《磷钨钒杂多酸论文：磷钨钒杂多酸阻聚性能及应用研究》由会员分享，可在线阅读，更多相关《磷钨钒杂多酸论文：磷钨钒杂多酸阻聚性能及应用研究（7页珍藏版）》请在金锄头文库上搜索。
1、 磷钨钒杂多酸论文：磷钨钒杂多酸阻聚性能及应用研究磷钨钒杂多酸论文：磷钨钒杂多酸阻聚性能及应用研究【中文摘要】杂多化合物是一类含有氧桥的多核配合物,由于具有独特的分子结构及分子易于设计和组装的特点,现已广泛应用于新型高效催化剂、药物、磁性材料、高质子导体、电致变色材料、无机填料添加剂、选择电极以及燃料电池等领域。本文以测定磷钨钒型杂多酸阻聚性能为目标。通过采取分步加入原料、分步酸化、回流煮沸、乙醚萃取的方法制备了四种 Dawson 型磷钨钒杂多酸H730H2O(标记为 Dawson-V1),H814H2O(标记为 Dawson-V2),H924 H2O(标记为 Dawson-V3), H836
2、H2O(标记为 Dawson-V4)和三种 Keggin 型磷钨钒杂多酸 H4PW11V04015H2O(标记为 Keggin-V1),H5PW10V2O4023H2O(标记为 Keggin-V2),H6PW9V3O4024H2O(标记为 Keggin-V3),并对其进行了 IR、XRG、TG 表征,确定化合物的结构和组成。利用差示扫描量热法(DSC)测定已合成的 Dawson 型和Keggin 型磷钨钒杂多酸对甲基丙烯酸甲酯的阻聚效果。实验结果表明,对同一种杂多酸而言,随着杂多酸样品量的不断增加,反应的速率常数不断减小,阻聚性能越好。对于不同的杂多酸而言,随着杂多酸中钨原子与钒原子数目比例的
3、降低,反应的数率常数随之减小,说明含钒原子数越多的杂多酸阻聚性能越好。从总体上来说 Dawson 型磷钨钒杂多酸的阻聚性能要优于 Keggin 型。在阻聚测定结果的实验基础上,选取阻聚性能最优的 H836H2O 为催化剂,讨论催化剂浓度,反应温度,醇酯物质的量比以及反应时间四个变化因素,制定 4 因素 3水平正交试验方案 L9(34),考察反应条件对酯化率的影响。通过实验条件和结果的综合比较从而得出 H836H2O 通过酯交换法催化合成 -甲基丙烯酸丁醇酯的最佳反应条件为：催化剂用量 0.6%(相对于反应物的质量分数),酯醇摩尔比 1.2：1,反应时间 8h,反应温度125。按最佳反应条件进行
4、酯交换反应,平均收率为 96.2%。并将H836H2O 应用于催化合成 -甲基丙烯酸月桂醇酯的反应中,讨论酸醇的原料比、催化剂用量、带水剂、反应时间四个变化因素,制定4 因素 3 水平正交试验方案 L9(34),考察反应条件对酯化率的影响。通过实验条件和结果的综合比较从而得出 H836H2O 通过酯化法催化合成 -甲基丙烯酸月桂醇酯的最佳反应条件为：月桂醇与 a-甲基丙烯酸的物质的量比为 1.3：1,催化剂的质量分数为 0.4%(相对于反应物的质量分数),带水剂为 10mL,反应时间 2h。在最佳反应条件下,酯转化率近 80%。【英文摘要】Heteropoly compounds are po
5、lynucler complexes with oxygen bridge, because they have unique molecular structure and they are easy to design and assemble, now it has widely used in new and efficient catalyst, Medicine, magnetic materials, high-quality sub-conductors, electrochromic materials, inorganic filler additives, selecti
6、ve electrode and fuel cell etc.This paper is to determine the inhibition effects of vanadium substituted heteropoly acid(W, P). Four novel vanadium atom substituted series of Dawson-type heteropoly acid (W, P) H7P2W17VO6230H2O (marked Dawson-V1), H8P2O6214H2O (marked Dawson-V2), H9P2W15V3O6224H2O (m
7、arked Dawson-V3) and H10P2W14V4 O6236H2O (marked Dawson-V4) and three novel vanadium atom substituted series of Keggin-type heteropoly acid (W, P) H4PW11V04015H20 (marked Keggin-V1),H5PW 10V2O4023H2O(marked Keggin-V2), H6PW9V3O4024H2O (marked Keggin-V3) were prepared by joining the raw materials ste
8、p by step, acidificating step by step, circumfluencing, boiling and extracting with diethyl ether. Their structure were determined by IR, XRD, TG.The inhibition effects of vanadium substituted Dawson-type and Keggin-type heteropoly acid (W, P) were measured by differential scanning calorimetry (DSC)
