CN111701619B - 一种用于合成kh-560硅烷偶联剂的固载型催化剂及其制备方法 - Google Patents
一种用于合成kh-560硅烷偶联剂的固载型催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于合成KH‑560硅烷偶联剂的固载型催化剂及其制备方法,包括:S1以氨基功能化的MOFs为底物,通过席夫碱反应或酰胺化反应将多齿N/O杂合配体修饰在MOFs孔道内,得到具有双齿功能配体修饰的MOFs;S2将后修饰的MOFs粉体浸入特定溶剂中,加入辅助配体和缚酸剂,搅拌回流;缓慢滴加一定计量的氯铂酸甲醇溶液后继续回流,并将回流后所得产品离心后真空干燥,得到Pt/MOFs催化剂。该固载型Pt/MOFs催化剂具有较高催化活性的同时,可多次循环重复使用,解决了现有制备方法催化剂分离困难及反应废液带来的环保问题。
Description
技术领域
本发明涉及催化剂制备技术领域,尤其涉及一种用于合成KH-560硅烷偶联剂的固载型催化剂及其制备方法。
背景技术
KH-560是硅烷偶联剂的主要品种之一(其化学名称为:γ-缩水甘油醚丙基三甲基硅烷,对应牌号:KH-560(中科院)或A-187(美国联合碳化公司)),由于该分子中含有环氧基团和可水解的-OCH3基团使其具有特殊的交联性能,被广泛的应用于有机高分子材料或无机填料的粘接改性及增强复合材料的机械强度,以改善集成电路材料与印刷电路板湿态的电绝缘性能。
KH-560的合成主要是以烯丙基缩水甘油醚和三甲氧基硅烷为原料,在催化剂的作用下硅氢加成制得。如,美国专利US4966981中公开的以氯铂酸-异丙醇为催化剂、以甲醇为溶剂合成KH-560,产率达90%;中国专利201811616847.7以铑系配合物为催化剂、目标产物为溶剂制得KH-560,产率最高可达95%;中国专利201410372177.4以三氯化钌络合物为催化剂、甲苯为溶剂,产率达92-96%等。虽然目前工业生产中很多方案都能有效合成KH-560,但是催化体系以均相贵金属催化剂为主,尽管均相催化剂的效果好,但存在催化剂分离困难、无法回收再利用且反应废液污染严重等问题,严重的制约了其工业化的进一步应用。因此,将均相催化剂多相化,即制备固载型的贵金属催化剂逐渐得到了人们的关注。如,文献doi:10.1002/aoc.4874报道了将铂金属席夫碱配合物锚装在介孔分子筛SBA-15上用于KH-560的催化合成,转化率达到86%;文献doi:10.1016/j.jorganchem.2011.02.021采用氨基甲氧基硅烷将铂金属锚装在泡沫二氧化硅上,催化剂循环使用五次后产率仅下降了7%(94%到87%);文献doi: 10.4028/www.scientific.net/AMR.233-235.1544将铂/碳催化剂作为催化剂,虽然转化率高达97%,但循环使用性能不佳。
可以看出,虽然多相催化能很好地降低贵金属催化剂的用量和回收难度,但同时存在着多种多样亟需解决的问题,如载体多是无序的活性炭、介孔氧化硅或是比表面较小的氧化铝,催化效率低、催化选择性不高等。
发明内容
本发明的目的是提供一种用于合成KH-560硅烷偶联剂的固载型催化剂及其制备方法,有效解决现有催化剂催化效率低、循环效率不高等技术问题。
本发明提供的技术方案如下:
一种用于合成KH-560硅烷偶联剂的固载型催化剂制备方法,包括:
S1 以氨基功能化的MOFs为底物,通过席夫碱反应或酰胺化反应将多齿N/O杂合配体修饰在MOFs孔道内,得到具有双齿功能配体修饰的MOFs;
S2 将后修饰的MOFs粉体浸入特定溶剂中,加入辅助配体和缚酸剂,搅拌回流;缓慢滴加一定计量的氯铂酸甲醇溶液后继续回流,并将回流后所得产品离心后真空干燥,得到Pt/MOFs催化剂。
在该技术方案中,MOFs是由无机金属离子和有机官能团通过共价键自组装形成的晶态有序孔道结构材料,其不仅具有与沸石分子筛相似的晶体结构,而且其比表面积相较分子筛更大,且孔道具有可设计和可剪裁性,材料更易被功能化,故选用氨基功能化的MOFs作为固体底物或载体用于高效的选择性催化反应。
本发明还提供了一种KH-560制备方法,包括:
以烯丙基缩水甘油醚和三甲氧基硅烷为原料、如权利要求1-6任意一项所述所述固载型催化剂制备方法制备得到的Pt/MOFs催化剂为催化剂,通过同步滴加搅拌烯丙基缩水甘油醚和三甲氧基硅烷的方式制备KH-560。
