CN111841627B - 一类二氧化硅基材料负载聚醚功能化离子液体催化剂及其制备方法 - Google Patents
一类二氧化硅基材料负载聚醚功能化离子液体催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一类二氧化硅基材料负载聚醚功能化离子液体催化剂及其制备方法,具体为将带有硅烷偶联基团的聚醚功能化离子液体与活化处理后的二氧化硅基材料表面的硅醇基反应,得到表面接枝聚醚功能化离子液体的二氧化硅基材料,这种新型的二氧化硅基材料负载的聚醚功能化离子液体催化剂具有应用于催化氢化、氢甲酰化和CO2催化转化反应的潜力。
Description
技术领域
本发明涉及化学化工技术领域,具体地涉及一类二氧化硅基材料负载聚醚功能化离子液体催化剂及其制备方法。
背景技术
近年来,随着对绿色化学的日益重视以及对环境友好溶剂的需求,绿色溶剂离子液体吸引了人们的极大关注。与传统的有机溶剂不同,离子液体具有极低的饱和蒸气压、高的热和化学稳定性、对过渡金属催化剂良好的溶解性以及结构的可设计性等优点,因此应用离子液体作为催化剂载体成为一种分离、回收和循环过渡金属催化剂的有效手段。尽管离子液体用于负载和分离过渡金属催化剂取得了一些成功的应用,但一个难以调和的问题也显现出来,即为了抑制催化剂的流失,通常大量的溶剂离子液体被应用于催化反应中以充分地溶解和固载催化剂,这既不符合绿色化学的要求,也导致了资源的浪费。而且大量溶剂离子液体的应用也使得离子液体中难以除去的微量杂质对金属催化剂产生的负效应(如使催化剂中毒)变得更加显著,导致催化效率的降低。因此,如何环境友好和经济地应用离子液体以构建高效的离子液体催化体系是当前迫切需要解决的难题。
固载化离子液体是近年来出现的一类新型材料,基于固载化离子液体而发展的固载离子液体(相)催化的概念融合了离子液体优良的溶解性和载体材料的高比表面积的优点,不但减少了离子液体的用量,而且提高了催化反应的活性和选择性,是近年来离子液体领域的研究热点之一,尤其是以二氧化硅基材料作为载体的固载化离子液体催化剂被大量报道,并在催化加氢、氢甲酰化、二氧化碳与环氧化物环加成等反应中得到广泛的应用。目前,在二氧化硅基材料表面负载离子液体催化剂的方法主要包括:物理浸渍法、化学键合法和化学键合-物理浸渍组合法。
基于物理吸附原理的浸渍法是制备固载化离子液体的常用方法,其优点是简单、方便,但离子液体容易从载体表面流失;化学键合法固载离子液体改善了物理浸渍法的不足,由于离子液体的阳离子或阴离子通过共价键与载体材料表面的活性官能团偶联,离子液体不易从载体表面流失,更有利于催化剂的稳定,延长催化剂的使用寿命,但由于载体表面活性基团的数量有限以及通常负载的均是小分子离子液体,单纯的化学键合法往往难以使离子液体在载体表面有效形成离子液体液膜;化学键合-物理浸渍组合法在一定程度上克服了物理浸渍和化学键合法的不足,降低了离子液体的流失并能够在材料表面有效形成离子液体液膜,但制备步骤繁复,二次浸渍吸附的离子液体仍存在流失问题。
发明内容
针对上述的在二氧化硅基材料表面负载离子液体催化剂的三种方法存在的局限性,本发明的目的旨在提供一类二氧化硅基材料负载的聚醚功能化离子液体催化剂。
本发明的另一目的旨在提供一种上述的一类二氧化硅基材料负载的聚醚功能化离子液体催化剂的制备方法。
本发明的一类二氧化硅基材料负载聚醚功能化离子液体催化剂,是在二氧化硅基材料表面接枝有式1、式2、式3和式4所示的结构:
其中,n=4–140,R1为C1–C16烷基或苯基;X为-OMs,-OTs,-OAc,Cl-,Br-,I-,BF4 -,PF6 -和具有以下结构的磺酸型水溶性膦配体阴离子:
式中1,2,3,4,5,6,7、8、9、10和11分别为不同的磺酸型水溶性膦配体的母体部分,m是膦配体上磺酸根的总数,m>1;R2为C6H4-3-SO3 -;o=0,1,2;p=0,1,2;q=r=0,1;s=t=0,1。
本发明的一类二氧化硅基材料负载聚醚功能化离子液体催化剂,是在二氧化硅基材料表面接枝有式1、式2、式3和式4所示的结构:
其中,n=4–45,R1为C1–C16烷基或苯基;X为-OMs,-OTs,-OAc,Cl-,Br-,I-,BF4 -,PF6 -和具有以下结构的磺酸型水溶性膦配体阴离子:
式中1,2,3,4,5,6,7、8、9、10和11分别为不同的磺酸型水溶性膦配体的母体部分,m是膦配体上磺酸根的总数,m>1;R2为C6H4-3-SO3 -;o=0,1,2;p=0,1,2;q=r=0,1;s=t=0,1。
二氧化硅基材料负载聚醚功能化离子液体催化剂的制备方法为:将带有硅烷偶联基团的聚醚功能化离子液体与活化处理后的二氧化硅基材料表面的硅醇基反应,得到表面接枝聚醚功能化离子液体的二氧化硅基材料。
