CN116410072A - 一种1,6-己二醛的制备方法 - Google Patents
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Abstract
本发明提供一种1,6‑己二醛的制备方法,包括如下步骤:将二齿膦配体单体与含有乙烯基的单体进行聚合反应,聚合反应结束后得到有机膦配体共聚物;在H2与CO混合气的保护下,将所述有机膦配体共聚物和金属铑前驱体在60‑120℃下反应1‑4h,制备得到催化剂;在所述催化剂中加入1,3‑丁二烯进行氢甲酰化反应,反应结束后制备得到1,6‑己二醛。本发明提供的催化剂,在实现非均相催化1,3‑丁二烯氢甲酰化反应的同时,可有效提高1,6‑己二醛的选择性,并且催化剂容易与反应产物分离,可有效解决催化剂回收利用和环境污染等问题。
Description
技术领域
本发明涉及一种1,6-己二醛的制备方法,涉及石油化工技术领域。
背景技术
烯烃氢甲酰化反应制备醛是工业上合成醛的重要方法,可以将廉价易得的烯烃高效地转化为附加值更高的精细化学品,因此,氢甲酰化反应成为生产规模最大的催化过程之一。但迄今为止,工业化生产中所用到的烯烃大部分为非共轭烯烃,对于共轭烯烃氢甲酰化反应制备多元醛仍具有挑战性,主要原因是反应的副产物多且区域选择性差,以最简单的共轭烯烃1,3-丁二烯为例,1,3-丁二烯氢甲酰化反应可发生1,4-加成羰基化、1,2-加成羰基化、C=C 双键异构化以及还原化、异构还原化等多种反应路径,同时存在反应速率慢和区域选择性差,并有十几种异构化产物和副产物同时生成。
1,3-丁二烯氢甲酰化反应研发过程中使用最多且活性最好的金属是铑, Rh基催化体系1,3-丁二烯氢甲酰化反应合成1,6-己二醛的选择性在约40%,远达不到实际工业应用的要求;此外,铑是贵金属,因此其前驱体化合物都很昂贵,而目前为止研发的催化剂为均相催化剂,贵金属铑催化剂在反应完成后无法回收,造成反应成本增加的同时也给环境带来压力。因此,如何解决1,3-丁二烯氢甲酰化制备1,6-己二醛的过程中,1,6-己二醛选择性低,催化剂无法回收的问题受到了越来越多的关注。
发明内容
本发明提供一种1,6-己二醛的制备方法,用于解决1,6-己二醛选择性差、催化剂无法回收的问题。
本发明提供了一种1,6-己二醛的制备方法,所述方法包括如下步骤:
将二齿膦配体单体与含有乙烯基的单体进行聚合反应,聚合反应结束后得到有机膦配体共聚物;在H2与CO混合气的保护下,将所述有机膦配体共聚物和金属铑前驱体在60-120℃下反应1-4h,制备得到催化剂;在所述催化剂中加入1,3-丁二烯进行氢甲酰化反应,反应结束后制备得到1,6-己二醛;
所述二齿膦配体单体具有式1所示的结构:
本发明提供了一种1,6-己二醛的制备方法,通过使用有机膦配体共聚物作为载体和配体,形成单点配位结构催化,实现非均相催化1,3-丁二烯的氢甲酰化反应,图1为本发明一实施例提供的制备方法的流程示意图,如图1所示,该方法具体包括如下步骤:
步骤1、将二齿膦配体单体与含有乙烯基的单体进行聚合反应,聚合反应结束后得到有机膦配体共聚物,其反应过程如下所示:
步骤1-1、根据公开号为CN 113004326A的中国专利制备得到化合物1,将化合物1放入反应釜中,添加乙烯化试剂、催化剂和溶剂,在氮气保护下回流反应过夜,冷却至室温,减压蒸馏除去溶剂,柱层析纯化,分离得到化合物2;
步骤1-2、在氮气保护下,向反应器中加入氯化膦类化合物(R1-Cl和/ 或R2-Cl)和溶剂,降温至0℃,另外取化合物2和三乙胺溶于溶剂中,在0 ℃将化合物2和三乙胺混合溶液滴加到反应器中,自然升至室温反应,加水淬灭反应,加乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到式1所示的化合物;其中,溶剂选自四氢呋喃、甲苯和N,N-二甲基甲酰胺中的一种或多种。
步骤1-3、向反应器中加入式1所示的化合物,加含有乙烯基的单体、 AIBN和溶剂,在氮气保护下进行聚合反应,聚合反应结束后冷却至室温,加甲醇沉淀、过滤、洗涤、真空干燥,得到如式2所示的有机膦配体聚合物。
所述二齿膦配体单体与含有乙烯基的单体的摩尔比为1:(1-10);所述聚合反应的温度为60-100℃,时间为2-6h;溶剂选自四氢呋喃、2-甲基四氢呋喃和甲苯中的一种或多种。
制备得到的有机磷配体化合物可以使用式2所示的结构表示,其中,所述有机膦配体共聚物的分子量为70000-100000g/mol,35≤m≤55,35≤n≤55, m:n=1:(1-10)。
步骤2、在H2与CO混合气的保护下,将所述有机膦配体共聚物和金属铑前驱体在60-120℃下反应1-4h,制备得到催化剂;
所述金属铑前驱体可以为本领域常规材料,具体可选自Rh(CO)2(acac)、 Rh(AcO)2、RhCl3、Rh(NO3)3、RhH(CO)(PPh3)3、[Rh(CO)2Cl]2、RhH(CO)(PPh3)3、 [Rh2(m-Cl)2(cod)2]、[Rh(cod)2]BF4中的一种或多种,进一步地,所述金属铑前驱体为Rh(CO)2(acac)。
将上述制备方法制备得到的有机膦配体聚合物和金属铑前驱体加入反应釜中,并加入一定量的溶剂进行分散,其中,所述金属铑前驱体与所述有机膦配体共聚物的质量比为(1:1)-(1:50),进一步地,所述金属铑前驱体与所述有机膦配体共聚物的质量比为(1:5)-(1:20)。
