CN116550384B - 一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法 - Google Patents
一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法；以聚醚醚酮超强纤维为基体，首先将氯甲基功能化聚醚醚酮纤维的部分氯甲基在碱作用下与氨基酸反应，酸化后得氨基酸功能化聚醚醚酮纤维，随后将其在缚酸剂作用下与5,6,7,8‑四氢[1,2,4]三唑并[4,3‑a]吡啶反应，制得含三唑鎓离子和羧酸根阴离子的聚醚醚酮纤维负载三唑鎓盐；该超强纤维负载三唑鎓盐在特定温度下原位生成负载型氮杂环卡宾，可用于高效催化糠偶姻缩合和环加成反应等，反应毕降至室温氮杂环卡宾复原其前体三唑鎓盐，且催化体系便于分离操作和循环应用，为工业催化合成提供了新途径。
Description
技术领域
本发明涉及一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法，尤其是一种适用于温控循环原位生成NHC催化极性反转反应的催化剂，属于绿色催化技术领域。
背景技术
最近几年，与绿色催化相关的有机催化备受关注，并取得了显著进展，2021年的诺贝尔化学奖也授予了开辟有机小分子不对称催化领域的两位化学家。其中， NHC作为有机小分子催化剂因其独特的结构和电子属性，能够促使羰基等极性反转而在合成化学中应用广泛，且近两年连续入选中科院发布的化学与材料科学领域Top 10热点前沿。当前，NHC用于催化时通常从其前体原位生成且通过均相体系进行，然而这些游离态的NHC因其较高的反应活性，易二聚或受周围环境影响以及空气、水分敏感性等导致其结构破坏而难以进行分离回收、长期储存，且催化剂用量大、成本高，污染严重。因此，探索和研究高效可循环的NHC催化材料开发更为绿色的催化工艺仍将是该领域的一个侧重点。针对NHC催化难以循环的弊端，有两条途径被用于NHC的便捷回收与重复利用，即合成聚合态NHC和制备负载型NHC。通过聚合等方式获取聚合态NHC的方法可设计性较强，且活性位分布均匀，但相关操作要求也较高。其中，所设计单体的反应活性及聚合过程的控制条件等均对聚合反应的聚合度以及聚合物的分子量有较大影响，此外，所得NHC前体聚合物的结构、形态等也会对后续的催化应用与循环产生诸多影响。因此，该方法一般来讲操作过程较为繁琐，使用成本高且不利于规模化工业应用。相比而言，制备负载型NHC也具有较强的可设计性，载体种类以及负载方式多样，可根据所催化反应的要求而选择，当然其性能优劣也受限于载体材料的特性以及功能化负载方式的调控等。例如，美国科罗拉多州立大学华裔科学家Eugene Y.-X.Chen等，通过设计二氧化硅或聚苯乙烯树脂负载的（苯并）咪唑类鎓盐，将其在强碱作用下脱去质子原位生成负载型NHC用于催化糠偶姻缩合反应，催化结束通过加入HCl猝灭反应获得质子后复原进而开展循环应用，虽然该催化体系具有较好的循环使用性能，但该工艺操作时需反复添加碱、酸来达到催化剂再生循环的目的，而且整个流程需要在真空手套箱内完成。合成聚合态NHC和制备负载型NHC各有利弊，不过一些负载型NHC可凭借既有材料的简单功能化即可完成制备，在一定程度上更为便捷。此外，无论是聚合态NHC还是负载型NHC，二者在实现NHC循环再生的方式上是没有区别的，在诸多方式中，温敏型NHC由于循环操作过程中无需额外添加试剂（如强碱DBU、KOtBu等以及无水HCl、HBF4.Et2O等），仅通过简单的温度控制一方面为所催化的反应提供能量，另一方面也借此实现了NHC循环应用，这一方式虽然有能耗但在工业操作中最容易完成。因此，设计和制备便捷、经济的负载温敏型NHC，开发更为清洁的催化技术，具有十分重要的研究价值。
发明内容
本发明的目的在于提供一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法，该温敏型催化剂以聚醚醚酮为基体，其特征在于基体上共价键合5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶鎓离子和羧酸根阴离子。该纤维负载鎓盐特定温度可原位生成NHC用于催化相关反应，降低温度后复原至前体鎓盐，温控循环可使用10次以上。
本发明的技术方案为：
一种超强纤维负载三唑鎓盐温敏型催化剂，以聚醚醚酮超强纤维为基体，通过化学接枝的方式制得阳离子为5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶鎓离子，阴离子为羧酸根的负载型鎓盐作为NHC前体。
本发明的一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法，优选步骤如下：
1) 等摩尔量的氨基酸与碱共混于溶剂去离子水中，随后氯甲基功能化增重为32%的聚醚醚酮纤维与氨基酸按质量比为1:1.0~5.0添加至上述混合液中，搅拌下逐步升温至特定温度反应，反应毕取出超强纤维，依次用酸液、去离子水冲洗至滤液呈中性，然后70~80oC干燥至恒重，得到氨基酸功能化超强纤维；
