酮乙二醇缩酮、丁酮1,2-丙二醇缩酮、2-苯基-1,3-二氧环戊烷、4-甲基-2-苯基-1,3-二氧环戊烷、2-丙基-1,3-二氧环戊烷、4-甲基-2-丙基-1,3-二氧环戊烷10个缩醛(酮)的反应条件进行了研究,较系统地研究了醛或酮与二元醇摩尔比、催化剂用量、反应时间诸因素对收率的影响.结果表明,在n(醛或酮):n(乙二醇或1,2-丙二醇)=1:1.3,催化剂的用量占反应物料总质量的0.4%,反应时间为40～60 min条件下,10种缩醛(酮)的收率为45.2%～92.2%.     

HZSM-5分子筛催化合成新型七元环缩醛(酮)的研究

研究了HZSM-5分子筛催化1,4-丁二醇与环己酮的缩合反应,系统考察了反应时间、酮与醇的配比、HZSM-5分子筛用量等因素对酮与醇缩合反应的影响。结果表明,当n(酮)∶n(1,4-丁二醇)摩尔比为1∶1.5,催化剂用量为2.5g/1 mol酮,反应2 h,选择性为99.8%,转化率为93.5%,催化剂循环使用四次后,转化率仍在90%以上,说明HZSM-5分子筛对该反应有非常高的催化活性和稳定性。研究HZSM-5分子筛催化1,4-丁二醇与丁酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正辛醛、苯甲醛等八种醛(酮),同样的实验条件下,缩合反应选择性一般在97%以上,转化率也一般在90%以上,表明,HZSM-5分子筛对醛(酮)与醇的缩合反应有较好的催化性能。     

The Synthesis Characterization and Polymerization of Novel Thiophene Substituted Maleimide

Ethyl 2-amino 4,5,6,7-tetrahydrobenzo thiophene-3-carboxylate maleimide (ETTCM) has been synthesized and investigated as a new thio-maleimide derivative. The structure of the prepared compounds has been elucidated by elemental and spectral analyses. The free radical polymerization of (ETTCM) has been conducted in several solvents using azobisisobutyronitrile (AIBN) as an initiator. The kinetic parameters of polymerization of ETTCM were investigated, and it was found that the polymerization reaction follows the conventional free radical scheme. The initial rate of polymerization, the overall activation energy Ea was determined (Ea = 57.013 kJmol^?1) and intrinsic viscosity was measured ([η] = 0.04 dl/g). The prepared polymer is a good chelating agent with some metal ions and a moderate antifungal and antibacterial effect. The monomer reactivity ratios for the copolymerization of ETTCM with methyl methacrylate MMA, vinyl acetate VA, and vinyl ether VE were calculated by two methods, the Kelen-Tüdös and a nonlinear method. Thermal stability of the ETTCM polymers and copolymers were investigated by thermogravimetric analysis.     

KHSO4催化合成缩醛(酮)的研究

研究了KHSO4催化乙二醇与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正己醛、正辛醛、苯甲醛等十余种醛(酮)的缩合反应.考察了反应时间、醛(酮)与醇的配比、KHSO4用量等因素对醛(酮)与醇缩合反应的影响.结果表明,当醛(酮)与乙二醇摩尔比为1:1.4,催化剂用量为2g/1mol醛(酮),反应2h,选择性一般在98%以上,转化率也一般在90%以上,表明,KHSO4对醛(酮)与醇的缩合反应有较好的催化性能.     

磷钨酸催化合成缩醛(酮)

以磷钨酸为催化剂,对苯甲醛、丁醛、丁酮与二元醇(乙二醇,1,2 丙二醇)为原料合成6种缩醛(酮)的反应条件进行了研究,较系统地研究了醛/酮与二元醇量比、催化剂用量、反应时间诸因素对收率的影响。结果表明,在醛/酮与二元醇(乙二醇,1,2 丙二醇)的投料摩尔比为1∶1 75,催化剂的用量占反应物料总质量的1 5%,反应时间1h条件下,6种缩醛(酮)的收率为55 2%～79 0%。     