9、. The results show that the polymerization velocity of MMA decreases continuously as the amount of the heteropoly acids in the same series and the polymerization velocity decreases continuously as the increasing of vanadium atomic number in the different series heteropoly acids, i.e. the greater van
10、adium atom number in the heteropoly acid, the better inhibition effect of heteropoly acid. On the whole, the inhibition effects of Dawson-type heteropoly acid are better than Keggin-type heteropoly acid.In the basis of the above experiment, H8P2W14V4O62H236H2O is identified as a catalyst to synthesz
11、e a-alcohol methacrylate esters. The influence of four factors of catalyst concentration、reaction temperature、molar ration of alcohol to ester and reaction time on the esterification rate was discussed by developing orthogonal pilot program Lg(34). The optimum conditions which determined by orthogon
12、al experiment were as follows:the molar ration of-Methyl methacrylate to n-butanol was 1.2:1, weight of heteropolyacid was 0.6% of total weight, reaction time was 8h, reaction temperature was 125. Under the optimum conditions, the yield was about 96.2%. H8P2W14V4O62H236H2O is also applized to cataly
13、ze the esterification between dodecanol and methacrylic acid. The influence of four factors of catalyst concentration、reaction time、molar ration of alcohol to acid and the volume of toluene on the esterification rate is discussed by developing orthogonal pilot program L9(34). The results show the be
14、st reaction conditions are that dodecanol and methacrylic acid molar ratio is 1.3:1, the mass fraction of catalyst is 0.4%, the volume of toluene is 10mL and reaction time is 2h. Under the optimum conditions, the yield was about 80%.【关键词】磷钨钒杂多酸 Keggin 型 Dawson 型 阻聚性能 不饱和酯【英文关键词】heteropoly acid Dawso
15、n-type Keggin-type inhibition unsaturated Esters【目录】磷钨钒杂多酸阻聚性能及应用研究 摘要 4-5 Abstract 5-6 1 绪论 9-27 1.1 多金属氧酸(盐)概述 9-13 1.1.1 多酸化合物的结构 10-12 1.1.2 多酸化合物的制备 12-13 1.2 多酸化合物的功能和应用 13-23 1.2.1 多酸化合物的催化化学 13-15 1.2.2 多酸化合物的药物化学 15-19 1.2.3 多酸超分子化合物的合成与非线性光学功能特性的研究 19-20 1.2.4 固体杂多化合物的质子导电功能特性 20-22 1.2.5 多阴离子的相转移化学 22 1.2.6 电质变色与(EC)显示材料 22-23 1.3 差示扫描量热法(DSC)综述 23-25 1.3.1 差示扫描量热法(DSC)简介 23 1.3.2 差示扫描量热法(DSC)原理 23-24 1.3.3 影响 DSC 实验结构的因素 24-25 1.4 国内外研究现状 25 1.5 选题的理论意义和应用价值 25-27 2 实验部分 27-33 2.1 试剂与仪器 27-28 2.2 多金属氧酸的合成 28-30 2.2.1 Keggin 型杂多酸 H_4PW_(11)VO_(40)15H_2O(K