本发明还提供了一种用于合成KH-560硅烷偶联剂的固载型催化剂,包括 MOFs及锚装在MOFs孔道内的Pt配合物,具体结构为:
本发明提供的用于合成KH-560硅烷偶联剂的固载型催化剂及其制备方法,以氨基功能化的MOFs为底物,通过化学键将Pt金属配合物锚装在其孔道内制备而成,该固载型Pt/MOFs催化剂具有较高催化活性的同时,可多次循环重复使用,解决了现有制备方法催化剂分离困难及反应废液带来的环保问题;同时,MOFs孔道的择型能力使得异构型副产物大大降低,进而大大提高了生产效率。此外,该工艺路线工艺简单,能制备品质稳定、收率高、成本相对低廉的KH-560硅烷偶联剂,具有较大的工业化生产潜力。
附图说明
下面将以明确易懂的方式,结合附图说明优选实施方式,对上述特性、技术特征、优点及其实现方式予以进一步说明。
图1为本发明中用于合成KH-560硅烷偶联剂的固载型催化剂制备方法的流程示意图。
具体实施方式
下面结合附图和实例进一步说明本发明的实质内容,但本发明的内容并不限于此。
针对现有催化剂催化效率低、循环效率不高等技术问题,本发明提供了一种全新的用于合成KH-560硅烷偶联剂的固载型催化剂制备方法,如图1所示,在一实施例中,该制备方法包括:
S1 以氨基功能化的MOFs为底物,通过席夫碱反应或酰胺化反应将多齿N/O杂合配体修饰在MOFs孔道内,得到具有双齿功能配体修饰的MOFs。具体,氨基功能化的MOFs为MiL-101-NH2、UiO-66-NH2或IRMOF-3;N/O杂合配体为水杨醛或哌嗪酸酐。
S2将后修饰的MOFs粉体浸入特定溶剂中,加入辅助配体和缚酸剂,搅拌回流;缓慢滴加一定计量的氯铂酸甲醇溶液后继续回流,并将回流后所得产品离心后真空干燥,得到Pt/MOFs催化剂,结构如下:
具体,特定溶剂为甲苯、THF或甲醇;辅助配体为乙酰丙酮、正丁醇或异丁醇中的一种或多种复配物;缚酸剂为三乙醇胺,且被修饰的MOFs粉体、氯铂酸、辅助配体、缚酸剂的摩尔比为1:0.1~1.0:0.5~2.0:0.5~2.0。
在步骤S1进行席夫碱反应或酰胺化反应之前还包括将MOFs活化的步骤:将MOFs粉体浸于特定溶剂中一定时间,且定期对该特定溶剂进行更换,将浸泡过后得到的产品进行离心并烘干得到活化的MOFs;特定溶剂为甲苯、THF或甲醇。具体,将活化的MOFs粉体及N/O杂合配体加入特定溶剂中,加热回流12 h得到具有双齿功能配体修饰的MOFs,其中,MOFs粉体与N/O杂合配体的投料摩尔比为1:1~10之间,且MOFs粉体的摩尔质量以-NH2基团计。
基于上述实施例制备得到的Pt/MOFs催化剂,本发明还提供了一种KH-560制备方法,包括:以烯丙基缩水甘油醚和三甲氧基硅烷为原料、如上述方法制备得到的Pt/MOFs催化剂为催化剂,通过同步滴加搅拌烯丙基缩水甘油醚和三甲氧基硅烷的方式制备KH-560。在这一过程中,充入2bar氮气,反应温度为80~90℃,反应时间为2-6h,且烯丙基缩水甘油醚、三甲氧基硅烷、Pt/MOFs催化剂的摩尔比为1:1:0.001~0.005其中,MOFs粉体的摩尔质量以-NH2基团计。
以下通过实例对对本发明作进一步的详细描述:
实施例1:
催化剂1的合成。(1)称取MiL-101-NH2粉体1mmol(以-NH2基团计),浸入10mL甲醇溶液中,超声震荡后室温静置1d(1天),离心倾倒掉上层溶液,再加入新鲜的甲醇溶剂,重复以上过程3次(浸泡3天,每天换一次新鲜甲醇溶液)。之后将离心后的固体粉末置于真空干燥箱中干燥4h,得到活化的MiL-101-NH2。(2)将活化的MIL-101-NH2加入20mL甲醇中,强烈搅拌下滴加2mmol的水杨醛,加热回流12h后将产物离心干燥,得到水杨醛修饰的MiL-101。(3)将水杨醛修饰的MiL-101加入20mL甲醇溶剂中,加入1mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流;缓慢滴加2ml含1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂1。
实施例2:
催化剂2的合成。(1)合成步骤同实施例1中的第(1)步。(2)将活化的MIL-101-NH2加入20mL甲醇中,强烈搅拌下滴加1mmol的水杨醛,加热回流12h,产物离心干燥,得到水杨醛修饰的MiL-101。(3)合成步骤同实施例1中的第(3)步,得到催化剂2。
实施例3:
