CN107236005A - 一种可用于氢甲酰化的助催化剂的合成方法及其应用方法 - Google Patents
一种可用于氢甲酰化的助催化剂的合成方法及其应用方法 Download PDFInfo
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Abstract
本发明是一种可用于氢甲酰化的助催化剂的合成方法,包括如下步骤:a.将[Pd(μ‑OH)2(PPh3)2][BF4]2悬浮于二氯甲烷中,所得的混合物的温度逐渐降至0±2℃;b.在剧烈搅拌下逐滴加入1.5~1.9物质的量的单位的乙醇,在室温下搅拌直至悬浮物完全溶解;c.在低于0℃的温度下减压蒸去所述的二氯甲烷;d.将剩下的物质用乙醇重结晶,即得到所需的最终产物。它实现了一种合成方法简单,产率高,用量比低的助催化剂的合成方法。
Description
技术领域
本发明涉及一种用于石化领域,尤其是涉及一种助催化剂的合成及应用。
背景技术
钯催化剂是一种以金属钯为主要活性组分,使用钯黑或钯的盐类将钯载于氧化铝、沸石等载体上,以钠、镉、铅等盐为助催化剂,制成的各种催化剂,是化学和化工反应过程经常采用的一种催化剂,具有催化活性高,选择性强,催化剂制作方便,使用量少,可以通过制造方法的变化和改进,与其他金属或助催化剂活性组分复配,优化性能。应用领域广,能够反复再生和活化使用,寿命长,废催化剂的金属钯可以回收再利用等优越性。许多钯催化剂品种都已成为专利产品应用于各行各业,具有新的结构及催化功能的钯催化剂仍在不断涌现,使许多难以实现的反应过程成为可能,使许多工业生产过程得到改善,是工艺过程简化、经济效益提高,因此钯催化剂的发展前景远大喜人。
发明内容
本发明主要是解决现有技术所存在的钯催化剂的合成方法复杂,产率低,用量比高等技术问题。提供了一种合成方法简单,产率高,用量比低的助催化剂的合成方法。
本发明的上述技术问题主要是通过下述技术方案得以解决的:一种可用于氢甲酰化的助催化剂的合成方法,其特征在于包括方法一或方法二,所述的方法一的操作按以下步骤:
a.将[Pd(μ-OH)2(PPh3)2][BF4]2悬浮于二氯甲烷中,所得的混合物的温度逐渐降至0±2℃;
b.在剧烈搅拌下逐滴加入1.5~1.9物质的量的单位的乙醇,在室温下搅拌直至悬浮物完全溶解;
c.在低于0℃的温度下减压蒸去所述的二氯甲烷;
d.将剩下的物质用乙醇重结晶,即得到所需的最终产物。
所述的方法二的操作按以下步骤:
a.将Pd(OTf)2(PPh3)2和甲苯放置在预先置换为氮气环境的反应釜中;
b.往所述的反应釜中通入4.5~5.5bar的氢气,该氢气的纯度为99.99%以上;
c.搅拌并加热所述的反应釜直到压力表的示数达到最低值;
d.将所得的溶液过滤,将滤液在旋转蒸发仪上浓缩成浓缩液;
e.将所述的浓缩液置放于-22~-18℃中结晶23~30小时,即得到所需的最终产物。
作为优选,所述的合成方法一的步骤a中所述的[Pd(μ-OH)2(PPh3)2][BF4]2为0.068物质的量的单位,所述的二氯甲烷为35~43物质的量的单位。
作为优选,所述的合成方法二的步骤a中所述的Pd(OTf)2(PPh3)2为0.01物质的量的单位,所述的甲苯为1.8~2.2物质的量的单位,。
作为优选,将所述的合成方法二的步骤c中的所述的反应釜加热方法为将所述的反应釜置于油浴中,所述的油浴温度为55~65℃。
作为优选,所述的合成方法二的步骤d中所述的滤液浓缩至45~55ml。
本发明所述的一种可用于氢甲酰化的助催化剂的合成方法合成的所述的助催化剂的使用方法,其特征在于所述的方法的操作按以下步骤:
a.将Rh(acac)(CO)2、三苯基膦和助催化剂溶解于甲苯中,将所得溶液充分搅拌;
b.将所述的溶液转移到预先置换为氮气环境的反应釜中;
