製備芳香磺酸基修飾之固體酸Preparation of phenol-or Thiophenyl-Sulfonic Acid Functionalized Solid Acids

專利類型

發明

專利國別 (專利申請國家)

美國

專利申請案號

14/139,961

專利證號

US 9,062,081 B1

專利獲證名稱

製備芳香磺酸基修飾之固體酸Preparation of phenol-or Thiophenyl-Sulfonic Acid Functionalized Solid Acids

專利所屬機關 (申請機關)

國立臺灣大學

獲證日期

2015/06/23

技術說明

酸觸媒在工業界的應用極為普遍，目前工業界常使用的硫酸、氫氟酸與對甲基苯磺酸等液體強酸的價格便宜、反應性好，但其最大缺點是操作危險、與產物的分離困難，造成製程的成本增加。而且，產生之酸廢液會污染環境，處理也很麻煩。 因此，固體強酸的開發一直是科學界與工業界很有興趣的課題。本發明是以3-氯丙基三甲氧基矽烷為起始物，在無溶劑下，與對甲酚或噻吩進行Friedel–Crafts反應，之後可以經由共沈澱或嫁接後修飾法將甲酚基或噻吩基引入在各種金屬氧化物材料上，包括介孔二氧化矽材料、矽膠、二氧化鋯等，最後再以濃硫酸進行磺酸化修飾，得到含苯酚磺酸官能基之固體酸。本發明的含苯酚磺酸官能基或噻吩磺酸官能基之固體酸在低溫下即具有極強的酸性，其熱穩定性遠勝過於Amberlyst-15 樹脂。而且本發明之反應原料價格低廉、無溶劑的使用、反應步驟簡單，極適合大規模的生產。此結果已經提出美國及臺灣之專利申請。 Acid catalysts are widely used in industrial processes. Currently, the most commonly used acid catalysts are liquid strong acids including sulfuric acid, hydrofluoric acid, and methylbenzoic acid. They have the advantages of cheap prices and high activities. However, the drawbacks are the danger in process operation and the difficulties of product separation, which increase the cost of manufacture. Moreover, waste acids are environmental hazard and difficult to discard. A novel solid acid catalyst was developed in the present discovery. A phenolic or thiophenyl silane was prepared first, and it was ready to attach to various solid supports through covalent bonding by either coprecipitation or grafting method. After sulfonation, the resultant materials are strong solid acids. Because the new solid acid has great potential to take the place of liquid strong acids in industrial processes, the research result is in the process of applying for ROC and US patents.

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