CN106669830A - 一种具有介孔结构的有机硅负载磷钨酸的复合材料、制备及用其制偶联产物的方法 - Google Patents
一种具有介孔结构的有机硅负载磷钨酸的复合材料、制备及用其制偶联产物的方法 Download PDFInfo
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Abstract
一种具有介孔结构的有机硅负载磷钨酸的复合材料、制备及用其制偶联产物的方法,属于化工领域,具有以下化学组成:H3PW12O40/(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n,即:PW12/PMO。本发明产品采用Keggin结构多酸(H3PW12O40)作为活性组分;桥联有机硅烷试剂(1,2-双(三乙氧基硅基)乙烷—BTSE)为有机硅前驱体;非离子表面活性剂(P123,M=5800)作为结构导向剂,采用一步水解共缩合结合水热处理技术设计制备一种具有介孔结构的有机硅负载磷钨酸的复合材料。本发明的复合材料PW12/PMO制备工艺简单,反应专属性好,用于催化对二苯甲醇和α-硝基二硫缩烯酮进行的碳碳偶联反应转化率高,产品纯度高和反应过程清洁。
Description
技术领域
本发明涉及一种具有介孔结构的有机硅负载磷钨酸的复合材料、制备及用其作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法。
背景技术
20世纪70年代以来,多金属氧酸盐作为催化剂,在石油化工和精细化学品合成领域越来越受到催化工作者的青睐。杂多酸不仅是一种酸强度很强的纯质子酸,还是一类性能优异的酸催化和氧化还原的“双功能”性催化剂。酸强度测定结果表明,杂多酸的酸性很大程度上强于普通的H3PO4 、HF、HBr、HCl、HNO3等无机酸,并且其催化性能可以通过改变杂原子、配原子及其反荷阳离子来调控,因此,杂多酸作为催化活性高、选择性好、无污染的绿色环保型固体酸催化剂,具有得天独厚的优势和广阔的应用前景。但是纯多酸作为催化剂有比表面积小、腐蚀设备、污染环境、易溶于极性溶剂、催化活性不能充分发挥以及不可回收再利用等缺点,在很大程度上限制了杂多酸在工业生产中的推广应用。因此需要研究杂多酸的改性和非均相化,以期解决杂多酸作为均相催化剂不易回收的问题。
目前,人们通过采用把杂多酸负载在多种多孔材料载体上的方式来提高了杂多酸的比表面积、热稳定性、催化活性及其重复使用性等,从而实现杂多酸非均相的酸催化和氧化还原功能。但杂多酸通过酸碱作用而负载于载体上的催化剂在反应中容易发生杂多酸溶脱的现象,导致了催化剂失活。同时这些负载催化剂主要应用于酸催化反应,因此将杂多酸催化剂硅烷化改性,以获得高效、不易失活,能重复利用的催化剂,对杂多酸的工业化应用具有重要的意义。
经过研究发现,在介孔材料纳米孔道内引入有机基团后,在保持介孔结构的同时,又改善了介孔孔道界面的疏水性,有利于提高介孔材料的水热稳定性,因此,我们考虑利用桥联有机硅合成有序介孔载体,从而达到改善孔道界面疏水性的目的。与传统的无机二氧化硅负载多酸的复合材料(多酸/SiO2)相比,具有更大的比表面积和孔体积,并且有机官能团的引入调节了催化剂孔道内部和表面的亲/疏水性质,使反应产物更容易从表面脱附,从而使反应物更容易与有限的活性点接触,且避免了催化剂的失活。因此,我们提出了一种具有介孔结构的有机硅负载磷钨酸的复合材料及制备方法,合成了PW12/PMO复合材料。
发明内容
本发明提供了利用有机硅负载磷钨酸的复合材料作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法。
一种具有有序介孔结构的基于磷钨酸的有机硅复合催化剂及制备方法,其步骤和条件如下:
(1)采用的催化剂为有机硅负载磷钨酸的复合材料;所述的PW12/PMO具有以下化学组成:H3PW12O40/(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n;
经检测,得到PW12/PMO中H3PW12O40的含量为10.07-33.36 wt%,PW12/PMO为有序介孔结构,平均孔径在5.49-5.64 nm;
(2)对二苯甲醇和α-硝基二硫缩烯酮及复合材料PW12/PMO的质量比为1:1.09:0.14~1:1.09:0.70,对二苯甲醇和溶剂乙腈的质量比为1:21.68;
(3)加入正辛烷作为内标,正辛烷与对二苯甲醇的摩尔比为1:1;
(4)将称量好的复合材料置于25 mL两口圆底烧瓶中,放入真空干燥箱内110℃真空活化2 h。把称量好的对二苯甲醇和α-硝基二硫缩烯酮以及量取好的乙腈加入到该烧瓶中,置于带加热的磁力搅拌器中,加热到70℃,反应时间为6-24 h,得到目标物。
获得的目标产物,用气相色谱仪Agilent GC6890分析,分析条件:色谱柱Agilent 19091N-133
HP-INNOWAX Polyethylene Glycol,FID检测器,进样口温度为250℃,检测器温度为280℃,气相色谱进行对二苯甲醇定性,对二苯甲醇转化率分析,气相数据分析方法采用归一法。
(5)催化剂的回收利用:反应后,通过乙醇萃取的方式分离回收催化剂,将催化剂在100℃下干燥24-48 h;再按照步骤(1)、(2)、(3)和(4)的反应条件进行反应;该催化剂可重复使用3次。
有益效果:
(1)本发明的复合材料PW12/PMO具有有序介孔结构,平均孔径 在5.49-5.64 nm;
(2)本发明的复合材料PW12/PMO反应活性高,选择性好,使用过程对生产设备无腐蚀,是一种环境友好型复合材料;
(3)本发明的复合材料PW12/PMO作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物专属性好,转化率高,反应过程清洁,适于工业化推广;
(4)复合材料可以回收重复利用。
附图说明
图1是本发明的具有介孔结构的有机硅负载磷钨酸的复合材料垂直于孔道结构的TEM图。由图可以发现复合材料具有明显的二维六方(p6mm)的有序介孔结构,介孔分布均匀且呈有序排列。
具体实施方式:
实施例 1 (1)本发明采用的催化剂为有机硅负载磷钨酸的复合材料;(2)对二苯甲醇和α-硝基二硫缩烯酮及复合材料PW12/PMO的质量比为1:1.09:0.14,对二苯甲醇和溶剂乙腈的质量比为1:21.68;(3)加入正辛烷作为内标,正辛烷与对二苯甲醇的摩尔比为1:1;(4)将称量好的复合材料置于25 mL两口圆底烧瓶中,放入真空干燥箱内110℃真空活化2 h。把称量好的182 mg(1 mmol)对二苯甲醇和198 mg(1.2 mmol)α-硝基二硫缩烯酮以及量取好的5 mL乙腈加入到该烧瓶中,置于带加热的磁力搅拌器中,加热到70℃,反应时间为12 h,得到目标物。
反应之后的体系离心,分离复合材料,取上层清液用气相色谱仪Agilent GC6890分析,分析条件:色谱柱 Agilent 19091N-133
HP-INNOWAX Polyethylene Glycol,FID检测器,进样口温度为250℃,检测器温度为280℃,气相色谱进行对二苯甲醇定性,对二苯甲醇转化率分析,气相数据分析方法采用归一法。