生物质基甘油缩醛和缩酮的合成研究进展

甘油作为一种重要的生物质基平台化合物,可以和羰基化合物在酸性催化剂的作用下发生缩合反应生成缩醛和缩酮,缩醛和缩酮可广泛应用于燃料添加剂、香料、兽药制剂、塑化剂和多元醇等领域。从甘油缩醛和缩酮的合成机理出发,简单比较了传统的液体酸催化剂与固体催化剂的催化性能,重点介绍了丙酮甘油缩酮、环己酮甘油缩酮、苯甲醛甘油缩醛、甘油甲醛缩醛和甘油乙酰丙酸酯缩酮等几种重要甘油缩醛和缩酮的合成工艺,并概述了其生产技术,最后展望了生物质基甘油缩醛和缩酮的开发应用前景。     

细乳液聚合制备新型红色荧光聚合物纳米粒子

本文采用一步细乳液聚合法,将一种疏水性的红色荧光染料甲基丙烯酸尼罗红酯(NRME)引入聚合物纳米粒子中,成功制备了新型水分散性红色荧光聚合物纳米粒子。光谱研究表明NRME已经成功结合进入纳米粒子。通过控制NRME在纳米粒子中的含量,可以获得不同荧光强度的聚合物纳米粒子。这类新型荧光纳米粒子在生物医学等领域有着潜在的应用价值。     

新型有机盐光引发剂的双光子聚合特性研究

本文运用激光微细加工技术，通过对不同浓度引发剂的甲基丙烯酸类树脂的聚合行为进行评价，研究了1-甲基-2-[2-（9-戊基-咔唑-3-基）-乙烯基]-3，3-二甲基吲哚碘盐（Ⅰ）作为双光子光引发剂的聚合特性，结果表明该化合物在扫描速度为44μm／s时，双光子聚合阈值为139kJ／cm%2；当激光能量密度为286kJ／cm^2时，引发聚合的曝光时间阈值为0．7ms．实验结果为进一步作为双光子聚合三维结构的微细加工提供了可靠依据．     

合成缩醛(酮)的催化剂研究进展

综述了固体超强酸、杂多酸、固载杂多酸、脱铝超稳沸石、树脂、分子筛、铌酸、漆酚衍生物、维生素C、碘、硫酸盐、氯化物、蒙脱土等40多种催化剂催化合成缩醛(酮)的方法和反应条件。评述了各类催化剂的催化性能、特点、能否重复使用等内容。结果表明:固体超强酸、固载杂多酸、HY型分子筛、脱铝超稳沸石、硫酸铜、高分子载体氯化物等几种环境友好催化剂是合成缩醛(酮)的优良催化剂。     

多省并醌聚合物的合成与表征

以蒽醌(AQ)和均苯四甲酸二酐(PMA)为原料,在路易斯酸的催化作用下,采用固态加热法、熔盐法和溶剂热法合成了多省并醌聚合物(PAQR)。通过X射线衍射(XRD)、傅里叶红外光谱(FTIR)和热重分析(TG)以及元素分析仪分析了产物的结构,并利用阻抗分析仪研究了该聚合物的性能。结果表明:由熔盐法合成的PAQR具有更高的产率,达42%;采用溶剂热法合成的聚合物具有最高的聚合度和共轭程度,且介电性能较好。     

Synthesis of Novel Polyamide-Hyperbranched Polymers via Self Condensing Atom Transfer Radical Polymerization

Novel inimer was synthesized from p-amino phenol via successive preparative methods by using both bromoisobutyrylbromide and acryloyl chloride. The new inimer was well characterized via Infrared Spectra (IR) and ¹ Fréchet , J.M.J. ; Tomalia , D.A. , Ed. Dendrimers and Other Dendritic Polymers , Wiley : West Sussex , 2001 .[Crossref] , [Google Scholar]H nuclear magnetic resonance (NMR). New hyperbranched polyamide (H₁) was prepared via Atom Transfer Radical Polymerization (ATRP). Several reaction conditions (ligands, solvents, temperatures, etc.) were studied. However, the N,N,N′,N″,-pentamethyldiethylenetriamine (PMDETA)/CuBr catalytic system showed good results in toluene at 100°C. Three arm star methylmethacrylate (MMA) homopolymers reacted with (H₁) in different percentages to form copolymers with low polydispersity values, especially at 1:115 for poly MMA:H₁. The formed polymers were characterized via Gel Permeation Chromatography (GPC), ¹ Fréchet , J.M.J. ; Tomalia , D.A. , Ed. Dendrimers and Other Dendritic Polymers , Wiley : West Sussex , 2001 .[Crossref] , [Google Scholar]HNMR, thermal analyses, and Transmission Electron Microscopy (TEM).     

