CN1891338A - 活性炭负载碘化亚铜催化剂、制备方法和用途 - Google Patents
活性炭负载碘化亚铜催化剂、制备方法和用途 Download PDFInfo
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Abstract
本发明提供的活性炭负载碘化亚铜可用作二烷基二硫与芳烃化合物之间的烷硫基化反应的催化剂，它是用活性炭浸渍在硫酸铜和碘或硫酸铜和碘化钾的乙醇/水溶剂中，由甲醛、氧化硫、亚硫酸钠或硫代硫酸钠还原而制成的。
Description
技术领域
本发明是属于化学反应催化剂领域。特别涉及用于二烷基二硫与芳烃化合物反应，制备烷硫基芳烃化合物的活性炭负载碘化亚铜催化剂。
技术背景
许多烷硫基芳烃(例如苯甲硫醚、对甲硫基苯酚、2，4-二氨基-3，5-二甲硫基甲苯、2，6-二氨基-3，5-二甲硫基甲苯等)是重要的精细合成中间体原料，广泛应用于农药和橡塑助剂的合成。二烷基二硫与芳烃的亲电取代反应是制备烷硫基芳烃的重要方法之一，其中的二烷基二硫主要包括二甲基二硫、二乙基二硫、二苄基二硫、二环己基二硫等，芳烃主要包括由推电子基团活化的芳香族化合物，例如苯酚、苯胺、2，4-二氨基甲苯、2，6-二氨基甲苯、2，4(2，6)-甲苯二胺混合物、对甲基苯胺等。最为重要的是Lewis酸作为上述反应的催化剂是必不可少的，常用的Lewis酸催化剂有碘化亚铜、氯化锌、三氯化铝等，碘化亚铜的催化效果最好。美国专利US4594453、US5015770、US5210304、US5302755等报道了二甲基二硫与2，4(2，6)-甲苯二胺混合物反应，制备2，4-二氨基-3，5-二甲硫基甲苯和2，6-二氨基-3，5-二甲硫基甲苯混合物的方法，使用的催化剂都是碘化亚铜。
市售碘化亚铜产品通常为20目的大颗粒粉体，由于碘化亚铜大颗粒粉体比重较大，所以用在二烷基二硫与芳烃的亲电取代反应制备烷硫基芳烃化合物的过程中，反应体系中出现碘化亚铜大颗粒粉沉降严重，催化效能低，造成碘化亚铜催化剂的耗量增大等问题。为了能够减少碘化亚铜催化剂的用量，提高其催化效能，工业一般是采用将20目大颗粒粉体碘化亚铜粉碎为200～400目微细粉体的方法。但是，碘化亚铜催化剂是一种光敏感化合物，微细粉体碘化亚铜在粉碎和催化应用两过程中的感光分解损失比较严重。碘化亚铜的价格又比较高，所以碘化亚铜作为催化剂的损耗高，所占2，4-二氨基-3，5-二甲硫基甲苯和2，6-二氨基-3，5-二甲硫基甲苯混合物的生产成本比例高。
发明内容
本发明提供的活性炭负载碘化亚铜催化剂，目的在于减小催化剂与有机反应体系之间的密度差，提高碘化亚铜在有机反应体系中的分散度，提高其催化效能；利用活性炭的黑色保护碘化亚铜，避免碘化亚铜在使用和储存过程中的感光分解损失，以降低烷硫基芳烃化合物的生产成本。
本发明提供的活性炭负载碘化亚铜催化剂的制备方法是活性炭浸渍在硫酸铜和碘化钾的水中，由甲醛、二氧化硫、亚硫酸钠或硫代硫酸钠等还原剂还原而制成的。或者活性炭浸渍在硫酸铜和碘的乙醇水混合溶剂中，由甲醛、二氧化硫、亚硫酸钠或硫代硫酸钠等还原剂还原而制成。
本发明提供的活性炭负载碘化亚铜催化剂的制备方法所述的活性炭可以是球状、柱状、圆桶状、无定形颗粒状，也可以是粉末状的。为了提高碘化亚铜在活性炭表面上或空腔中的分散度，活性炭浸渍在硫酸铜和碘化钾的水溶液中或活性炭浸渍在硫酸铜和碘的乙醇水混合溶剂中，应先加热煮沸1～4小时，然后再加入还原剂甲醛、二氧化硫、亚硫酸钠或硫代硫酸钠等，这样生成的碘化亚铜就可以在活性炭中分散均匀。