实施例 2 (2)对二苯甲醇和α-硝基二硫缩烯酮及复合材料PW12/PMO的质量比为1:1.09:0.28;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、50 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为12 h。其余的同实施例1。
实施例 3 (2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.42;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、75 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为12 h。其余的同实施例1。
实施例 4 (2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.56;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、100 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为12 h。其余的同实施例1。
实施例 5 (2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.70;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、125 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为12 h。其余的同实施例1。
实施例 6 (2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.56;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、100 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为3 h。其余的同实施例1。
实施例 7(2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.56;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、100 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为6 h。其余的同实施例1。
实施例 8 (2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.56;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、100 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为9 h。其余的同实施例1。
实施例 9 (2)对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.56;称取182 mg(1 mmol)对二苯甲醇、198 mg(1.2 mmol)α-硝基二硫缩烯酮、100 mg催化剂;(4)当温度达到70 ℃时,开始计时反应,反应时间为24 h。其余的同实施例1。
复合材料的再利用实验:
实施例 10:把实施例4中反应后的反应液离心,分离催化剂和反应液,把回收的催化剂用乙醇洗涤三次,将催化剂置于100℃干燥箱内抽真空干燥24 小时。再按实施例4的条件进行反应。结果见表1。
用气相色谱仪Agilent GC6890分析,分析条件:色谱柱 Agilent 19091N-133
HP-INNOWAX Polyethylene Glycol,FID检测器,进样口温度为250℃,检测器温度为280℃;
分析结果见表1。表1表明,本发明有机硅负载磷钨酸的复合材料作为催化剂催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法,选择最优反应条件,反应温度为70℃,对二苯甲醇和α-硝基二硫缩烯酮及催化剂PW12/PMO的质量比为1:1.09:0.56,最佳反应时间为12 h,对二苯甲醇转化率高,选择性好,适于工业化推广使用。
表 1
Claims (5)
1.一种具有介孔结构的有机硅负载磷钨酸的复合材料(PW12/PMO)的应用,其特征在于,把PW12/PMO作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物。
2.一种具有介孔结构的有机硅负载磷钨酸的复合材料(PW12/PMO)作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法,其特征在于,步骤和条件如下:
(1)采用的催化剂为有机硅负载磷钨酸的复合材料,具有以下化学组成:H3PW12O40/(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n;
(2)对二苯甲醇和α-硝基二硫缩烯酮及复合材料PW12/PMO的质量比为1:1.09:0.14~1:1.09:0.70,对二苯甲醇和溶剂乙腈的质量比为1:21.68;
(3)加入正辛烷作为内标,正辛烷与对二苯甲醇的摩尔比为1:1;
(4)将称量好的复合材料置于25 mL两口圆底烧瓶中,放入真空干燥箱内110℃真空活化2 h;把称量好的182 mg(1 mmol)对二苯甲醇和198 mg(1.2 mmol)α-硝基二硫缩烯酮以及量取好的5 mL乙腈加入到该烧瓶中,置于带加热的磁力搅拌器中,加热到70℃,反应时间为6-24 h,得到目标物;
(5)复合材料的回收利用:反应后,通过乙醇萃取的方式分离回收催化剂,将复合材料在100℃下干燥24-48 h;再按照步骤(1)、(2)、(3)和(4)的反应条件进行反应;该复合材料可重复使用3次。
3.如权利要求2所述的一种具有介孔结构的有机硅负载磷钨酸的复合材料作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法,其特征在于,所述的步骤(1)的复合材料载体为有机硅(HO)3-n(SiO)nSi-C2H4-Si(OSi)n(OH)3-n。
4.如权利要求2所述的一种具有介孔结构的有机硅负载磷钨酸的复合材料作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法,其特征在于,所述的步骤(4)对二苯甲醇和α-硝基二硫缩烯酮的转化率高。
5.如权利要求2所述的一种具有介孔结构的有机硅负载磷钨酸的复合材料作为催化剂用于催化对二苯甲醇和α-硝基二硫缩烯酮进行碳碳偶联反应制备偶联产物的方法,其特征在于,所述的步骤(5)复合材料的回收利用为3次。
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