将带有硅烷偶联基团的聚醚功能化离子液体与活化处理后的二氧化硅基材料表面的硅醇基反应,得到表面接枝聚醚功能化离子液体的二氧化硅基材料,所述的带有硅烷偶联基团的聚醚功能化离子液体为:
其中,n=4–140,R1为C1–C16烷基或苯基;当X为-OMs,-OTs,-OAc,Cl-,Br-,I-,BF4 -,PF6 -时,l=1;当X为具有以下结构的磺酸型水溶性膦配体阴离子时,l=m,m是膦配体上磺酸根的总数,m>1:
式中1,2,3,4,5,6,7、8、9、10和11分别为不同的磺酸型水溶性膦配体的母体部分,m是膦配体上磺酸根的总数,m>1;R2为C6H4-3-SO3 -;o=0,1,2;p=0,1,2;q=r=0,1;s=t=0,1。
将带有硅烷偶联基团的聚醚功能化离子液体与活化处理后的二氧化硅基材料表面的硅醇基反应,得到表面接枝聚醚功能化离子液体的二氧化硅基材料,所述的带有硅烷偶联基团的聚醚功能化离子液体为:
其中,n=4–45,R1为C1–C16烷基或苯基;当X为-OMs,-OTs,-OAc,Cl-,Br-,I-,BF4 -,PF6 -时,l=1;当X为具有以下结构的磺酸型水溶性膦配体阴离子时,l=m,m是膦配体上磺酸根的总数,m>1:
式中1,2,3,4,5,6,7、8、9、10和11分别为不同的磺酸型水溶性膦配体的母体部分,m是膦配体上磺酸根的总数,m>1;R2为C6H4-3-SO3 -;o=0,1,2;p=0,1,2;q=r=0,1;s=t=0,1。
负载聚醚功能化离子液体催化剂的二氧化硅基材料为硅胶或分子筛。
将二氧化硅基材料在120-300℃干燥6-12h,进行活化。
二氧化硅基材料负载聚醚功能化离子液体催化剂的制备方法为:将活化处理后的二氧化硅基材料分散在无水甲苯中,加入带有硅烷偶联基团的聚醚功能化离子液体,在惰性气氛下,40-80℃条件下反应20-96h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体的二氧化硅基材料。
本发明的意义在于,通过化学键合法将聚醚功能化的离子液体固载到二氧化硅基材料表面,由于聚醚功能化离子液体具有较高的分子量,而且醚键具有高的柔性和构象自由度,使得聚醚链能够在材料表面延展,有效形成离子液体膜层,无需再二次物理浸渍离子液体,不但降低了离子液体的用量,也解决了离子液体催化剂易流失的难题,同时制备方法简单,从而克服了现有技术中存在的缺陷。
具体实施方式
以下实施例旨在说明本发明而不是对本发明进一步限定。
实施例1
介孔硅胶与聚醚离子液体12(X=-OMs;l=1;n=16;R1=Ph)交联
将2g介孔硅胶在300℃干燥6h,进行活化。将活化处理后的介孔硅胶分散在30mL无水甲苯中,加入6.9g带有硅烷偶联基团的聚醚功能化离子液体12(X=-OMs;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=-OMs;l=1;n=16;R1=Ph)的介孔硅胶。
实施例2
MCM-41分子筛与聚醚离子液体12(X=-OMs;l=1;n=16;R1=Ph)交联
将2g MCM-41在200℃干燥10h,进行活化。将活化处理后的MCM-41分散在30mL无水甲苯中,加入6.9g带有硅烷偶联基团的聚醚功能化离子液体12(X=-OMs;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=-OMs;l=1;n=16;R1=Ph)的MCM-41。
实施例3
SBA-15分子筛与聚醚离子液体12(X=-OMs;l=1;n=16;R1=Ph)交联
将2g SBA-15在200℃干燥10h,进行活化。将活化处理后的SBA-15分散在30mL无水甲苯中,加入6.9g带有硅烷偶联基团的聚醚功能化离子液体12(X=-OMs;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=-OMs;l=1;n=16;R1=Ph)的SBA-15。
实施例4
硅胶与聚醚离子液体12(X=Br-;l=1;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入6.8g带有硅烷偶联基团的聚醚功能化离子液体12(X=Br-;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=Br-;l=1;n=16;R1=Ph)的硅胶。
实施例5
