磷鎢釩雜多酸論文：磷鎢釩雜多酸阻聚性能及應(yīng)用研究

磷鎢釩雜多酸論文：磷鎢釩雜多酸阻聚性能及應(yīng)用研究【中文摘要】雜多化合物是一類含有氧橋的多核配合物,由于具有獨(dú)特的分子結(jié)構(gòu)及分子易于設(shè)計(jì)和組裝的特點(diǎn),現(xiàn)已廣泛應(yīng)用于新型高效催化劑、藥物、磁性材料、高質(zhì)子導(dǎo)體、電致變色材料、無機(jī)填料添加劑、選擇電極以及燃料電池等領(lǐng)域。本文以測定磷鎢釩型雜多酸阻聚性能為目標(biāo)。通過采取分步加入原料、分步酸化、回流煮沸、乙醚萃取的方法制備了四種Dawson型磷鎢釩雜多酸H730H2O(標(biāo)記為Dawson-V1),H814H2O(標(biāo)記為Dawson-V2),H924 H2O(標(biāo)記為Dawson-V3), H836H2O(標(biāo)記為Dawson-V4)和三種Keggin型磷鎢釩雜多酸H4PW11V04015H2O(標(biāo)記為Keggin-V1),H5PW10V2O4023H2O(標(biāo)記為Keggin-V2),H6PW9V3O4024H2O(標(biāo)記為Keggin-V3),并對(duì)其進(jìn)行了IR、XRG、TG表征,確定化合物的結(jié)構(gòu)和組成。利用差示掃描量熱法(DSC)測定已合成的Dawson型和Keggin型磷鎢釩雜多酸對(duì)甲基丙烯酸甲酯的阻聚效果。實(shí)驗(yàn)結(jié)果表明,對(duì)同一種雜多酸而言,隨著雜多酸樣品量的不斷增加,反應(yīng)的速率常數(shù)不斷減小,阻聚性能越好。對(duì)于不同的雜多酸而言,隨著雜多酸中鎢原子與釩原子數(shù)目比例的降低,反應(yīng)的數(shù)率常數(shù)隨之減小,說明含釩原子數(shù)越多的雜多酸阻聚性能越好。從總體上來說Dawson型磷鎢釩雜多酸的阻聚性能要優(yōu)于Keggin型。在阻聚測定結(jié)果的實(shí)驗(yàn)基礎(chǔ)上,選取阻聚性能最優(yōu)的H836H2O為催化劑,討論催化劑濃度,反應(yīng)溫度,醇酯物質(zhì)的量比以及反應(yīng)時(shí)間四個(gè)變化因素,制定4因素3水平正交試驗(yàn)方案L9(34),考察反應(yīng)條件對(duì)酯化率的影響。通過實(shí)驗(yàn)條件和結(jié)果的綜合比較從而得出H836H2O通過酯交換法催化合成-甲基丙烯酸丁醇酯的最佳反應(yīng)條件為：催化劑用量0.6%(相對(duì)于反應(yīng)物的質(zhì)量分?jǐn)?shù)),酯醇摩爾比1.2：1,反應(yīng)時(shí)間8h,反應(yīng)溫度125。按最佳反應(yīng)條件進(jìn)行酯交換反應(yīng),平均收率為96.2%。并將H836H2O應(yīng)用于催化合成-甲基丙烯酸月桂醇酯的反應(yīng)中,討論酸醇的原料比、催化劑用量、帶水劑、反應(yīng)時(shí)間四個(gè)變化因素,制定4因素3水平正交試驗(yàn)方案L9(34),考察反應(yīng)條件對(duì)酯化率的影響。通過實(shí)驗(yàn)條件和結(jié)果的綜合比較從而得出H836H2O通過酯化法催化合成-甲基丙烯酸月桂醇酯的最佳反應(yīng)條件為：月桂醇與a-甲基丙烯酸的物質(zhì)的量比為1.3：1,催化劑的質(zhì)量分?jǐn)?shù)為0.4%(相對(duì)于反應(yīng)物的質(zhì)量分?jǐn)?shù)),帶水劑為10mL,反應(yīng)時(shí)間2h。在最佳反應(yīng)條件下,酯轉(zhuǎn)化率近80%?！居⑽恼縃eteropoly compounds are polynucler 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, selective 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 (marked 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 step 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). 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 vanadium 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 synthesze 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 orthogonal 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 catalyze 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 best 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%.【關(guān)鍵詞】磷鎢釩雜多酸 Keggin型 Dawson型 阻聚性能 不飽和酯【英文關(guān)鍵詞】heteropoly acid Dawson-type Keggin-type inhibition unsaturated Esters【目錄】磷鎢釩雜多酸阻聚性能及應(yīng)用研究摘要4-5Abstract5-61 緒論9-271.1 多金屬氧酸(鹽)概述9-131.1.1 多酸化合物的結(jié)構(gòu)10-121.1.2 多酸化合物的制備12-131.2 多酸化合物的功能和應(yīng)用13-231.2.1 多酸化合物的催化化學(xué)13-151.2.2 多酸化合物的藥物化學(xué)15-191.2.3 多酸超分子化合物的合成與非線性光學(xué)功能特性的研究19-201.2.4 固體雜多化合物的質(zhì)子導(dǎo)電功能特性20-221.2.5 多陰離子的相轉(zhuǎn)移化學(xué)221.2.6 電質(zhì)變色與(EC)顯示材料22-231.3 差示掃描量熱法(DSC)綜述23-251.3.1 差示掃描量熱法(DSC)簡介231.3.2 差示掃描量熱法(DSC)原理23-241.3.3 影響DSC實(shí)驗(yàn)結(jié)構(gòu)的因素24-251.4 國內(nèi)外研究現(xiàn)狀251.5 選題的理論意義和應(yīng)用價(jià)值25-272 實(shí)驗(yàn)部分27-332.1 試劑與儀器27-282.2 多金屬氧酸的合成28-302.2.1 Keggin型雜多酸H_4PW_(11)VO_(40)15H_2O(Keggin-V1)的合成28-292.2.2 Dawson型雜多酸H_7P_2W_(17)VO_(62)30H_2O(Dawson-V1)的合成29-302.3 多金屬氧酸對(duì)甲基丙烯酸甲酯阻聚作用的測定302.4 多金屬氧酸催化合成不飽和酯30-332.4.1 催化劑的選擇302.4.2 H_8P_2W_(14)V_4O_(62)H_236H_2O催化甲基丙烯酸甲酯與正丁醇的酯交換應(yīng)30-312.4.3 H_8P_2W_(14)V_4O_(62)H_236H_2O催化-甲基丙烯酸和月桂醇的酯化反應(yīng)31-333 結(jié)果與討論33-653.1 三種Keggin型磷鎢釩雜多酸結(jié)構(gòu)的表征33-363.1.1 Keggin型磷鎢釩雜多酸的紅外光譜分析333.1.2 Keggin型磷鎢釩雜多酸的XRD分析33-353.1.3 Keggin型磷鎢釩雜多酸的熱重分析(TG)35-363.2 四種Dawson型磷鎢釩雜多酸結(jié)構(gòu)的表征36-423.2.1 Dawson型磷鎢釩雜多酸的紅外光譜分析36-373.2.2 Dawson型磷鎢釩雜多酸的雜多酸的XRD分析37-393.2.3 Dawson型磷鎢釩雜多酸的熱重分析(TG)39-413.2.4 Dawson型磷鎢釩雜多酸的合成條件討論41-423.3 多金屬氧酸對(duì)甲基丙烯酸