c.往所述的反应釜中持续通入预先混合好的顺-2-丁烯气体或顺,反-2辛烯,同时持续通入合成气以始终保持反应釜内气压为20±0.5bar;
d.持续搅拌所述的反应釜并将所述的反应釜加热至120±5℃,搅拌时长为4±0.5小时,
e.将所述的反应釜自然冷却到室温,气相色谱分析所得液体中含有正戊醛,异戊醛或壬醛混合物。
作为优选,所述的使用方法的步骤a中所述的Rh(acac)(CO)2为0.001物质的量的单位,所述的三苯基膦为0.05~0.07物质的量的单位,所述的助催化剂为0.0009~0.0011物质的量的单位,所述的甲苯为0.42~0.52物质的量的单位,所述的充分搅拌的时长为1~1.5小时。
作为优选,所述的使用方法的步骤c中所述的顺-2-丁烯气体为CO、H2和丁烯混合后的气体,其混合比例为0.8:0.8:1~1:1:1,所述的顺,反-2辛烯为9~11物质的量的单位。
作为优选,所述的使用方法的步骤e中的所述的气相色谱分析所得液体中含有的所述的正戊醛为0.44~0.54物质的量的单位,所述的异戊醛0.040~0.048物质的量的单位,或所述的气相色谱分析结果显示烯烃转化率为90~100%,所得液体中含有壬醛混合物7.6~9.6物质的量的单位,醛类物质收率为80~95%。
本发明带来的有益效果是,该助催化剂的合成方法简单,产率高达60~95%,应用此使用方法用量比低至万分之一到千分之一。
具体实施方式
下面通过实施例,对本发明的技术方案作进一步具体的说明。
实施例1:
将100g [Pd(μ-OH)2(PPh3)2][BF4]2 (0.068摩尔,分子量1473.22)悬浮于于二氯甲烷2.5L中,所得的溶液逐渐降温到0oC,剧烈搅拌下逐滴加入乙醇100ml。室温搅拌24小时或者悬浮物完全溶解,此时溶液为红色,蒸去二氯甲烷溶剂,得到红色粗产品。粗品用乙醇重结晶得到红色固体33.2g,产率94%。
实施例2:
将9.29克Pd(OTf)2(PPh3)2和200毫升甲苯溶剂放置在预先置换为氮气环境的300毫升高压釜中,往高压釜中通入5 Bar的高纯氢气(99.99%),此时开动搅拌并将反应釜置于预热到60oC的油浴中并持续搅拌5小时,直到压力表视数不再降低。此时将所得溶液过滤,滤液浓缩至50ml后置放于-20oC的冰柜中冷冻结晶,得到红色产品3.34g,产率64%。
实施例3:
将0.258g Rh(acac)(CO)2 (0.001mol), 13.1克三苯基膦(0.05mol, 50倍过量)和1.54g助催化剂1.54克(0.001mol)预先溶解于50毫升甲苯溶剂中,将所得溶液充分搅拌1小时并将溶液转移到预先置换为氮气环境的5L高压釜中,往高压釜中通入预先混合好的顺-2-丁烯气体(CO:H2:丁烯比例为0.9:0.9:1)和合成气至20 Bar并不断通入混合气保持压力稳定在20 Bar,此时开动搅拌并将高压釜加热至120oC,持续搅拌4小时。将高压釜自然冷却到室温,气相色谱分析所得液体中含有正戊醛42.3g,异戊醛3.71g。
实施例4:
将0.258g Rh(acac)(CO)2 (0.001mol), 13.1克三苯基膦(0.05mol, 50倍过量)和1.54g助催化剂1.54克(0.001mol)预先溶解于50毫升甲苯溶剂中,将所得溶液充分搅拌1小时并将溶液转移到预先置换为氮气环境的5L高压釜中,往高压釜中加入顺,反-2辛烯 1120克 ,10摩尔并通入合成气至20 Bar,此时开动搅拌并将高压釜加热至120oC,持续搅拌4小时,并随时保持气体压力在20 Bar。将高压釜自然冷却到室温,气相色谱分析结果显示烯烃转化率为95%。所得液体中含有壬醛混合物1237g, 醛类物质收率为87%。
本发明带来的有益效果是,该助催化剂的合成方法简单,产率高达60~95%,应用此使用方法用量比低至万分之一到千分之一。
Claims (9)