硅胶与聚醚离子液体12(X=-OMs;l=1;n=4;R1=CH3)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在15mL无水甲苯中,加入1.2g带有硅烷偶联基团的聚醚功能化离子液体12(X=-OMs;l=1;n=4;R1=CH3),在惰性气氛下,60℃条件下反应24h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=-OMs;l=1;n=4;R1=CH3)的硅胶。
实施例6
硅胶与聚醚离子液体12(X=-OMs;l=1;n=34;R1=CH3)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入6.0g带有硅烷偶联基团的聚醚功能化离子液体12(X=-OMs;l=1;n=34;R1=CH3),在惰性气氛下,80℃条件下反应72h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=-OMs;l=1;n=34;R1=CH3)的硅胶。
实施例7
硅胶与聚醚离子液体12(X=-OMs;l=1;n=4;R1=n-C12H25)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入2.3g带有硅烷偶联基团的聚醚功能化离子液体12(X=-OMs;l=1;n=4;R1=n-C12H25),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=-OMs;l=1;n=4;R1=n-C12H25)的硅胶。
实施例8
硅胶与聚醚离子液体13(X=-OMs;l=1;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入6.9g带有硅烷偶联基团的聚醚功能化离子液体13(X=-OMs;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体13(X=-OMs;l=1;n=16;R1=Ph)的硅胶。
实施例9
硅胶与聚醚离子液体14(X=-OMs;l=1;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入7.2g带有硅烷偶联基团的聚醚功能化离子液体14(X=-OMs;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体14(X=-OMs;l=1;n=16;R1=Ph)的硅胶。
实施例10
硅胶与聚醚离子液体15(X=-OMs;l=1;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入7.3g带有硅烷偶联基团的聚醚功能化离子液体15(X=-OMs;l=1;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体15(X=-OMs;l=1;n=16;R1=Ph)的硅胶。
实施例11
硅胶与聚醚离子液体12(X=(SO3 -)m-1;l=m=3;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入7.3g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-1;l=m=3;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-1;l=m=3;n=16;R1=Ph)的硅胶。
实施例12
硅胶与聚醚离子液体12(X=(SO3 -)m-2;l=m=4;o=p=0;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入5.0g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-2;l=m=4;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-2;l=m=4;n=16;R1=Ph)的硅胶。
实施例13
硅胶与聚醚离子液体12(X=(SO3 -)m-4;l=m=2;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入5.8g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-4;l=m=2;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-4;l=m=2;n=16;R1=Ph)的硅胶。
实施例14
