CN112221538A - 氟烷基改性纤维素负载钯催化剂的制备方法 - Google Patents
氟烷基改性纤维素负载钯催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种氟烷基改性纤维素负载钯催化剂的制备方法。所述方法先将微晶纤维素分散在N,N‑二甲基甲酰胺中,在冰浴条件下加入NaH,再加入全氟卤代烷,搅拌过夜,得到全氟卤代烷修饰的纤维素载体,然后将全氟卤代烷修饰的纤维素载体与氯化钯溶液混合研磨,放置过夜,再加入甲酸钠研磨,再次放置过夜,离心干燥得到氟烷基改性纤维素负载钯催化剂。本发明以天然高分子纤维素作为载体,其结构中含有大量羟基,可有效稳定金属纳米粒子,并采用全氟碳链对纤维素载体进行改性,进一步稳定金属钯纳米粒子,提高催化剂的稳定性。将本发明制备的催化剂用于硝基苯的还原反应中,产物收率最高可达100%。
Description
技术领域
本发明属于催化剂制备技术领域,涉及一种氟烷基改性纤维素负载钯催化剂的制备方法。
背景技术
负载型金属纳米颗粒催化剂具有高活性、易回收、耐用性强的优点。将金属纳米颗粒固定在固体载体上能够有效改善减小纳米颗粒尺寸导致的颗粒团聚问题,从而提高纳米催化剂的回收性。
高分子聚合物,包括天然聚合物和合成聚合物,一直被当做金属纳米颗粒的良好载体和稳定剂。其中天然高分子纤维素,由于其来源丰富、无毒、生物可降解及可再生的特性,受到了科研人员的极大关注。纤维素作为催化剂载体具有以下优点:(1)在大部分溶剂中具有较高的稳定性和良好的分散性;(2)含有大量羟基,可有效稳定金属纳米粒子;(3)在自然界中含量丰富,对环境无毒无害;(4)纤维素结构中含有的大量羟基,使得纤维素可参与许多反应,具有可衍生化的优良性。
然而纤维素直接负载金属催化剂的稳定性差,使用过程中金属或金属离子容易脱落,还有可能会形成微晶, 因此该类催化剂回收重复使用效果不是很理想。2001年,Quignard等首次将纤维素负载钯催化剂应用于Tsuji–Trost烯丙基化反应。而后,不同形态和结构的纤维素陆续被应用到负载催化剂的制备中。常见的纤维素负载催化剂的制备方法按还原剂的种类分为三种:外加还原剂,还原基团修饰的纤维素作为还原剂,纤维素本身作为还原剂。并且纤维素催化剂常用于有机反应中的还原、偶联反应。
氟作为自然界中分布广泛的元素之一,拥有着高电负性,较小的原子半径以及极低的可极化性。含氟化合物具有特殊的性质,且随氟含量的不同,性质有所不同。有机氟化合物特别是全氟化合物具有非常特殊的物理化学性质,被用于药物化学、精细化工品以及太阳能电池等领域中。含氟材料作为负载催化剂的载体的应用未见报道。
发明内容
本发明的目的在于提供一种氟烷基改性纤维素负载钯催化剂的制备方法。
本发明的目的通过以下技术方案实现:
氟烷基改性纤维素负载钯催化剂的制备方法,包括以下步骤:
步骤1,将微晶纤维素搅拌溶解在N,N-二甲基甲酰胺(DMF)中,搅拌2~3h,随后在冰浴的条件下加入NaH,搅拌反应45min~60min,反应结束后加入全氟卤代烷,搅拌反应10~24h,反应结束后将反应后的溶液抽滤,用水和乙醇依次洗涤,烘干,得到氟改性纤维素载体;
步骤2,在氟改性纤维素载体中加入氯化钯溶液,研磨,静置24h以上,再加入甲酸钠作为还原剂,研磨,静置24h以上,最后水洗,离心,干燥,得到氟烷基改性纤维素负载钯催化剂。
优选地,步骤1中,所述的全氟卤代烷选自三氟碘甲烷、全氟碘代乙烷、全氟碘代丁烷、全氟碘代己烷、全氟碘代辛烷、全氟碘代癸烷、全氟溴代丁烷、全氟溴代己烷、全氟溴代辛烷或全氟溴代癸烷。
优选地,步骤1中,所述的微晶纤维素和NaH质量比为1:0.7。
优选地,步骤1中,分批加入NaH。
优选地,步骤1中,所述的微晶纤维素与全氟卤代烷质量比为1:0.5~0.75。
优选地,步骤2中,研磨时间均为10~20min。
与现有技术相比,本发明具有以下优点:
本发明以来源丰富、无毒、生物可降解及可再生的天然高分子纤维素作为载体,并采用全氟碳链对纤维素载体进行改性,对金属钯纳米粒子起稳定作用,提高了催化剂的稳定性。将本发明制备的催化剂用于硝基苯的还原反应中,产物收率最高可达100%。
附图说明
图1为本发明制备方法的合成路线示意图。
具体实施方式
实施例1