本发明提供的活性炭负载碘化亚铜作为二烷基二硫与芳烃的亲电取代反应催化剂具有以下的优点：活性炭负载碘化亚铜催化剂相对有机反应体系的密度差减小，活性炭负载碘化亚铜催化剂在有机反应体系的均分散性高，相等重量的活性炭负载碘化亚铜催化活性相比碘化亚铜催化剂的催化活性中心多；利用活性炭的黑色可以有效保护碘化亚铜免于感光分解，提高活性炭负载碘化亚铜催化剂的循环使用效率，降低烷硫基芳烃化合物生产中催化剂的消耗量；活性炭负载碘化亚铜催化剂与有机反应物体系和有机反应产物体系的过滤分离方便，简化了活性炭负载碘化亚铜催化剂分出过程。
以下实施例进一步说明本发明提供的活性炭负载碘化亚铜催化剂、制备方法以及应用。
实施例1
活性炭负载碘化亚铜催化剂及制备方法
在装有搅拌器、回流冷凝器、滴液漏斗的反应烧瓶中，加入0.21摩尔五水硫酸铜、0.2摩尔碘化钾、200克60目活性炭、去离子水200毫升，搅拌下，升温至沸腾保持2小时。冷却至室温，搅拌滴入0.22摩尔亚硫酸钠的饱和水溶液，反应1小时后，收集滤饼，滤饼先用去离子水洗涤3～5次，后用无水乙醇洗涤3～5次，抽空干燥，即可制得活性炭负载碘化亚铜催化剂。
实施例2
活性炭负载碘化亚铜催化剂及制备方法
在装有搅拌器、回流冷凝器、滴液漏斗的反应烧瓶中，加入0.21摩尔五水硫酸铜、0.2摩尔精碘、200克60目活性炭、乙醇100毫升、去离子水100毫升，搅拌下均匀，升温至沸腾2小时。冷却至室温，搅拌滴入37％的甲醛水溶液20克，反应1小时后，收集滤饼，滤饼先用去离子水洗涤3～5次，后用无水乙醇洗涤3～5次，抽空干燥，即可制得活性炭负载碘化亚铜催化剂。
实施例3
活性炭负载碘化亚铜催化剂的应用
在装有搅拌器、回流冷凝器、滴液漏斗的反应烧瓶中，加入刚蒸馏过的2，4-二氨基甲苯和2，6-二氨基甲苯混合物(80∶20)100克和实施例1所制备的活性炭负载碘化亚铜催化剂30克。N2保护下，搅拌升温至130～135℃，3小时内滴入二甲基二硫160克，滴完二甲基二硫继续保持130～135℃反应2小时。冷却至50℃附近，真空抽滤，滤液真空蒸馏可分出2，4-二氨基-3，5-二甲硫基甲苯和2，6-二氨基-3，5-二甲硫基甲苯混合物231克，产率94.4％。滤饼循环使用可达8次以上，依然保持高产率。
Claims (9)
1.一种用于二烷基二硫与芳烃化合物反应，制备烷硫基芳烃化合物的活性炭负载碘化亚铜催化剂。其特征在于化学沉淀的碘化亚铜沉积在活性炭上，碘化亚铜含量在5～300％之间。
2.依照权利要求1所述的活性炭负载碘化亚铜催化剂，其特征在于是活性炭浸渍在硫酸铜和碘化钾的水中，由还原剂还原而制成的。
3.依照权利要求1所述的活性炭负载碘化亚铜催化剂，其特征在于是活性炭浸渍在硫酸铜和碘的乙醇水混合溶剂中，由还原剂还原而制成的。
4.依照权利要求1所述的活性炭负载碘化亚铜催化剂，其特征在于活性炭是球状、柱状、圆桶状、无定形颗粒状或粉末状。
5.依照权利要求2所述的还原剂，其特征在于还原剂是甲醛、二氧化硫、亚硫酸钠、硫代硫酸钠。
6.依照权利要求3所述的还原剂，其特征在于还原剂是甲醛、二氧化硫、亚硫酸钠、硫代硫酸钠。
7.依照权利要求3所述的乙醇水混合溶剂，其特征在于乙醇水体积比是2∶8～8∶2.