所述溶剂选自正己烷、环己烷、苯、甲苯、二甲苯、四氢呋喃和二氧六环中的一种或多种,进一步地,所述溶剂选自正己烷、四氢呋喃、甲苯中的一种或多种。
随后即可密封反应釜,并持续通入H2与CO混合气,在60-120℃下反应 1-4h,即可制备得到催化剂,其中,混合气用于保护催化剂,所述H2与CO 的混合气的压力为1-10MPa,H2和CO的体积比为(1:10)-(10:1),进一步地,所述混合气的压力为2-5Mpa,H2和CO的体积比为(1:5)-(1:1),控制温度搅拌反应一定时间即可得到催化剂。
步骤3、在所述催化剂中加入1,3-丁二烯进行氢甲酰化反应,反应结束后制备得到1,6-己二醛;
在催化剂中加入1,3-丁二烯,具体可以将1,3-丁二烯溶于溶剂中配制成 1,3-丁二烯溶液,其中,所述金属铑前驱体与所述1,3-丁二烯的摩尔比为(1:50) -(1:50000),进一步地,所述金属铑前驱体与所述1,3-丁二烯的摩尔比为(1:200) -(1:1000),溶剂可以为己烷、甲苯、四氢呋喃中的一种或多种,进一步地,溶剂为己烷、甲苯中的一种或多种,1,3-丁二烯溶液的浓度为0.1-10mol/L,进一步地,1,3-丁二烯溶液的浓度为0.5-3mol/L。
随后控制反应温度为50-150℃进行氢甲酰化反应,反应时间一般为1-24h 即可结束反应,待反应体系冷却到室温后释放未反应的气体,即可得到1,6- 己二醛,进一步地,控制反应温度为60-120℃,反应时间为5-15h。
通过气相色谱内标法测得1,3-丁二烯的转化率大于等于90%,1,6-己二醛的选择性大于等于49%。
通过使用本发明提供的有机配体共聚物作为载体和配体,形成单点配位结构催化,实现非均相催化1,3-丁二烯氢甲酰化反应的同时,可有效提高1,6-己二醛的选择性,并且催化剂容易与反应产物分离,可有效解决催化剂回收利用和环境污染等问题。
附图说明
图1为本发明一实施例提供的制备方法的流程示意图;
图2为实施例1中有机膦配体共聚物制备过程中化合物2的核磁氢谱;
图3为实施例1中有机膦配体共聚物制备过程中化合物3的核磁氢谱;
图4为实施例1中有机膦配体共聚物制备过程中化合物3的核磁膦谱;
图5为实施例1中有机膦配体共聚物L1的核磁氢谱;
图6为实施例1中有机膦配体共聚物L1的核磁膦谱;
图7为实施例8中有机膦配体共聚物L2的核磁膦谱;
图8为实施例9中有机膦配体共聚物L3的核磁膦谱。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合本发明的实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
步骤1、有机膦配体共聚物L1的制备:
步骤1-1、以1,8-二羟基蒽醌为原料,参考CN113004326A制备得到化合物1。
步骤1-2、取5g化合物1加入反应器中,加100ml的甲苯、12g的乙烯基三正丁基锡和0.73g的四(三苯基膦)钯,在氮气保护下回流反应过夜,反应结束后,冷却至室温,减压蒸馏除去溶剂,柱层析纯化,洗脱剂为石油醚:乙酸乙酯=2:1,分离得到化合物2,化合物2的核磁数据如下,H谱如图 2所示:
1H NMR(400MHz,DMSO)δ9.39(s,1H),7.16(dt,J=11.2,8.2Hz,2H), 6.60(d,J=8.5Hz,1H),5.56(d,J=1.4Hz,1H),5.18(dd,J=11.0,1.4Hz,1H), 5.10(d,J=1.7Hz,1H),1.51(s,2H)。
步骤1-3、取1.27g的加入反应器中,在氮气保护下加6ml超干四氢呋喃,降温至0℃,另外取400mg化合物2和418mg三乙胺溶于2ml 超干四氢呋喃,在0℃将此混合液滴加到上述反应器中,自然升至室温,反应1h。加入20ml水淬灭,加20ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到化合物3,化合物3的核磁数据如下,H谱和膦谱分别如图3、图4所示;
1H NMR(400MHz,CDCl3)δ7.22(d,J=8.5Hz,2H),7.14(dd,J=17.4, 11.0Hz,2H),7.03(d,J=3.8Hz,5H),6.97(d,J=8.5Hz,2H),6.92(d,J=8.3 Hz,5H),5.61(dd,J=17.4,1.2Hz,2H),5.42(s,1H),5.34(dd,J=11.0,1.2Hz, 2H),5.15(s,0H),2.31(d,J=7.2Hz,12H),2.21(d,J=3.6Hz,12H),1.67(q,J= 9.1Hz,4H)。
步骤1-4、取400mg的化合物3加入反应器中,加500mg的苯乙烯、45mg的AIBN以及9ml的超干四氢呋喃,在氮气保护下100℃反应4h,反应结束后冷却至室温,加20ml甲醇沉淀,过滤,甲醇洗涤,真空干燥,得到有机膦配体共聚物L1,其氢谱和膦谱分别如图5、6所示,反应过程如下图:
有机膦配体共聚物L1的分子量为85000g/mol,m=40,n=50,m:n=1:1.25。
步骤2、在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
