CN102861611A - 一种有机骨架多孔固体酸的应用 - Google Patents
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Abstract
本发明涉及一种有机骨架多孔固体酸的应用;用于催化酯化和酰基化反应的催化剂,所用的催化剂的制备是将二乙烯基苯单体加入到含偶氮二异丁睛、四氢呋喃和水的混合溶剂中,常温常压下水热处理,室温挥发干溶剂,得到聚二乙烯基苯;将聚二乙烯基苯研磨成200目粉末,氮气条件下脱气处理;将聚二乙烯基苯块加入1,1’,2-三氯乙烷中,炸裂成小块,胀大;取1,1’,2-三氯乙烷,浓硫酸混合均匀,加入硫酸银为催化剂,加入经过处理的聚二乙烯基苯,磺化,过滤,二氧六环洗涤,水洗至中性,干燥,用稀硫酸活化、水洗到中性,干燥;本方法所述的催化剂用于催化酯化和酰基化反应中具有较高的催化活性和转换率。
Description
技术领域
本发明涉及一种有机骨架多孔固体酸的的应用。
背景技术
随着化学工业的发展,固体酸催化剂得到广泛应用,尤其是在石油化工和精细化工领域起着举足轻重的作用,传统的酸催化剂有沸石分子筛,硫化金属氧化物,酸功能化的介孔材料,杂多酸等,但其缺点如:亲水骨架结构,沸石材料的孔径限制等影响了无机固体酸材料的广泛应用。与传统无机骨架的酸催化剂相比,纯有机骨架固体酸材料以其独特的骨架疏水性能,简单而方便的功能化过程,较好的催化性能而受到越来越广泛的研究。
美国专利:B01J31/10;B01J47/00;C07C37/20等公布了一种强酸性阳离子交换树脂,其骨架是二乙烯基苯和苯乙烯共聚物,活性官能团为磺酸根,作为一种新型的有机骨架固体酸材料,疏水性的骨架结构和高的酸中心含量使得该材料广泛应用于酸催化反应和离子交换等领域,包括酯化,酯交换,醚化,取得了很好的效果(J.Catal.2008,254,205.),现已被工业化。在工业应用中占有非常重要的位置。但其低比表面积,匮乏的孔结构,稳定性较差的骨架结构限制其广泛应用。
发明内容
本发明的目的是提供一种有机骨架多孔固体酸的应用,采用多孔聚二乙烯基苯为材料,利用其良好的溶胀性能,通过磺化反应取得有机骨架固体酸用于催化酯化和酰基化反应的催化剂,与传统的树脂相比交联度 高,稳定性高,具有大的比表面积和丰富的孔结构。
本发明所述的有机骨架多孔固体酸的合成方法是:
(1)将2g二乙烯基苯(DVB)单体加入到含0.03-0.05g偶氮二异丁睛和10-20毫升四氢呋喃,1-2毫升水的混合溶剂中,常温常压下搅拌>3小时后,75-150摄氏度水热处理1-2天后取出,开盖,室温挥发干溶剂,得到高比表面积,丰富介孔结构的聚二乙烯基苯(PDVB);
(2)将2-3g聚二乙烯基苯(PDVB)研磨成200目粉末,100-150℃氮气条件下脱气处理10h;
(3)将2.0g聚二乙烯基苯(PDVB)块加入30毫升1,1’,2-三氯乙烷,PDVB材料迅速发生溶胀,PDVB很快炸裂成小块,同时伴随体积迅速胀大;
(4)取30毫升1,1’,2-三氯乙烷,70mL,质量浓度98%的浓硫酸混合均匀,加入0.2g硫酸银为催化剂,搅拌均匀后,加入进过(3)处理的聚二乙烯基苯(PDVB),强力搅拌,温度升高到90℃磺化12h,结束反应,产物过滤,二氧六环洗涤,水洗至中性,80℃干燥,用0.1M稀硫酸活化4小时后大量水洗到中性,干燥,待用。
本发明的磺酸功能化的介孔聚二乙烯基苯具有大的比表面积(523m2/g)。
本发明的磺化的介孔聚二乙烯基苯材料具有较高的磺酸根含量(2.45mmol/g)。
本发明的磺酸功能化的介孔聚二乙烯基苯具有稳定的骨架结构(575℃)和稳定的酸中心(305℃)。
本发明磺酸功能化的介孔聚二乙烯基苯在催化酯化反应和付克酰基化反应中表现出了良好的催化活性和再生性能,循环利用5次后活性降 低了11.3%。
本发明的特点是通过溶剂热的方法合成具有丰富介孔结构的聚二乙烯基苯材料,比表面积为600-700m2/g,平均孔径为15-23nm,孔容为0.7-1.4ml/g。材料对大部分有机溶剂包括:苯及其同系物,烷烃,醇等具有非常好的溶胀性能,我们利用这个特点,结合该材料丰富的孔结构和大的比表面积,通过先溶胀后磺化的新合成路线成功的合成了新型的稳定,高效有机骨架固体酸材料,同时磺化后材料保持着大比表面积和丰富孔结构,磺化后磺酸根量含量为2.0~3.5mmol/g,氢离子交换容量为2.2~3.7mmol/g。比表面积为280-500m2/g。与上述专利技术相比本发明的固体酸具有独特的骨架疏水性能,简单而方便的功能化过程,较好的催化性能和再生功能。
表1是合成磺化材料在酯化反应和酰基化反应中的催化活性。
具体实施方式
说明本发明中具有高效稳定结构,高比表面积,高磺酸根含量的新型固体酸材料的合成方法。
实施例中,样品命名分为两部分:PDVB代表介孔聚二乙烯基苯,“-SO3H”代表磺酸根功能化后的介孔聚二乙烯基苯材料。
实施例1:
首先以四氢呋喃和水为混合溶剂来合成介孔聚二乙烯基苯材料,即为PDVB。
