CN106563509B - 一种催化剂的制备方法及其应用 - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了一种催化剂的制备方法及其应用,其特征在于,包括如下步骤:(1)在极性非质子性溶剂中,在碱的存在下,将水杨醛和烯丙基卤代烃进行亲核取代反应得到亲核取代产物;(2)将步骤(1)产物加热发生Claisen重排反应;(3)在有机溶剂中,将步骤(2)产物与乙二胺缩合得到Salen配体;(4)在醚类溶剂中,在自由基引发剂和助引发剂的存在下,将Salen配体与二乙烯基苯共聚得到具有介孔结构的Salen有机聚合物;(5)在醇与水的混合溶剂中,以Salen有机聚合物为载体制备得到具有介孔结构Salen有机聚合物Co催化剂;本发明制备的催化剂应用于安息香的催化氧化,不仅具有很好的催化活性,而且能多次使用而不降低催化活性。
Description
技术领域:
本发明属于有机材料合成领域,尤其涉及了一种具有介孔结构的Salen有机聚合物及其Co催化剂的制备方法,并将该催化剂应用于安息香的催化氧化得到苯偶酰。
背景技术:
金属Salen配合物是一类重要的有机反应催化剂,它可在非常温和的条件下以高产率、高选择性地催化许多重要有机反应,如:Diels-Alder反应,烯烃环氧化,Strecker反应,催化氧化等。另外,从结构上分析,Salen配体还具有合成简单,结构容易修饰,并可与多种金属(Cr、Al、Co、Cu、Zn、Ni等)配合等优点而收到了化学家的广泛关注。经典的金属Salen催化反应一般均相体系中进行。虽然均相反应具有催化活性高、反应选择性好等优点,但是难以对催化剂进行回收和重复使用。因此,均相金属催化剂反应不仅容易造成对产物的污染,而且会大大增加了生产成本,难以应用于工业化生产。非均相催化具有催化剂容易回收,并可重复使用等特点,收到了越来越多关注。
在非均相Salen有机聚合物金属催化剂研究方面,K.C.Gupta小组报道了以AIBN为聚合反应引发剂,将具有烯丙基的希夫碱(水杨醛与乙二胺)与苯乙烯、二乙烯苯、明胶、膨润土等反应得到了无孔道结构的高分子球。然后,以此高分子球为载体,以CoCl2。6H2O为金属源制备了一种非均相Co催化剂,并将其应用于双氧水的催化分解(Chinese Journal ofPolymer Science,2004,22(1):31-42)。
发明内容:
本发明所要解决的问题是克服传统金属Salen催化剂不易回收并且不能重复使用的缺陷,提供了一种方法可制备得到具有介孔结构特征的Salen有机聚合物,进而制备得到了一种可多次重复使用的非均相Co催化剂,其可用于安息香的催化氧化得到苯偶酰。
为了解决上述技术问题,本发明通过下述技术方案得以解决:
一种具有介孔结构的Salen有机聚合物Co催化剂的制备方法,其特征在于,包括如下步骤:
步骤(1):在极性非质子性溶剂中,在碱的存在下,将水杨醛和烯丙基卤代烃在一定温度下搅拌一定时间,反应液经萃取、洗涤以及浓缩等得到产物苯基烯丙基醚(P-1);
步骤(2):将步骤(1)所得产物在一定温度下加热发生Claisen重排反应得到Claisen重排反应产物(P-2);
步骤(3):在有机溶剂中,将步骤(2)所得产物与乙二胺缩合得到Salen配体(P-3);
步骤(4):在醚类溶剂中,在自由基引发剂和助引发剂的存在下,将步骤(3)所得Salen配体(P-3)与二乙烯基苯(DVB)以一定的质量比混合,混合物先在室温下搅拌,再在100℃下回流热晶化,冷却后转入水热反应釜中120℃加热,挥发溶剂后得到介孔Salen有机聚合物(MS-Salen);
步骤(5):在醇与水的混合溶剂中,将步骤(4)所得介孔Salen配体(MS-Salen)与钴盐混合,在室温条件下搅拌一定时间后,将溶剂减压蒸发、真空干燥得到介孔Salen有机聚合物Co催化剂(MS-Salen@Co)。
本发明涉及的反应方程式如下:
作为优选,步骤(1)中:
所述极性非质子性溶剂为N,N-二甲基甲酰胺、二甲基亚砜、THF或乙腈;
所述的烯丙基卤代烃为烯丙基氯或烯丙基溴;
所用的碱为NaOH、K2CO3或Na2CO3。
步骤(2)中:所述的温度为180-250℃。
步骤(3)中:所述有机溶剂为甲醇、乙醇、异丙醇。
步骤(4)中:
所述的自由基引发剂为偶氮二异庚腈。
所述的助引发剂为三氯化铁和过硫酸铵。
所述的醚类溶剂为四氢呋喃或乙醚。
所述的Salen配体与二乙烯基苯的质量比1:0.5-2。
步骤(5)中:
所述的介孔Salen有机聚合物(MS-Salen)与硫酸钴的质量比为20-40:1。
所述的醇与水的混合溶剂为乙醇与水、甲醇与水或异丙醇与水。