8.依照权利要求1所述的活性炭负载碘化亚铜催化剂，其特征在于用作二烷基二硫与芳烃的烷硫基化反应的催化剂，制备烷硫基芳烃化合物。
9.依照权利要求8所述的二烷基二硫，其特征在于包括：二甲基二硫、二乙基二硫、二苄基二硫、二环己基二硫。
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| CN105825990A (zh) * | 2016-03-30 | 2016-08-03 | 淮北师范大学 | 一种CuI-Fe3O4磁性纳米复合物的制备方法 |
| CN105883895A (zh) * | 2016-05-25 | 2016-08-24 | 浙江汇能生物股份有限公司 | 一种碘化亚铜的制备方法 |
| CN106115764A (zh) * | 2016-06-23 | 2016-11-16 | 淮北师范大学 | 一锅球磨固相法制备CuI纳米粉体的方法 |
| CN106187823A (zh) * | 2016-07-04 | 2016-12-07 | 江苏省原子医学研究所 | 一种制备间碘苄胍的方法 |
| CN115612857A (zh) * | 2022-10-25 | 2023-01-17 | 昆明理工大学 | 一种选择性回收废旧电路板浸出液中金(iii)的方法 |
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| EP0132915B1 (en) * | 1983-07-20 | 1988-02-24 | Hidefumi Hirai | Method of preparing solid adsorbent for unsaturated hydrocarbon and process for separation of unsaturated hydrocarbon from gas mixture |
| US5210304A (en) * | 1991-03-11 | 1993-05-11 | Ethyl Corporation | Process for preparing hydrocarbyl aromatic amines |
| US5302755A (en) * | 1991-05-31 | 1994-04-12 | Ethyl Corporation | Method for DMTDA production |
| ATE402142T1 (de) * | 1998-06-18 | 2008-08-15 | Hoffmann La Roche | Verfahren für arylalkylsulfid |
| JP4493824B2 (ja) * | 2000-09-28 | 2010-06-30 | 日本パイオニクス株式会社 | 有害ガスの浄化方法及び浄化剤 |
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2006
- 2006-05-23 CN CNB2006100843991A patent/CN100431699C/zh not_active Expired - Fee Related
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| CN105825990A (zh) * | 2016-03-30 | 2016-08-03 | 淮北师范大学 | 一种CuI-Fe3O4磁性纳米复合物的制备方法 |
| CN105825990B (zh) * | 2016-03-30 | 2017-11-14 | 淮北师范大学 | 一种CuI‑Fe3O4磁性纳米复合物的制备方法 |
| CN105883895A (zh) * | 2016-05-25 | 2016-08-24 | 浙江汇能生物股份有限公司 | 一种碘化亚铜的制备方法 |
| CN106115764A (zh) * | 2016-06-23 | 2016-11-16 | 淮北师范大学 | 一锅球磨固相法制备CuI纳米粉体的方法 |
| CN106187823A (zh) * | 2016-07-04 | 2016-12-07 | 江苏省原子医学研究所 | 一种制备间碘苄胍的方法 |
| CN115612857A (zh) * | 2022-10-25 | 2023-01-17 | 昆明理工大学 | 一种选择性回收废旧电路板浸出液中金(iii)的方法 |
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