1.大連工業大學 輕工與化學工程學院;2.大連工業大學 國家海洋食品工程技術研究中心
1.School of Light Industry and Chemical Engineering,Dalian Polytechnic University;2.National Engineering Research Center of Seafood,Dalian Polytechnic University
以四氯化鋯、磷鉬酸水合物、1,2,4,5-苯四甲酸和（3-巰基丙基）三甲氧基硅烷為原料，通過原位合成法及接枝共聚法制得負載磷鉬酸的磺酸基功能化UiO-66（HPMo@UiO-66-SO3H）。采用XRD、FTIR、SEM、EDS、XPS、N2吸附-脫附和TG-DTG對其進行了結構表征；應用HPMo@UiO-66-SO3H促進大豆卵磷脂與中碳鏈脂肪酸（辛酸和癸酸）酯交換合成富含辛酸和癸酸的中碳鏈結構磷脂，通過正交實驗優化了反應條件，并對比了HPMo@UiO-66-SO3H與HPMo、UiO-66、HPMo@UiO-66和UiO-66-SO3H的反應活性，考察了HPMo@UiO-66-SO3H的循環利用性。結果表明，HPMo@UiO-66-SO3H具有介孔結構，并含有大量HPMo和磺酸基活性組分，且組分間可顯著協同促進中碳鏈結構磷脂的合成反應；當HPMo@UiO-66-SO3H含量為大豆卵磷脂、辛酸和癸酸總質量的百分之5，m（大豆卵磷脂）∶m（辛酸）∶m（癸酸）=1∶10∶10，50 ℃下反應4 h時，產物的中碳鏈脂肪酸接入率高達百分之94.31（辛酸和癸酸接入率分別為百分之44.21和百分之50.10）；HPMo@UiO-66-SO3H可循環利用5次活性無明顯下降。提出了HPMo@UiO-66-SO3H促進酯交換制備中碳鏈結構磷脂過程的可能反應機理。
Sulfonic acid functionalized phosphomolybdic acid incorporated-UiO-66 (HPMo@UiO-66-SO3H) was prepared by an in-situ graft copolymerization method using zirconium (Ⅳ) chloride, phosphomolybdic acid hydrate, 1,2,4,5-benzenetetracarboxylic acid and (3-mercaptopropyl) trimethoxysilane as raw materials, and characterized by XRD, FTIR, SEM, EDS, XPS, N2 adsorption-desorption and TG-DTG. HPMo@UiO-66-SO3H was used to prepare medium-chain structured phospholipids enriched in caprylic acids and capric acids through transesterification between soybean lecithins and medium-chain fatty acids (caprylic acids and capric acids), and the reaction conditions were optimized by orthogonal experiment method. Moreover, the reactivity of HPMo@UiO-66-SO3H was compared with HPMo, UiO-66, HPMo@UiO-66 and UiO-66-SO3H materials, and the recycling of HPMo@UiO-66-SO3H was researched as well. As a result, it was certified that HPMo@UiO-66-SO3H exhibited a mesoporous structure possessing numerous HPMo and sulfonic acid active components, and a promising reactivity for the synthesis of medium-chain structured phospholipids due to the synergistic effect of the two components. The incorporation of medium-chain fatty acids in product reached as high as 94.31percent with 44.21 percent of caprylic acid and 50.10 percent of capric acid at 50 ℃ within 4 h when the HPMo@UiO-66-SO3H dosage was 5 percent of the total mass of soybean lecithins, caprylic acids and capric acids, and the m(soybean lecithins)∶m(caprylic acids)∶m(capric acids) was 1∶10∶10. Noticeably, HPMo@UiO-66-SO3H could be recycled 5 times with no obvious deactivation. A probable reaction mechanism of medium-chain structured phospholipid synthesis using HPMo@UiO-66-SO3H responsible for the process is presented.