更具体地,所述的介孔Salen有机聚合物Co催化剂(MS-Salen@Co)的制备过程如下:
步骤(1):称取2-羟基苯甲醛、烯丙基卤代烃、碱于极性非质子性溶剂中,在室温下搅拌,用TLC检测反应完全;向反应液加入水和乙酸乙酯;有机相用适量的水洗涤4次、用饱和食盐水洗涤1次,经无水Na2SO4干燥后减压浓缩得到产物苯基烯丙基醚(P-1);
步骤(2):将步骤(1)所得产物在180-250℃下加热5小时进行Claisen重排;
步骤(3):称取一定量的步骤(2)所得产物和乙二胺于乙醇中,在80℃下反应至反应完全,减压浓缩经柱层析得到产物Salen(P-3);
步骤(4):称取偶氮二异庚腈、二乙烯基苯、步骤(3)的产物(P-3)、三氯化铁和过硫酸铵于四氢呋喃中;向反应混合物加入水并在室温下搅拌3小时,然后在100℃下回流12小时进一步热晶化;反应物冷却后转入到水热反应釜中并在120℃下加热24小时,开盖挥发溶剂(湿度约60%,挥发24小时)得介孔Salen有机聚合物;用水洗去多孔材料中残留盐后,在80℃真空干燥得到孔道开放的介孔Salen有机聚合物;
步骤(5):称取介孔Salen有机聚合物和硫酸钴于四氢呋喃和水中,在室温下搅拌3小时后,减压浓缩、50℃下真空干燥得到介孔Salen有机聚合物Co催化剂。
本发明还提供一种所述的具有介孔结构Salen有机聚合物Co催化剂的应用方法,其方法如下:
在三颈瓶中,将安息香溶解于有机溶剂中,加入一定量的MS-Salen@Co和碳酸钾,在一定反应温度下,反应结束后过滤回收催化剂进行下次实验,滤液加入乙酸乙酯和水,水相用乙酸乙酯萃取2次,合并有机相,用饱和食盐水洗涤,用无水Na2SO4干燥,过滤、减压浓缩、重结晶得到高纯度的苯偶酰。
涉及的反应方程式如下:
作为优选:
所述的有机溶剂为乙醇、DMF、乙醇-水或DMF-水。
所述反应温度为60-100℃。
所述的MS-Salen@Co催化剂加入质量为:计算Co的物质的量为安息香物质的量的1%。
所述的碱为K2CO3或NaOH。
本发明由于采用了以上技术方案,具有显著的技术效果:
1、在非均相催化方面,具有孔道结构的催化剂由于对反应原料有富集以及对金属具有吸附作用,该种结构特征能够大大提高催化剂的催化性性能和重复使用性能。合成具有多孔结构非均相催化剂具有重要的应用价值,具体可参加本发明实施例。
2、用制备的催化剂MS-Salen@Co是一种新型的催化剂,并且对安息香的催化氧化具有很好的催化性能、容易回收、产物的处理方法简单、成本低、效果好。
3、所制备的催化剂MS-Salen@Pd为一种介孔催化剂,不仅对反应原料具有一定的富集作用,而且可防治Co在催化过程中的团结,从而可被重复利用并保持催化活性,具有很好工业应用价值。
附图说明:
图1为本发明实施例制备的Salen聚合物Co催化剂MS-Salen@Co的吸脱附等温曲线图;
图2为本发明实施例制备的Salen聚合物Co催化剂MS-Salen@Co的透射电镜图(TEM);
图3为本发明实施例制备的Salen聚合物Co催化剂MS-Salen@Co的扫描电镜图(SEM)。
具体实施方式:
下面结合具体实施例对本发明作进一步详细描述:
实施例1:
在250mL圆底烧瓶中,依次加入水杨醛(21.2mL,200mmol)、碳酸钾(41.4g,300mmol)、DMF(100mL),磁子。室温搅拌下,缓慢滴入烯丙基溴(20.74mL,240mmol),并在室温下反应12小时以上,并用TLC分析检测至反应完全。反应完全后,向反应液加入乙酸乙酯和水萃取,有机相先用水洗3次以去掉DMF,再用饱和食盐水洗1次,所得有机相用无水Na2SO4干燥,经过滤减压浓缩,得到产物即为苯基烯丙基醚。
产物的结构用1H-NMR和13C-NMR确定,其数据如下:
1H-NMR(400MHz,CDCl3)δppm 7.77(dd,J=7.6,1.6Hz,1H),7.48-7.44(m,1H),6.96(dd,J=8.0,8.0Hz,1H),6.91(d,J=8.4Hz,1H),6.06-5.97(m,1H),5.43-5.37(m,1H),5.29-5.26(m,1H),4.59-4.57(m,1H);
13C-NMR(100MHz,CDCl3)δppm 189.6,160.9,135.9,132.4,128.2,124.9,120.8,117.9,112.9,69.0。
实施例2:
在100mL的圆底烧瓶中,加入实施例1所得苯基烯丙基醚(1.026g)和磁子,圆底烧瓶接上冷凝管后在200℃的油浴中加热使其发生Claisen重排反应。反应4小时后,经TLC分析反应完全,生成的黄色油状液体即为Claisen重排反应产物。
产物的结构用1H-NMR和13C-NMR确定,其数据如下:
1H-NMR(400MHz,CDCl3)δppm 11.3(s,1H),9.89(s,1H),7.44(d,J=7.6Hz,1H),7.42(d,J=7.6Hz,1H),6.98(dd,J=7.6,7.6Hz,1H),6.06-5.95(m,1H),5.14-5.11(m,1H),5.09-5.08(m,1H),3.45(m,1H),3.44(m,1H);
13C-NMR(100MHz,CDCl3)δppm 196.7,159.5,137.1,135.8,131.9,128.8,120.3,119.6,116.2,33.0。
实施例3:
在一个250mL圆底烧瓶中,依次加入Claisen重排产物(1.6mL,0.018mol)、乙二胺(0.5mL,0.0075mol)、乙醇(50mL),在75℃水浴锅中加热搅拌5小时。反应液冷缺至室温后,加入乙酸乙酯和水,有机相先用水洗3次,再用饱和食盐水洗一次,所得有机相用无水Na2SO4干燥,经过滤减压浓缩,得到产物Salen。
产物Salen的结构用1H-NMR和13C-NMR确定,其数据如下:
1H-NMR(400MHz,CDCl3)δppm 13.6(s,1H),8.37(s,1H),7.21(d,J=7.2Hz,1H),7.14(d,J=7.6Hz,1H),6.84(dd,J=7.6,7.2Hz,1H),6.11-6.01(m,1H),5.12(d,J=11.2Hz,1H),5.09(s,1H);
13C-NMR(100MHz,CDCl3)δppm 166.7(×2),158.9(×2),136.6(×2),132.7(×2),129.7(×2),127.8(×2),118.4(×2),118.2(×2),115.7(×2),59.7(×2),33.7(×2)。
实施例4:
称取偶氮二异庚腈(0.5g),二乙烯基苯(2.5mL),Salen产物(1.5g),三氯化铁(0.01g),过硫酸铵助引发剂(0.025g),依次加入四氢呋喃(80mL)中,补加水(3mL)为助溶剂,室温搅拌3小时(搅拌速率约800rpm),100℃下回流12小时进一步溶剂热晶化,120℃反应釜处理24小时,取出反应釜,开盖挥发溶剂(湿度约60%,挥发24小时)得粗产品。水洗除去样品中残留盐,80℃真空干燥得到具有介孔结构特征的Salen有机聚合物MS-Salen。
实施例5:
称取介孔Salen有机聚合物MS-Salen(2g)和CoSO4(0.175g)于四氢呋喃(30mL)和水(10mL)中,在室温下搅拌3小时后,减压浓缩、在50℃下真空干燥6小时得到介孔Salen聚合物Co催化剂MS-Salen@Co;CoSO4的质量百分含量为8%。
产物检测:
本实施例制备的催化剂MS-Salen@Co的结构特点是具有介孔结构,我们用BET(图1),TEM(图2)和SEM(图3)对该催化剂的结构特点进行了表征:BET实验显示:Salen聚合物Co催化剂MS-Salen@Co的比表面积为214m2/g,其中介孔比表面积为208m2/g,微孔比表面积为6.2m2/g。氮气吸脱附等温曲线(图1)可知,所得催化剂具有明显介孔结构特征。图2为Salen聚合物Co催化剂MS-Salen@Co的透射电镜图(TEM),从图2可知,Salen聚合物Co催化剂MS-Salen@Co具有明显的介孔结构;图3为Salen聚合物Co催化剂MS-Salen@Co的扫描电镜图(SEM),从图3可知,Salen聚合物Co催化剂MS-Salen@Co是一种疏松的且具有介孔结构的材料。
实施例6:
取一个洁净干燥100mL三颈瓶,在三颈瓶中依次加入安息香(1.08g,5.1mmol)、乙醇20(20mL)/水(10mL)和磁子,待安息香溶解后加入MS-Salen@Co催化剂(294mg,含CoSO4为0.15mmol,3mol%)、KOH(3.57mmol)。向反应液的底部通入空气,水浴加热至75℃后,利用薄层色谱跟进反应至完全。当反应结束后,将反应液冷却到室温,用过滤的方法回收催化剂。催化剂依次用乙醇、水、乙醇洗涤。合并滤液并加入乙酸乙酯和水,水相用乙酸乙酯萃取两次,合并有机相,用饱和食盐水进行洗涤,再用无水Na2SO4干燥,经过过滤、减压浓缩、柱层析等步骤得到苯偶酰0.95克,产率为89%。
实施例9-13:
取一个洁净干燥100mL三颈瓶,依次加入安息香(2.16g,10.2mmol)、乙醇30(20mL)/水(15mL)和磁子,待安息香溶解后加入MS-Salen@Co催化剂(590mg,含CoSO4为0.30mmol,3mol%)、KOH(7.2mmol)。用空气泵向反应液的底部通入空气,水浴加热至75℃后,利用薄层色谱检测反应。反应结束后,将反应液冷却到室温,用过滤的方法回收催化剂。催化剂依次用乙醇、水、乙醇洗涤。合并滤液并加入乙酸乙酯和水,水相用乙酸乙酯萃取两次,合并有机相,有机相用饱和食盐水进行洗涤,再用无水Na2SO4干燥,经过滤、减压浓缩、柱层析等步骤得到苯偶酰。将回收所得的催化剂用相同的方法进行重复实验,结果见表1。