催化剂3的合成。(1)合成步骤同实施例1中的第(1)步。(2)将活化的MIL-101-NH2加入20mL甲醇中,强烈搅拌下滴加10mmol的水杨醛,加热回流12h,产物离心干燥,得到水杨醛修饰的MiL-101。(3)合成步骤同实施例1中的第(3)步,得到催化剂3。
实施例4:
催化剂4的合成。(1)合成步骤同实施例1中的第(1)步。(2)合成步骤同实施例1中的第(2)步。(3)将水杨醛修饰的MiL-101加入20mL甲醇溶剂中,加入1mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml含0.1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂4。
实施例5:
催化剂5的合成。(1)合成步骤同实施例1中的第(1)步。(2)合成步骤同实施例1中的第(2)步。(3)将水杨醛修饰的MiL-101加入20mL甲醇溶剂中,加入2.0mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml含0.1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂5。
实施例6:
催化剂6的合成。(1)合成步骤同实施例1中的第(1)步。(2)合成步骤同实施例1中的第(2)步。(3)将水杨醛修饰的MiL-101加入20mL甲醇溶剂中,加入1.0mmol的异丁醇和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml 含0.1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂6。
实施例7:
催化剂7的合成。(1)合成步骤同实施例1中的第(1)步。(2)将活化的MIL-101-NH2加入20mL甲醇中,强烈搅拌下滴加2mmol的哌嗪酸酐,加热回流12h,产物离心干燥,得到哌嗪羧酸修饰的MiL-101。(3)将哌嗪羧酸修饰的MiL-101加入20mL甲醇溶剂中,加入1mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml含1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂7。
实施例8:
催化剂8的合成。(1)称取UiO-66-NH2粉体1mmol(以-NH2基团计),浸入10mL甲醇溶液中,超声震荡后室温静置1d,离心倾倒掉上层溶液,再加入新鲜的甲醇溶剂,重复以上过程3次。将离心后的固体粉末置于真空干燥箱中干燥4h,得到活化的UiO-66-NH2。(2)将活化的UiO-66-NH2加入20mL甲醇中,强烈搅拌下滴加2mmol的水杨醛,加热回流12h,产物离心干燥,得到水杨醛修饰的UiO-66。(3)将水杨醛修饰的UiO-66加入20mL甲醇溶剂中,加入1mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml 含1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂8。
实施例9:
催化剂9的合成。(1)合成步骤同实施例8中的第(1)步。(2)将活化的UiO-66-NH2加入20mL甲醇中,强烈搅拌下滴加2mmol的哌嗪酸酐,加热回流12h,产物离心干燥,得到哌嗪羧酸修饰的UiO-66。(3)将哌嗪羧酸修饰的UiO-66加入20mL甲醇溶剂中,加入1mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml含1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂9。
实施例10
催化剂10的合成。(1)称取IRMOF-3晶体1mmol(以-NH2基团计),浸入10mL甲醇溶液中,超声震荡后室温静置1d,离心倾倒掉上层溶液,再加入新鲜的甲醇溶剂,重复以上过程3次。将离心后的固体粉末置于真空干燥箱中干燥4h,得到活化的IRMOF-3。(2)将活化的IRMOF-3加入20mL甲醇中,强烈搅拌下滴加2mmol的水杨醛,加热回流12h,产物离心干燥,得到水杨醛修饰的IRMOF-3。(3)将水杨醛修饰的IRMOF-3加入20mL甲醇溶剂中,加入1mmol的乙酰丙酮和1mmol的三乙醇胺,加热至回流,缓慢滴加2ml 含1mmol的氯铂酸甲醇溶液,再回流4h,最后将所得固体产品离心干燥,得到催化剂10。