硅胶与聚醚离子液体12(X=(SO3 -)m-6;l=m=2;o=2,q=r=1,s=t=0;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入6.1g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-6;l=m=2;o=2,q=r=1,s=t=0;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-6;l=m=2;o=2,q=r=1,s=t=0;n=16;R1=Ph)的硅胶。
实施例15
硅胶与聚醚离子液体12(X=(SO3 -)m-8;l=m=4;o=p=0;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入5.1g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-8;l=m=4;o=p=0;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-8;l=m=4;o=p=0;n=16;R1=Ph)的硅胶。
实施例16
硅胶与聚醚离子液体12(X=(SO3 -)m-9;l=m=2;o=p=2;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入5.6g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-9;l=m=2;o=p=2;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-9;l=m=2;o=p=2;n=16;R1=Ph)的硅胶。
实施例17
硅胶与聚醚离子液体12(X=(SO3 -)m-10;l=m=2;o=p=2;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入5.8g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-10;l=m=2;o=p=2;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-10;l=m=2;o=p=2;n=16;R1=Ph)的硅胶。
实施例18
硅胶与聚醚离子液体12(X=(SO3 -)m-11;l=m=2;o=p=2;n=16;R1=Ph)交联
将2g硅胶在300℃干燥6h,进行活化。将活化处理后的硅胶分散在30mL无水甲苯中,加入5.7g带有硅烷偶联基团的聚醚功能化离子液体12(X=(SO3 -)m-11;l=m=2;o=p=2;n=16;R1=Ph),在惰性气氛下,60℃条件下反应48h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到表面接枝聚醚功能化离子液体12(X=(SO3 -)m-11;l=m=2;o=p=2;n=16;R1=Ph)的硅胶。
Claims (3)
1.一种二氧化硅基材料负载聚醚功能化离子液体催化剂的制备方法,其特征在于,将带有硅烷偶联基团的聚醚功能化离子液体与活化处理后的二氧化硅基材料表面的硅醇基反应,得到式3或式4所示的二氧化硅基材料负载聚醚功能化离子液体催化剂,二氧化硅基材料为硅胶或分子筛:
所述的带有硅烷偶联基团的聚醚功能化离子液体为式14或式15所示的结构:
其中,n=16,R1为苯基;当X为-OMs,-OTs,-OAc,Cl-,Br-,I-,BF4 -,PF6 -时,l=1;当X为具有以下结构的磺酸型水溶性膦配体阴离子时,l=m,m是膦配体上磺酸根的总数,m>1:
式中1,2,3,4,5,6,7、8、9、10和11分别为不同的磺酸型水溶性膦配体的母体部分,m是膦配体上磺酸根的总数,m>1;R2为C6H4-3-SO3 -;o=0,1,2;p=0,1,2;q=r=0,1;s=t=0,1。
2.根据权利要求1所述的一种二氧化硅基材料负载聚醚功能化离子液体催化剂的制备方法,其特征在于,
将二氧化硅基材料在120-300℃干燥6-12h,进行活化。
3.根据权利要求1所述的一种二氧化硅基材料负载聚醚功能化离子液体催化剂的制备方法,其特征在于,
将活化处理后的二氧化硅基材料分散在无水甲苯中,加入带有硅烷偶联基团的聚醚功能化离子液体,在惰性气氛下,40-80℃条件下反应20-96h后,冷却至室温,过滤分离,用氯仿洗涤,并干燥,得到二氧化硅基材料负载聚醚功能化离子液体催化剂。
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