将2g DVB单体加入到含0.03-0.05g偶氮二异丁睛和10-20毫升四氢呋喃,1-2毫升水的混合溶剂中,常温常压下搅拌>3小时后,75-150摄氏度水热处理1-2天后取出,开盖,室温挥发干溶剂,即可得到高比表面积,丰富介孔结构的聚二乙烯基苯材料(PDVB)。
实施例2:
选择二氯甲烷为溶剂,浓硫酸为磺化试剂进行磺化反应。
(1)将2-3g PDVB研磨成超细粉末,100-150℃氮气条件下脱气处理10h;
(2)溶胀过程:将2.0g PDVB块加入过量的溶剂中,PDVB材料迅速发生溶胀,PDVB很快炸裂成小块,同时伴随体积迅速胀大。
(3)取30mL二氯甲烷,70mL浓硫酸混合均匀,加入0.2g硫酸银为催化剂,搅拌均匀后,加入上述PDVB,强力搅拌,温度升高到90℃磺化12h,结束反应,产物过滤,二氧六环洗涤,水洗至中性,80℃干燥,用0.1M洗硫酸活化4小时后大量水洗到中性,干燥,待用。
实施例3:
催化性能评价及其与传统催化材料的对比
乙酸和环己醇的酯化反应条件:0.2g催化剂,11.5mL环己醇,17.5mL冰醋酸混合均匀后100℃反应5h结束,十二烷为内标。
正己酸和乙醇的酯化反应条件:0.3g催化剂,6.26mL正己酸,11.67mL乙醇混合均匀后80℃反应5h结束,十二烷为内标。
十二酸和乙醇的酯化反应条件:0.15g催化剂,4mmol十二酸,50mmol乙醇混合均匀后70℃反应5h结束,十二烷为内标。
付克酰基化反应:0.3g催化剂,5.5mL苯甲醚,0.71mL乙酰氯混合均匀后60℃反应5h结束,十二烷为内标。
附表1给出了材料在催化酯化和酰基化反应中的催化活性,可以看出该材料对多种酸催化反应表现出了良好的催化活性反应转化率依次为:62.5,72.5,89.4,61.8%;在催化酯化反应中,循环利用5次后活性降低了11.3%,表明该材料具有较好的再生能力和抗毒化能力。
表1
a0.2g催化剂.b0.1g催化剂。
c0.2g催化剂在催化乙酸环己醇酯化反应中被循环利用四次。
d乙酸环己醇酯化反应。
e正己酸和乙醇酯化反应。
Claims (1)
1.一种有机骨架多孔固体酸的应用,其特征在于:用于催化酯化和酰基化反应的催化剂,催化剂的合成方法如下:
(1)将2g二乙烯基苯单体加入到含0.03-0.05g偶氮二异丁睛和10-20毫升四氢呋喃,1-2毫升水的混合溶剂中,常温常压下搅拌>3小时后,75-150摄氏度水热处理1-2天后取出,开盖,室温挥发干溶剂,得到具有介孔结构的聚二乙烯基苯;
(2)将2-3g聚二乙烯基苯研磨成200目粉末,100-150℃氮气条件下脱气处理10h;
(3)将2.0g聚二乙烯基苯块加入30毫升1,1’,2-三氯乙烷中,聚二乙烯基苯块迅速发生溶胀,炸裂成小块,同时伴随体积迅速胀大;
(4)取30毫升1,1’,2-三氯乙烷,70mL浓硫酸混合均匀,加入0.2g硫酸银为催化剂,搅拌均匀后,加入经过(3)处理的聚二乙烯基苯,强力搅拌,温度升高到90℃磺化12h,结束反应,产物过滤,用二氧六环洗涤,水洗至中性,80℃干燥,用0.1M稀硫酸活化4小时后大量水洗到中性,干燥。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101143911A (zh) * | 2007-08-31 | 2008-03-19 | 吉林大学 | 具有超强吸附特性的介孔聚二乙烯基苯材料及其合成方法 |
CN101864019A (zh) * | 2010-05-13 | 2010-10-20 | 上海现代药物制剂工程研究中心有限公司 | 聚苯乙烯磺酸钠离子交换树脂的制备方法 |
-
2011
- 2011-07-08 CN CN201110191278.8A patent/CN102861611B/zh active Active
-
2012
- 2012-07-06 WO PCT/CN2012/000938 patent/WO2013007103A1/zh active Application Filing
- 2012-07-06 US US14/131,496 patent/US9056823B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101143911A (zh) * | 2007-08-31 | 2008-03-19 | 吉林大学 | 具有超强吸附特性的介孔聚二乙烯基苯材料及其合成方法 |
CN101864019A (zh) * | 2010-05-13 | 2010-10-20 | 上海现代药物制剂工程研究中心有限公司 | 聚苯乙烯磺酸钠离子交换树脂的制备方法 |
Non-Patent Citations (1)
Title |
---|
刘志广等: "低交换容量阳离子交换树脂的制备及离子色谱分离性能的考察", 《离子交换与吸附》 * |
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