己二胺为核酯为端基的半代树枝状大分子的合成

以己二胺和丙烯酸甲酯为原料合成了以己二胺为核酯为端基的半代树枝状大分子,其结构经IR和元素分析表征。在己二胺50 mmol,n(丙烯酸甲酯)∶n(己二胺)=6∶1,于50℃反应12 h的条件下,收率99.4%。     

Kinetic study of methoxycarbonylation of 1,6‐hexanediamine with dimethyl carbonate using Mn(OAc)2 catalyst

Clean synthesis of dimethylhexane‐1,6‐dicarbamate (HDC) from methoxycarbonylation of 1,6‐hexanediamine (HDA) with dimethyl carbonate (DMC) was studied. Among several heterogeneous and homogeneous catalysts, Mn(OAc)₂ was screened as the most effective catalyst over which the kinetic balance could be reached within 2–3 h. Then the kinetic model of the methoxycarbonylation of HDA with DMC using Mn(OAc)₂ catalyst, under the real reaction conditions was established. Results indicated that the reaction orders were confirmed to be 4.5 for the first step reaction and 4.3 for the second step reaction by the numerical differential method. In addition, the activation energies for the first and second step reaction were 47.0514 and 60.4504 kJ·mol⁻¹ and the frequency factors were 1.4645 × 10² and 3.6519 × 10⁴ min⁻¹, respectively. Moreover, the kinetic model correlated well with experimental data. This study not only provides a highly efficient catalyst for the methoxycarbonylation of HDA with DMC but also gives the guidance for the design of the reactor by studying its kinetic under real reaction conditions.     

The Preparation of Functionalized Crosslinked Macroporous Chitosan Microspheres and their Adsorption Properties for Bilirubin

Summary: glutaraldehyde cross-linked macroporous chitosan microspheres (CS) were prepared by inverse phase suspension reaction with sugar as porogenic agent. The microspheres were modified with different reagents of 1, 6 hexanediamine (HDA) and low generation polyamidoamine (PAMAM) dendrimers including PAMAM G1.0, PAMAM G2.0, PAMAM G3.0. The content of amino groups on CS, CS-PAMAM G1.0, CS-PAMAM G2.0, CS-PAMAM G3.0, CS-HDA was 3.56, 5.10, 5.47, 6.47, 4.66 mmol/g, respectively. The bilirubin adsorption on the above five microspheres was carried out in 0.05M phosphate buffer solution (pH = 7.2–7.4) at 37 °C. The results indicated all the modified CS microspheres were better than unmodified CS microspheres for bilirubin adsorption. CS-HDA has the best adsorption property even if the content of the amino groups was not very high.     

合成六亚甲基1,6-二氨基甲酸甲酯的新方法

以碳酸二甲酯(DMC)和1,6-己二胺(HDA)为原料合成了六亚甲基1,6-二氨基甲酸甲酯(HDU)。研究了部分Lewis酸对反应的催化活性。其中Zn(NO3)2的催化活性最好。HDA 50 mmol,n(DMC)∶n(HDA)=10∶1,n[Zn(NO3)2]∶n(HDA)=1∶10时,在150℃油浴中回流(90℃)反应3 h,HDU收率可达97%。     

己二胺为核低代树枝状大分子的合成与性能

以己二胺和丙烯酸甲酯为原料,甲醇为溶剂,采用迈克尔加成和酰胺化缩合反应合成了低代己二胺为核的树枝状大分子。主要考察了反应条件对己二胺为核1.0G树枝状大分子收率的影响,当n(己二胺为核0.5G树枝状大分子)∶n(己二胺)=1∶6,反应温度50℃,反应时间24h,收率为69.36%。研究了以己二胺为核的1.0G树枝状大分子对O/W型模拟乳液的破乳性能。结果表明:在45℃、添加量为200ppm、60min的条件下,己二胺为核的1.0G树枝状大分子的破乳率达到80.28%。     

壳聚糖微球负载的己二胺型聚酰胺-胺树状大分子的制备及对胆红素的吸附

通过反相悬浮反应制备了戊二醛交联的壳聚糖微球。以所制备的壳聚糖微球为载体,合成了己二胺型低代数聚酰胺-胺（Polyamidoamine,简称PAMAM）树枝状大分子（Genaration≤3）。考察了该微球在生理条件下对水溶液中胆红素的吸附行为,以及溶液的pH值,离子强度,温度,胆红素初始浓度,牛血清白蛋白等因素对吸附的影响。结果表明,吸附剂对胆红素具有良好的吸附性能,CS-G2.0,CS-G3.0,CS-G1.0,CS-G0和CS微球的平衡吸附率分别为94.61%,93.44%,92.97%,86.47%,52.38%,CS-G1.0-G3.0微球在0.5h吸附率已经超过70%,1h基本接近平衡,对胆红素的吸附量高达42.78mg/g。     

胡椒酸己二胺的合成

以胡椒碱为起始原料,与KOH反应生成胡椒酸钾盐,经酸化后制得胡椒酸(2); 2与乙醇经酯化反应制得胡椒酸乙酯(3); 3与己二胺在金属钠催化下经氨解反应合成了胡椒酸己二胺(4),其结构经¹H NMR, ¹³C NMR和IR确证。合成4的最佳反应条件为：催化剂用量2 wt%, n(3):n(己二胺)=0.6, m(乙醇):m(3)=2.5,于65～75 ℃反应48 h,收率83.5%。该工艺在微型实验基础上放大十倍,收率大于79%。