CN111519430A - 一种腈纶纤维固载dabco催化剂的制备方法及其应用 - Google Patents
一种腈纶纤维固载dabco催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种腈纶纤维固载DABCO催化剂的制备方法及其应用,属于绿色催化技术领域。本发明旨在解决现有固载DABCO催化剂载体材料性能不足、制备过程复杂、催化活性不理想、催化位点易流失等问题,主要包括如下三个步骤:一、功能分子的合成;二、乙二胺功能化腈纶纤维的合成;三、腈纶纤维固载DABCO催化剂的合成。该催化剂对于醛、丙二腈、1‑萘酚一锅三组分反应具有载体廉价易得、催化剂制备过程简单、催化活性高、易分离、循环性能好、溶剂绿色、成本低等优点。另外,该纤维催化剂易于二次加工,可以制成多种形状,方便工业催化固定床制备,具有较好的工业应用价值。
Description
技术领域
本发明属于绿色催化技术领域,涉及一种腈纶纤维固载DABCO催化剂的制备方法及其应用。
背景技术
现今社会经济快速发展的同时,环境污染问题也日益严峻。传统化学的污染主要来源于化学反应中过量原料的加入。反应中催化剂不仅能减少反应所需的能量,还能减少反应试剂的用量并提高产物的选择性。所以,催化在绿色化学十二原则中占据了重要的地位。虽然传统小分子均相催化剂可以高效的催化有机反应,但其从反应体系中分离的过程不仅操作复杂,而且不可避免的需要用到大量的有机试剂从而造成二次污染。此外,某些小分子催化剂价格昂贵且制作过程复杂,而其难以回收的缺点更增加了这些小分子催化剂的应用成本。近年来,为了减少环境污染和催化剂的应用成本,越来越多的学者通过不同方法把小分子催化剂固载到各种载体上从而实现了催化剂的循环使用。此外,固载催化剂大多以固体形式存在,更有利于工业固定床催化的应用,这比小分子催化更具应用前景。
1,4-二氮杂二环[2.2.2]辛烷(DABCO),又名三乙烯二胺或三亚乙基二胺,是一种笼状二氮杂双环化合物。作为一种中等位阻的弱碱,DABCO具有无毒高效、廉价环保等优点,因此其被广泛应用作各种有机反应催化剂,如Baylis-Hillman反应、氮杂环丙烷的开环反应、醚类的氧化脱保护反应、区域选择性亲和取代反应等等。但因为均相小分子催化剂很难从体系中分离从而造成资源浪费和环境污染等问题,DABCO的应用也受到了一定的限制。
2-氨基-2-苯并吡喃衍生物作为杂环化合物广泛的存在于自然界的植物体内,是合成其他重要化合物的不可或缺的中间体,其广泛应用于染料、化妆品、医学药品和生物可降解农药等,并可作为光学材料。同时,其在植物体内的广泛存在性决定了2-氨基-2-苯并吡喃衍生物亦是许多天然产品的重要组成成分。传统催化剂如DMAP、Na2CO3、TiCl4、十六烷基三甲基溴化铵、甲磺酸等小分子也可催化合成2-氨基-2-苯并吡喃衍生物,但存在反应步骤较多,反应中使用的溶剂挥发性强,毒性大,废液处理困难等不足。因此,探索绿色、环境友好的2-氨基-2-苯并吡喃衍生物合成方法仍具有重要的科研价值。
腈纶纤维(PANF)是一种广泛应用于纺织业的合成纤维,由于其不规则的螺旋形构象、没有十分严格的结晶区等独特的结构特点,其具有热稳定和化学稳定性、很强的机械强度和防蛀性等优点。此外,腈纶纤维内部和表面含有大量具有化学活性的氰基,这些氰基经过简单的化学方法可以转化为多种其他官能团,而这些官能团可作为固载小分子催化剂的桥联键。
鉴于此,特提出本发明。
发明内容