2) 将所得氨基酸功能化超强纤维与5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶按质量比为1:0.5~2.0共混于乙腈中，并加入氨基酸功能化超强纤维氨基酸含量2.5~4.0倍摩尔当量的缚酸剂搅拌下反应，反应毕取出超强纤维并用乙醇、去离子水冲洗，然后70~80 oC干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
所述步骤1) 优选的氨基酸为甘氨酸或丙氨酸，碱为氢氧化钠或碳酸钠，酸液为甲酸或冰醋酸；优选的反应温度为95~100oC，反应时间为4~8 h。
所述步骤2) 优选的缚酸剂为二异丙基乙胺；优选反应温度为80~85oC，反应时间为6~12 h。
本发明的优点在于，将阳离子为5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶鎓离子和阴离子为羧酸根的鎓盐共同键合于超强纤维聚醚醚酮的表层，该负载鎓盐作为温敏型NHC前体,特定温度可原位生成负载型NHC用于催化多种极性反转反应，降温后NHC复原其前体鎓盐，经温度控制催化循环可达20次以上。
附图说明
图1：超强纤维负载三唑鎓盐温敏型催化剂结构示意图；
图2：超强纤维负载三唑鎓盐温敏型催化剂温控循环催化Stetter反应效果；
图3：超强纤维负载三唑鎓盐温敏型催化剂温控循环催化环加成反应合成吡喃酮效果。
具体实施方式
具体实施例进一步说明本发明的实施过程。
实施例1在100 mL的三口烧瓶中加入0.5 g甘氨酸、70 mL水和0.71 g碳酸钠，搅拌均匀后，加入0.5 g氯甲基功能化增重32%的聚醚醚酮纤维。逐步加热至100 oC，搅拌下反应8 h，冷至室温取出超强纤维，依次用甲酸、去离子水冲洗至滤液呈中性，然后于75 oC的干燥箱中真空干燥至恒重，得氨基酸功能化超强纤维；
在100 mL的三口烧瓶中加入上述干燥的氨基酸功能化超强纤维，0.3 g 5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶和70 mL乙腈，并添加0.3 g二异丙基乙胺，逐步加热至85oC，搅拌下反应12 h，冷至室温取出超强纤维，依次用乙醇、去离子水冲洗，然后于75 oC的干燥箱中真空干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
实施例2在100 mL的三口烧瓶中加入0.5 g丙氨酸、70 mL水和0.23 g氢氧化钠，搅拌均匀后，加入0.5 g氯甲基功能化增重32%的聚醚醚酮纤维。逐步加热至100 oC，搅拌下反应8 h，冷至室温取出超强纤维，依次用冰醋酸、去离子水冲洗至滤液呈中性，然后于温度75oC的干燥箱中真空干燥至恒重，得氨基酸功能化超强纤维；
在100 mL的三口烧瓶中加入上述干燥的氨基酸功能化超强纤维，0.4 g 5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶和70 mL乙腈，并添加0.4 g二异丙基乙胺，逐步加热至85oC，搅拌下反应12 h，冷至室温取出超强纤维，依次用乙醇、去离子水冲洗，然后于温度75 oC的干燥箱中真空干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
实施例3在100 mL的三口烧瓶中加入1.0 g甘氨酸、70 mL水和1.41 g碳酸钠，搅拌均匀后，加入0.5 g氯甲基功能化增重32%的聚醚醚酮纤维。逐步加热至95 oC，搅拌下反应6h，冷至室温取出超强纤维，依次用甲酸、去离子水冲洗至滤液呈中性，然后于75 oC的干燥箱中真空干燥至恒重，得氨基酸功能化超强纤维；
在100 mL的三口烧瓶中加入上述干燥的氨基酸功能化超强纤维，0.4 g 5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶和70 mL乙腈，并添加0.4 g二异丙基乙胺，逐步加热至85oC，搅拌下反应10 h，冷至室温取出超强纤维，依次用乙醇、去离子水冲洗，然后于75 oC的干燥箱中真空干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
实施例4在100 mL的三口烧瓶中加入1.0 g丙氨酸、70 mL水和0.46 g氢氧化钠，搅拌均匀后，加入0.5 g氯甲基功能化增重32%的聚醚醚酮纤维。逐步加热至95 oC，搅拌下反应6 h，冷至室温取出超强纤维，依次用冰醋酸、去离子水冲洗至滤液呈中性，然后于温度80oC的干燥箱中真空干燥至恒重，得氨基酸功能化超强纤维；