室温条件下,将1g微晶纤维素溶解到20mlDMF中,水浴搅拌3h。随后冰浴条件下加入400mgNaH,冰浴搅拌30min。再加入300mgNaH,冰浴搅拌15min。随后加入0.75g全氟碘代丁烷,搅拌过夜。抽滤后依次加入水和乙醇洗涤,烘干。取300mg制得的氟改性纤维素,加入0.6ml,5mg/ml的氯化钯溶液,研磨10min,放置一天。再加入1mmol甲酸钠,研磨20min,放置一天。加水洗涤,离心,干燥得到氟烷基改性纤维素负载钯催化剂。
将氟烷基改性纤维素负载钯催化剂用于硝基苯的还原反应,实验过程为:
取24.5mg催化剂于试管中,通入氢气,加入0.2mmol硝基苯与3ml水的混合溶液,搅拌反应3h,所得产物收率为99.425%。
实施例2
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代丁烷质量为0.5g,硝基苯还原反应所得产物收率为100%。
对比例1
反应步骤与实施例1完全相同,不同之处在于:
所用催化剂为纤维素负载钯催化剂,未经过氟改性处理。硝基苯还原反应所得产物收率为75.215%。
对比例2
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代丁烷质量为1g,硝基苯还原反应所得产物收率为94.424%。
对比例3
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代丁烷质量为0.25g,硝基苯还原反应所得产物收率为94.5%。
实施例3
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代丁烷质量为0.5g,硝基苯还原反应时长2.5h,硝基苯还原反应产物收率为62.324%。
实施例4
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代烷为全氟碘代己烷,质量为0.5g,硝基苯还原反应时长2.5h,硝基苯还原反应产物收率为61.756%。
实施例5
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代烷为全氟碘代辛烷,质量为0.5g,硝基苯还原反应时长2.5h,硝基苯还原反应产物收率为64.560%。
实施例6
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟碘代烷为全氟碘代癸烷,质量为0.5g,硝基苯还原反应时长2.5h,硝基苯还原反应产物收率为63.069%。
实施例7
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟卤代烷为全氟溴代丁烷,质量为0.5g,硝基苯还原反应产物收率为90.343%。
实施例8
反应步骤与实施例1完全相同,不同之处在于:
加入的全氟卤代烷为全氟溴代辛烷,质量为0.5g,硝基苯还原反应产物收率为95.394%。
对比例4
反应步骤与实施例1完全相同,不同之处在于:
纤维素改性反应所用碱为三级丁醇钾(t-BuOK),硝基苯还原产物收率为92.125%。
Claims (6)
1.氟烷基改性纤维素负载钯催化剂的制备方法,其特征在于,包括以下步骤:
步骤1,将微晶纤维素搅拌溶解在N,N-二甲基甲酰胺中,搅拌2~3h,随后在冰浴的条件下加入NaH,搅拌反应45min~60min,反应结束后加入全氟卤代烷,搅拌反应10~24h,反应结束后将反应后的溶液抽滤,用水和乙醇依次洗涤,烘干,得到氟改性纤维素载体;
步骤2,在氟改性纤维素载体中加入氯化钯溶液,研磨,静置24h以上,再加入甲酸钠作为还原剂,研磨,静置24h以上,最后水洗,离心,干燥,得到氟烷基改性纤维素负载钯催化剂。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的全氟卤代烷选自三氟碘甲烷、全氟碘代乙烷、全氟碘代丁烷、全氟碘代己烷、全氟碘代辛烷、全氟碘代癸烷、全氟溴代丁烷、全氟溴代己烷、全氟溴代辛烷或全氟溴代癸烷。
3.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的微晶纤维素和NaH质量比为1:0.7。
4.根据权利要求1所述的制备方法,其特征在于,步骤1中,分批加入NaH。
5.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的微晶纤维素与全氟卤代烷质量比为1:0.5~0.75。
6.根据权利要求1所述的制备方法,其特征在于,步骤2中,研磨时间均为10~20min。
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