实施例11
催化剂催化合成KH-560测试。
通过移液枪将8.6L三甲氧基硅烷和7.8 mL烯丙基缩水甘油醚加入高压反应釜,加入内标十二烷5 mL,混合均匀。之后加入固体催化剂,密封。通入氮气,充放气3次排空反应釜内空气,保持反应釜压力2bar,机械搅拌360r/min,温度设置80~90℃,连续反应2-6h。GC定性分析反应主、副产物,然后减压蒸馏分离获得产品,计算KH-560收率(表1)。
实施例12
催化剂的回收循环催化测试。将反应后的催化剂离心回收,不加洗涤直接进行第二次、第三次循环使用,反应条件同实施例11所述,再次计算其收率(表1)。
表1不同催化剂催化合成KH-560的收率
催化剂 | 催化剂1 | 催化剂2 | 催化剂3 | 催化剂4 | 催化剂5 | 催化剂6 | 催化剂7 | 催化剂8 | 催化剂9 | 催化剂10 |
KH-560收率 | 85% | 74% | 78% | 56% | 68% | 55% | 82% | 75% | 74% | 86% |
KH-560收率a | 83% | 74% | 78% | 54% | 66% | 54% | 81% | 73% | 74% | 45% |
KH-560收率b | 82% | 73% | 77% | 50% | 65% | 53% | 74% | 72% | 74% | 11% |
其中,a催化剂回收第二次使用的收率,b催化剂回收第三次使用的收率。
从表中可以看出,即便到了回收第三次使用,催化剂1~催化剂10均具有较好收率。
应当说明的是,上述实施例均可根据需要自由组合。以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范。
Claims (7)
1.一种用于合成KH-560硅烷偶联剂的固载型催化剂制备方法,其特征在于,包括:
S1 以氨基功能化的MOFs为载体,通过席夫碱反应或酰胺化反应将多齿N/O杂合配体修饰在MOFs孔道内,得到具有双齿功能配体修饰的MOFs;
S2 将后修饰的MOFs粉体浸入特定溶剂中,加入辅助配体和缚酸剂,搅拌回流;缓慢滴加一定计量的氯铂酸甲醇溶液后继续回流,并将回流后所得产品离心后真空干燥,得到Pt/MOFs催化剂;
在步骤S1中,氨基功能化的MOFs为MiL-101-NH2;N/O杂合配体为水杨醛或哌嗪酸酐;在步骤S2中,特定溶剂为甲苯、THF或甲醇;辅助配体为乙酰丙酮、正丁醇或异丁醇中的一种或多种复配物;缚酸剂为三乙醇胺;在步骤S2中,被修饰的MOFs粉体、氯铂酸、辅助配体、缚酸剂的摩尔比为1:0.1~1.0:0.5~2.0:0.5~2.0。
2.如权利要求1或所述的制备方法,其特征在于,在步骤S1进行席夫碱反应或酰胺化反应之前还包括将MOFs活化的步骤:
将MOFs粉体浸于特定溶剂中一定时间,且定期对该特定溶剂进行更换,将浸泡过后得到的产品进行离心并烘干得到活化的MOFs;所述特定溶剂为甲苯、THF或甲醇。
3.如权利要求2所述的制备方法,其特征在于,在步骤S1中包括:
将活化的MOFs粉体及N/O杂合配体加入特定溶剂中,加热回流12 h得到所述具有双齿功能配体修饰的MOFs,其中,MOFs粉体与N/O杂合配体的投料摩尔比为1:1~10之间,且MOFs粉体的摩尔质量以-NH2基团计。
4.一种KH-560制备方法,其特征在于,包括:
以烯丙基缩水甘油醚和三甲氧基硅烷为原料、如权利要求1-3任意一项所述的制备方法制备得到的Pt/MOFs催化剂为催化剂,通过同步滴加搅拌烯丙基缩水甘油醚和三甲氧基硅烷的方式制备KH-560。
5.如权利要求4所述的KH-560制备方法,其特征在于,所述烯丙基缩水甘油醚、三甲氧基硅烷、Pt/MOFs催化剂的摩尔比为1:1:0.001~0.005其中,MOFs粉体的摩尔质量以-NH2基团计。
6.如权利要求4或5所述的KH-560制备方法,其特征在于,在制备KH-560的催化反应过程中,充入2bar氮气,反应温度为80~90℃,反应时间为2-6h。
7.一种如权利要求1-3任意一项所述的制备方法制备得到用于合成KH-560硅烷偶联剂的固载型催化剂,其特征在于,所述固载型催化剂中包括MOFs及锚装在MOFs孔道内的Pt配合物,MOFs为MiL-101-NH2,具体结构为:
。
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