在100 mL的三口烧瓶中加入上述干燥的氨基酸功能化超强纤维，0.5 g 5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶和70 mL乙腈，并添加0.5 g二异丙基乙胺，逐步加热至85oC，搅拌下反应8 h，冷至室温取出超强纤维，依次用乙醇、去离子水冲洗，然后于温度80 oC的干燥箱中真空干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
实施例5在100 mL的三口烧瓶中加入2.5 g甘氨酸、70 mL水和2.66 g氢氧化钠，搅拌均匀后，加入0.5 g氯甲基功能化增重32%的聚醚醚酮纤维。逐步加热至95 oC，搅拌下反应4 h，冷至室温取出超强纤维，依次用甲酸、去离子水冲洗至滤液呈中性，然后于75 oC的干燥箱中真空干燥至恒重，得氨基酸功能化超强纤维；
在100 mL的三口烧瓶中加入上述干燥的氨基酸功能化超强纤维，2.0 g 5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶和70 mL乙腈，并添加2.0 g二异丙基乙胺，逐步加热至80oC，搅拌下反应6 h，冷至室温取出超强纤维，依次用乙醇、去离子水冲洗，然后于75 oC的干燥箱中真空干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
取实施例3中的超强纤维负载酸碱双功能催化剂0.1 g缠绕在反应器的搅拌桨上（模拟转框式反应），用于5-羟甲基糠醛的糠偶姻缩合反应（反应条件：10.0 mmol 5-羟甲基糠醛和20 mL二氧六环，氮气保护下逐步升温至85 oC反应8 h）,反应毕降至室温将反应液排出，经后处理得1.21 g 糠偶姻产品，产物收率达96%。按上述操作，温控循环催化10次，产物收率未见明显降低（图2）。
取实施例3中的超强纤维负载酸碱双功能催化剂0.1 g缠绕在反应器的搅拌桨上（模拟转框式反应），用于邻苯二醛和硝基苯乙烯的环加成反应（反应条件：10.0 mmol邻苯二醛，10.0 mmol硝基苯乙烯和20 mL甲苯，氮气保护下逐步升温至85 oC反应6 h）,反应毕降至室温后将反应液排出，经后处理得2.23 g 2-苯基-1,4-萘醌，产物收率达95%。按上述操作，温控循环催化应用10次，产物收率未见明显降低（图3）。
本发明的公开和提出的一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法，本领域技术人员可通过借鉴本文内容，适当改变原料、工艺参数、结构设计等环节实现。本发明的方法与技术已通过较佳实施例子进行描述，相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术进行改动或适当变更与组合，来实现本发明技术。特别需要指出的是，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容中。
Claims (5)
1.一种超强纤维负载三唑鎓盐温敏型催化剂的制备方法，其特征是通过聚醚醚酮纤维化学接枝的方式制得阳离子为5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶鎓离子，阴离子为羧酸根的负载型鎓盐，该超强纤维负载三唑鎓盐特定温度可原位生成氮杂环卡宾用于催化反应，降低温度后复原至前体鎓盐，示意图如下，其中R为CH2或CHCH3：
，
该超强纤维负载三唑鎓盐温敏型催化剂的具体制备步骤如下：
1) 将等摩尔量的氨基酸与碱共混于溶剂去离子水中，随后将氯甲基功能化增重为32%的聚醚醚酮纤维与氨基酸按质量比为1:1.0~5.0添加至上述混合液中，搅拌下逐步升温至特定温度反应，反应毕取出超强纤维，依次用酸液、去离子水冲洗至滤液呈中性，然后70~80℃干燥至恒重，得到氨基酸功能化超强纤维；
2) 将所得氨基酸功能化超强纤维与5,6,7,8-四氢[1,2,4]三唑并[4,3-a]吡啶按质量比为1:0.5~2.0共混于乙腈中，并加入氨基酸功能化超强纤维氨基酸含量2.5~4.0倍摩尔当量的缚酸剂，搅拌下逐步升温至特定温度反应，反应毕取出超强纤维并用乙醇、去离子水冲洗，然后70~80℃干燥至恒重，得超强纤维负载三唑鎓盐温敏型催化剂。
2. 如权利要求1所述的方法，其特征在于所述步骤1) 的氨基酸为甘氨酸或丙氨酸，碱为氢氧化钠或碳酸钠，酸液为甲酸或冰醋酸。
3. 如权利要求1所述的方法，其特征在于所述步骤2) 的缚酸剂为二异丙基乙胺。
4. 如权利要求1所述的方法，其特征在于所述步骤1) 反应温度为95~100℃，反应时间为4~8 h。
5. 如权利要求1所述的方法，其特征在于所述步骤2) 反应温度为80~85 ℃，反应时间为6~12 h。
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| CN106519558A (zh) * | 2016-10-11 | 2017-03-22 | 天津大学 | 咪唑鎓盐型聚醚醚酮/功能化介孔硅杂化膜制备及应用 |
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