针对现有固载DABCO催化剂载体材料性能不足、制备过程复杂、催化活性不理想、催化位点已流失等问题,提出了一种腈纶纤维固载DABCO催化剂的制备方法及其应用,载体廉价易得、催化剂制备过程简单、催化活性高、成本低、循环性能好。
同时本发明为了结合DABCO小分子催化剂和腈纶纤维的优点,把DABCO固载于腈纶纤维上并用于催化一锅三组分合成2-氨基-2-苯并吡喃衍生物的新方法。该催化剂制备方法简单,所得到的腈纶纤维固载DABCO催化剂中既含有活性叔胺催化位点,而且还还有亲水性季铵盐位点。这使得该催化剂具有较好的亲水性,能够与水溶液更好的浸润,所以可以在绿色溶剂水中高效催化合成2-氨基-2-苯并吡喃衍生物。此外该催化剂还表现出了优异的循环使用性能,具有较好的工业应用价值。
为解决上述技术问题,本发明采用以下述技术方案实现:
一种腈纶纤维固载DABCO催化剂的制备方法,包含如下步骤:
1)功能小分子的合成:将三乙烯二胺搅拌溶解于乙酸乙酯中,然后加入氯乙酸甲酯或溴乙酸甲酯,室温下搅拌反应一定时间,将反应后的混合物抽滤得到白色固体,然后用无水乙醚洗涤,干燥过夜,得到含氯或溴离子的DABCO衍生物功能小分子;
2)乙二胺功能化腈纶纤维的合成;
3)腈纶纤维固载DABCO催化剂的合成:在烧瓶中加入干燥的乙二胺功能化腈纶纤维、功能小分子、无水碳酸钠和去离子水,电磁搅拌下回流反应2-12h,然后取出纤维,抽滤,洗涤、干燥得到腈纶纤维固载DABCO催化剂。
进一步,所述步骤(1)中三乙烯二胺与氯乙酸甲酯或溴乙酸甲酯的摩尔比为0.1:(0.05-2)。
进一步,所述步骤(1)中室温下搅拌反应的时间为24h。
进一步,所述步骤(2)中乙二胺功能化腈纶纤维的合成方法如下:在烧瓶中按质量比1:2加入乙二胺和水,再加入干燥的腈纶纤维,电磁搅拌下回流反应1-10h;然后取出纤维,抽滤,用50-60℃的去离子水洗涤至滤液pH=7,再经真空60℃干燥过夜,得到浅黄色乙二胺功能化腈纶纤维。
进一步,所述步骤(3)中乙二胺功能化腈纶纤维与无水碳酸钠的质量比为0.5:(0.5-3),功能小分子的量为5-25eq,即功能性小分子的物质的量为固载到腈纶纤维上乙二胺物质的量的5-25倍。
进一步,所述步骤(3)中以0.5g乙二胺功能化腈纶纤维的质量为基准,需要去离子水的量为30mL。
进一步,所述步骤(3)中洗涤采用50-60℃的去离子水水洗至滤液pH=7,干燥是在真空60℃干燥过夜。
利用本发明所述的制备方法制得的腈纶纤维固载DABCO催化剂用于催化合成2-氨基-2-苯并吡喃衍生物。
本发明的有益效果:
(1)本发明以腈纶纤维为载体制备固载DABCO催化剂。该催化剂载体廉价易得、催化剂制备过程简单、催化活性高、成本低、循环性能好。有效解决了现有固载DABCO催化剂载体材料性能不足、制备过程复杂、催化活性不理想、催化位点易流失等问题。
(2)将本发明制备的腈纶纤维固载DABCO催化剂应用于一锅三组分合成2-氨基-2-苯并吡喃衍生物中,由于所得到的腈纶纤维固载DABCO催化剂中既含有活性叔胺催化位点,而且还还有亲水性季铵盐位点,这使得该催化剂具有较好的亲水性,能够与水溶液更好的浸润,所以可以在绿色溶剂水中高效催化合成2-氨基-2-苯并吡喃衍生物。如对氯苯甲醛、丙二腈、1-萘酚的一锅三组分反应中,该催化剂表现出了优异的催化活性,产率高达96%。而且纤维催化剂用镊子夹出后,经过简单的清洗就可以直接用于下个循环,且循环十次后反应产率没有明显降低。此外,该纤维催化剂便于制成多种形状,更有利于工业固定床催化的应用,具有潜在工业应用价值。