1.一种可用于氢甲酰化的助催化剂的合成方法,其特征在于包括方法一或方法二,所述的方法一的操作按以下步骤:
a.将 [Pd(μ-OH)2(PPh3)2][BF4]2悬浮于二氯甲烷中,所得的混合物的温度逐渐降至0±2℃;
b.在剧烈搅拌下逐滴加入1.5~1.9物质的量的单位的乙醇,在室温下搅拌直至悬浮物完全溶解;
c.在低于0℃的温度下减压蒸去所述的二氯甲烷;
d.将剩下的物质用乙醇重结晶,即得到所需的最终产物;
所述的方法二的操作按以下步骤:
a.将Pd(OTf)2(PPh3)2和甲苯放置在预先置换为氮气环境的反应釜中;
b.往所述的反应釜中通入4.5~5.5bar的氢气,该氢气的纯度为99.99%以上;
c.搅拌并加热所述的反应釜直到压力表的示数达到最低值;
d.将所得的溶液过滤,将滤液在旋转蒸发仪上浓缩成浓缩液;
e.将所述的浓缩液置放于-22~-18℃中结晶23~30小时,即得到所需的最终产物。
2.根据权利要求1所述的一种可用于氢甲酰化的助催化剂的合成方法,其特征在于所述的方法一的步骤a中所述的[Pd(μ-OH)2(PPh3)2][BF4]2为0.068物质的量的单位,所述的二氯甲烷为35~43物质的量的单位。
3.根据权利要求1所述的一种可用于氢甲酰化的助催化剂的合成方法,其特征在于所述的方法二的步骤a中所述的Pd(OTf)2(PPh3)2为0.01物质的量的单位,所述的甲苯为1.8~2.2物质的量的单位,。
4.根据权利要求1所述的一种可用于氢甲酰化的助催化剂的合成方法,其特征在于将所述的方法二的步骤c中的所述的反应釜加热方法为将所述的反应釜置于油浴中,所述的油浴温度为55~65℃。
5.根据权利要求1或4所述的一种可用于氢甲酰化的助催化剂的合成方法,其特征在于所述的方法二的步骤d中所述的滤液浓缩至45~55ml。
6.采用权利要求1所述的一种可用于氢甲酰化的助催化剂的合成方法合成的所述的助催化剂的使用方法,其特征在于所述的方法的操作按以下步骤:
a.将Rh(acac)(CO)2、三苯基膦和助催化剂溶解于甲苯中,将所得溶液充分搅拌;
b.将所述的溶液转移到预先置换为氮气环境的反应釜中;
c.往所述的反应釜中持续通入预先混合好的顺-2-丁烯气体或顺,反-2辛烯,同时持续通入合成气以始终保持反应釜内气压为20±0.5bar;
d.持续搅拌所述的反应釜并将所述的反应釜加热至120±5℃,搅拌时长为4±0.5小时,
e.将所述的反应釜自然冷却到室温,气相色谱分析所得液体中含有正戊醛,异戊醛或壬醛混合物。
7.根据权利要求6所述的一种可用于氢甲酰化的助催化剂的合成方法合成的所述的助催化剂的使用方法,其特征在于所述的方法的步骤a中所述的Rh(acac)(CO)2为0.001物质的量的单位,所述的三苯基膦为0.05~0.07物质的量的单位,所述的助催化剂为0.0009~0.0011物质的量的单位,所述的甲苯为0.42~0.52物质的量的单位,所述的充分搅拌的时长为1~1.5小时。
8.根据权利要求6所述的一种可用于氢甲酰化的助催化剂的合成方法合成的所述的助催化剂的使用方法,其特征在于所述的方法的步骤c中所述的顺-2-丁烯气体为CO、H2和丁烯混合后的气体,其混合比例为0.8:0.8:1~1:1:1,所述的顺,反-2辛烯为9~11物质的量的单位。
9.根据权利要求6或7或8所述的一种可用于氢甲酰化的助催化剂的合成方法合成的所述的助催化剂的使用方法,其特征在于所述的方法的步骤e中的所述的气相色谱分析所得液体中含有的所述的正戊醛为0.44~0.54物质的量的单位,所述的异戊醛0.040~0.048物质的量的单位,或所述的气相色谱分析结果显示烯烃转化率为90~100%,所得液体中含有壬醛混合物7.6~9.6物质的量的单位,醛类物质收率为80~95%。
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