表1、MS-Salen@Pd催化剂的循环使用实验
如表1所示,本发明制备的具有介孔结构的催化剂,由于对反应原料有富集以及对金属具有吸附作用,该种结构特征能够大大提高催化剂的催化性性能和重复使用性能,经试验证明,重复5次以上仍具有良好的催化性能,具有重要的应用价值。
总之,以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所作的均等变化与修饰,皆应属本发明专利的涵盖范围。
Claims (16)
1.一种催化剂的制备方法,其特征在于,包括如下步骤:
步骤(1):在极性非质子性溶剂中,在碱的存在下,将水杨醛和烯丙基卤代烃在一起搅拌后,反应液经萃取、洗涤以及浓缩后到产物苯基烯丙基醚;
步骤(2):将步骤(1)所得产物在一定温度下加热发生Claisen重排反应;
步骤(3):在有机溶剂中,将步骤(2)所得产物与乙二胺缩合得到Salen配体;
步骤(4):在醚类溶剂中,在自由基引发剂和助引发剂的存在下,将步骤(3)所得Salen配体与二乙烯基苯以一定的质量比混合,混合物先在室温下搅拌,再在100℃下回流热晶化,冷却后转入水热反应釜中120℃加热,挥发溶剂后得到介孔Salen配体MS-Salen;
步骤(5):在醇与水的混合溶剂中,将步骤(4)所得介孔Salen配体MS-Salen与硫酸钴混合,在室温条件下搅拌一定时间后,将溶剂减压蒸发、真空干燥得到具有介孔结构的Salen配体Co催化剂MS-Salen@Co。
2.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(1)所述的极性非质子性溶剂为DMF、CH3CN、DMSO或THF。
3.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(1)所述的烯丙基卤代烃为烯丙基氯或烯丙基溴。
4.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(1)所用的碱为NaOH、K2CO3或Na2CO3。
5.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(2)所述的温度为180-250℃。
6.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(3)所述的有机溶剂为甲醇、乙醇或异丙醇。
7.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(4)所述的醚类溶剂为四氢呋喃或乙醚。
8.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(4)所述的自由基引发剂为偶氮二异丁腈。
9.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(4)所述的助引发剂为三氯化铁和过硫酸铵。
10.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(4)所述的Salen配体与二乙烯基苯的质量比1:0.5-2。
11.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(5)所述的醇与水的混合溶剂为乙醇与水、甲醇与水或异丙醇与水。
12.根据权利要求1所述的一种催化剂的制备方法,其特征在于:步骤(5)所述的介孔Salen配体与硫酸钴的质量比为20-40:1。
13.一种权利要求1所述制备方法制备的催化剂在安息香的催化氧化中的应用,其特征在于,方法如下:在反应瓶中,将安息香溶解于醇的水溶液,加入MS-Salen@Co催化剂和碱,反应温度为80℃,反应时间为2-10小时,反应完成后过滤回收催化剂,滤液经NaOH水溶液洗涤,萃取、干燥、浓缩得到高纯度联苯类化合物。
14.根据权利要求13所述的一种催化剂的应用,其特征在于:所述的醇为甲醇、乙醇或异丙醇。
15.根据权利要求13所述的一种催化剂的应用,其特征在于:所述的MS-Salen@Co催化剂加入质量为:计算Co的物质的量为安息香物质的量的1%。
16.根据权利要求13所述的一种催化剂的应用,其特征在于:所述的碱为K2CO3或NaOH。
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