附图说明
图1为2-氨基-2-苯并吡喃产物的核磁共振氢谱。
具体实施方式
下面结合具体实施例,对本发明做进一步说明。应理解,以下实施例仅用于说明本发明而非用于限制本发明的范围,该领域的技术熟练人员可以根据上述发明的内容作出一些非本质的改进和调整。
实施例1
本实施例的腈纶纤维固载DABCO催化剂的制备方法如下:
(1)将三乙烯二胺(11.22g,0.1mol)在室温下搅拌溶解于乙酸乙酯(200mL)中,然后逐滴加入溴乙酸甲酯(8.68g,0.08mol),室温条件下搅拌反应24h。将反应后的混合物抽滤得到白色固体,然后用无水乙醚洗涤,干燥过夜,得到含溴离子DABCO衍生物,反应过程如下所示:
(2)在50mL烧瓶中加入乙二胺和水(体积比为1∶2)共计30mL,再加入1.0g干燥的腈纶纤维,电磁搅拌下回流3h。然后取出纤维,抽滤,用50-60℃的去离子水洗涤至滤液pH=7。再经真空干燥(60℃)过夜,得到浅黄色乙二胺功能化腈纶纤维PANF-E,反应过程如下所示;
(3)在50mL烧瓶中加入0.5g(1.48mmol/g)干燥的乙二胺胺化纤维、含溴负离子DABCO衍生物DABCO-Br(15eq.)、0.5g无水碳酸钠、30ml去离子水,电磁搅拌下回流反应3h。然后取出纤维,抽滤,用50-60℃的去离子水水洗至滤液pH=7。再经真空干燥(60℃)过夜,得到含溴负离子腈纶纤维固载DABCO催化剂PANF-DABCO-Br,反应过程如下所示:
元素分析如下所示:
与PANF相比,PANF-E的碳含量和氮含量明显降低,而氢含量则明显升高,这是由于固载上的乙二胺基团的碳含量比PANF低,而氢含量比PANF高的缘故;氮含量下降主要是因为纤维在胺化过程中氰基的氨解形成酰胺并释放一分子氨气所造成的,另外氰基的水解和交联反应也是存在的。固载DABCO后,由于固载上的DABCO官能团的碳、氢和氮含量均比PANF-E要低,所以其各元素含量均降低。这也说明了DABCO小分子在纤维上的固载成功。
实施例2
本实施例的腈纶纤维固载DABCO催化剂的制备方法如下:
(1)将三乙烯二胺(11.22g,0.1mol)在室温下搅拌溶解于乙酸乙酯(200mL)中,然后逐滴加入氯乙酸甲酯(8.68g,0.08mol),室温条件下搅拌反应24h。将反应后的混合物抽滤得到白色固体,然后用无水乙醚洗涤,干燥过夜,得到含氯离子DABCO衍生物,反应过程如下所示:
(2)乙二胺功能化腈纶纤维PANF-E按实施例1的方法合成;
(3)在50mL烧瓶中加入0.5g(1.48mmol/g)干燥的乙二胺胺化纤维、含氯负离子DABCO衍生物DABCO-Cl(15eq.)、0.5g无水碳酸钠、30ml去离子水,电磁搅拌下回流反应3h。然后取出纤维,抽滤,用50-60℃的去离子水水洗至滤液pH=7。再经真空干燥(60℃)过夜,得到含溴负离子腈纶纤维固载DABCO催化剂PANF-DABCO-Cl,反应过程如下所示:
元素分析如下所示:
与PANF相比,PANF-E的碳含量和氮含量明显降低,而氢含量则明显升高,这是由于固载上的乙二胺基团的碳含量比PANF低,而氢含量比PANF高的缘故;氮含量下降主要是因为纤维在胺化过程中氰基的氨解形成酰胺并释放一分子氨气所造成的,另外氰基的水解和交联反应也是存在的。固载DABCO后,由于固载上的DABCO官能团的碳、氢和氮含量均比PANF-E要低,所以其各元素含量均降低。又因为氯的原子质量比溴小,所以PANF-DABCO-Cl的碳、氢、氮元素含量比PANF-DABCO-Br略有增加。这也说明了DABCO小分子在纤维上的固载成功。