新型含氟表面活性剂的制备及其在含氟丙烯酸酯乳液聚合中的应用

全氟辛酸盐(PFOA)类表面活性剂由于其优异的性能而被广泛应用,但也会对环境和人体造成危害,因此已经逐渐被限制和禁止使用.为了解决这一问题,本项目设计合成了满足当前环保要求的全氟己基乙酸盐类(APHA)表面活性剂,并对其结构和表面性能进行了研究,结果表明这类新型阴离子含氟表面活性剂的表面张力明显优于目前广泛使用的PFOA类表面活性剂.另外,以所制备的全氟己基乙酸铵作为含氟乳化剂,研究了甲基丙烯酸十二氟庚酯/甲基丙烯酸甲酯(DFHMA/MMA)的乳液聚合反应,通过对反应动力学、乳液粒径及乳液稳定性的研究,表明该含氟表面活性剂具有良好的乳化效果,能够作为PFOA的替代品使用.     

HMCM-22沸石分子筛催化合成缩醛(酮)

研究了在HMCM-22沸石分子筛催化下乙二醇与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正辛醛、苯甲醛等多种醛（酮）的缩合反应。重点研究了乙二醇与环己酮的反应条件,考察了反应时间、醛（酮）与醇的配比、HMCM-22沸石的用量及催化剂重复使用等因素对反应的影响,优化了反应条件。结果表明,在醛（酮）与乙二醇物质的量比为1：1．2、催化剂用量为2g／mol醛（酮）、反应2h的条件下,转化率可达90％以上,选择性可达99％以上。表明HMCM-22沸石分子筛对该缩合反应有较好的催化活性和选择性。     

Synthesis and Functional Evaluation of Soy Fatty Acid Methyl Ester Ketals as Bioplasticizers

A facile synthesis of the soy fatty acid methyl ester ketal has been accomplished using acetone in the presence of catalytic anhydrous ferric chloride starting from commercially available soy biodiesel (soy fatty acid methyl ester) after evaluating various synthetic procedures. The soy ketal product was fully characterized by nuclear magnetic resonance, infra-red and chromatography. The physical and analytical properties of soy ketal as determined by thermogravimetric analysis, viscosity acid and saponification values are acceptable for plasticizer applications. Soy ketal was compounded with polyvinyl chloride for evaluation of plasticizer properties such as efficiency, gelation, viscosity, volatility, thickening/aging behavior and stability. The thickening and aging behaviors of the soy ketal bioplasticizer are better than those of petroleum-based plasticizers such as diisononyl phthalate and diisononyl-cyclohexane dicarboxylate, but they need improvement in the areas of thermal stability and water extractability.     

Organocatalytic Reactions of Indoles with Quinone Imine Ketals: An Alternative Metal‐Free Approach to Bioactive meta‐Indolylanilines

An organocatalytic metal‐free strategy has been established for the synthesis of pharmaceutically relevant meta‐indolylanilines in generally excellent yields (up to 99 %). This strategy took advantage of the reaction of indoles and quinone imine ketals (QIKs) in the presence of racemic phosphoric acid, which proceeded via a 1,4‐addition/alcohol elimination reaction sequence. The control experiment demonstrated that the dual hydrogen‐bonding activation mode of the catalyst to the substrates played a crucial role in the reaction. This protocol provides a metal‐free and step‐economical approach to meta‐anilines bearing either 3‐indolyl or 2‐indolyl moiety, which is of high value for the synthesis of compounds with potential bioactivities.

     

三氯化铝催化合成甘油类缩醛（酮）的研究

研究了在AlCl3催化下,丙三醇与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正辛醛、二苯甲酮、苯甲醛等十余种醛(酮)的缩合反应。系统考察了反应时间、醛(酮)与醇的配比、AlCl3的用量及催化剂重复使用等因素对反应的影响,优化了反应条件。结果表明,当醛(酮)与丙三醇物质的量比为1∶1.2,催化剂用量为2g/mol醛(酮),反应2h,转化率可达99.2%,选择性可达100%。证明AlCl3对该缩合反应有较好的催化活性和选择性。