将上述腈纶纤维固载DABCO催化剂应用于对氯苯甲醛、丙二腈、1-萘酚一锅三组分合成2-氨基-2-苯并吡喃,反应按如下方案进行。
在50mL圆底烧瓶中加入对氯苯甲醛(1mmol),丙二腈(1mmol),1-萘酚(1mmol)、腈纶纤维固载DABCO催化剂(15mol%)和15mL的水,磁力搅拌下回流1h。反应结束后,用镊子取出纤维催化剂。用乙酸乙酯多次冲洗纤维以收集纤维上吸附的产物。然后合并有机相,旋蒸除去溶剂,剩余固体用乙醇重结晶后得到2-氨基-2-苯并吡喃产物。反应产物经核磁氢谱表征(1H NMR(400MHz,DMSO):如图1所示。)
实验结果表1和表2所示。
表1 不同催化剂用于催化合成2-氨基-2-苯并吡喃的活性评价
表2 催化对氯苯甲醛、丙二腈、1-萘酚一锅三组分反应的循环性能评价
循环 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
产率(%) | 96 | 96 | 94 | 95 | 94 | 92 | 89 | 88 | 88 | 87 |
。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (9)
1.一种腈纶纤维固载DABCO催化剂的制备方法,其特征在于,包括如下步骤:
(1)功能小分子的合成:将三乙烯二胺搅拌溶解于乙酸乙酯中,然后加入氯乙酸甲酯或溴乙酸甲酯,室温下搅拌反应一定时间,将反应后的混合物抽滤得到白色固体,然后用无水乙醚洗涤,干燥过夜,得到含氯或溴离子的DABCO衍生物功能小分子;
(2)乙二胺功能化腈纶纤维的合成;
(3)腈纶纤维固载DABCO催化剂的合成:在烧瓶中加入干燥的乙二胺功能化腈纶纤维、功能小分子、无水碳酸钠和去离子水,电磁搅拌下回流反应2-12 h,然后取出纤维,抽滤,洗涤、干燥得到腈纶纤维固载DABCO催化剂。
2.根据权利要求1所述的制备方法,其特征在于:所述步骤(1)中三乙烯二胺与氯乙酸甲酯或溴乙酸甲酯的摩尔比为0.1:(0.05-2)。
3.根据权利要求1所述的制备方法,其特征在于:所述步骤(1)中室温下搅拌反应的时间为24 h。
4.根据权利要求1所述的制备方法,其特征在于:所述步骤(2)中乙二胺功能化腈纶纤维的合成方法如下:在烧瓶中按质量比1:2加入乙二胺和水,再加入干燥的腈纶纤维,电磁搅拌下回流反应1-10h;然后取出纤维,抽滤,用50-60℃的去离子水洗涤至滤液pH=7,再经真空60℃干燥过夜,得到浅黄色乙二胺功能化腈纶纤维。
5.根据权利要求1所述的制备方法,其特征在于:所述步骤(3)中乙二胺功能化腈纶纤维与无水碳酸钠的质量比为0.5:(0.5-3),功能小分子的量为5-25eq,即功能性小分子的物质的量为固载到腈纶纤维上乙二胺物质的量的5-25倍。
6.根据权利要求1所述的制备方法,其特征在于:所述步骤(3)中以0.5 g乙二胺功能化腈纶纤维的质量为基准,需要去离子水的量为30 mL。
7.根据权利要求1所述的制备方法,其特征在于:所述步骤(3)中洗涤采用50-60℃的去离子水水洗至滤液pH=7,干燥是在真空60℃干燥过夜。
8.利用权利要求1-7任意所述的制备方法制得的腈纶纤维固载DABCO催化剂。
9.根据权利要求8所述的腈纶纤维固载DABCO催化剂用于催化合成2-氨基-2-苯并吡喃衍生物。
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