步骤3、降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在60℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为95.3%,1,6-己二醛的选择性为51.5%。
实施例2
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加3ml甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为99.2%,1,6-己二醛的选择性为49.2%。
实施例3
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加3ml甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在100℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为99.8%,1,6-己二醛的选择性为52.6%。
实施例4
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,在2MPa、80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为92.8%,1,6-己二醛的选择性为55.8%。
实施例5
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至6MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为99.8%,1,6-己二醛的选择性为57.9%。
实施例6
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应8h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为91.5%,1,6-己二醛的选择性为56.5%。
实施例7
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应15h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为99.7%,1,6-己二醛的选择性为49.0%。
实施例8
有机膦配体共聚物L2的制备方法可参考实施例1,区别在于:
取300mg的化合物3加入反应器中,加入1.22g的三(4-乙烯基苯基) 膦、35mg的AIBN以及15ml的超干四氢呋喃,在氮气保护下100℃反应5 h,反应结束后冷却至室温,加20ml甲醇沉淀,过滤,甲醇洗涤,真空干燥,得到有机膦配体共聚物L2,其膦谱如图7所示,所涉及的反应过程如下所示:
有机膦配体共聚物L2的分子量91000g/mol,m=36,n=52,m:n=1:1.44。
在手套箱中,分别取20mg有机膦配体共聚物L2和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为99.5%,1,6-己二醛的选择性为53.4%。
实施例9
在手套箱中,称取9.3mg的有机膦配体共聚物L3和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为99.6%,1,6-己二醛的选择性为50.9%。
实施例10
有机膦配体共聚物L4的制备方法可参考L1,区别在于,化合物3中R1和R2为步骤4中,含有乙烯基的单体为三(4-乙烯基苯基) 膦,有机膦配体共聚物L4的分子量为88000g/mol,m=45,n=50,m:n=1:1.11。
在手套箱中,称取20mg的有机膦配体共聚物L4和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为95.5%,1,6-己二醛的选择性为51.8%。
实施例11
在手套箱中,称取9.2mg的有机膦配体共聚物L5和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为90.8%,1,6-己二醛的选择性为55.6%。
实施例12
有机膦配体共聚物L6的制备方法可参考L1,区别在于,化合物3中R1为R2为/>步骤4中,含有乙烯基的单体为三 (4-乙烯基苯基)膦,有机膦配体共聚物L6的分子量为98000g/mol,m=50, n=54,m:n=1:1.08。
在手套箱中,称取9.2mg有机膦配体共聚物L6和1mg的金属铑前驱体 Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,制备得到1,6-己二醛。
通过气相色谱内标法测得1,3-丁二烯的转化率为92.2%,1,6-己二醛的选择性为56.9%。
为了更清楚的了解本发明,对实施例1-12所使用的催化剂以及反应过程参数进行了列表说明,详见表1-2:
表1实施例1-12所使用的有机膦配体共聚物
表2实施例1-12提供的反应参数
通过表2可知,本发明提供的有机膦配体共聚物可有效催化1,3-丁二烯氢甲酰化反应,并且1,3-丁二烯的转化率均大于等于90%,1,6-己二醛的选择性均大于等于49%。
实施例13
在手套箱中,称取8.5mg的有机膦配体共聚物L1和1mg的金属铑前驱体Rh(acac)(CO)2,加入到高压釜中,随后加入3ml的甲苯,密封高压釜,通入压力为2MPa、体积比为1:1的H2与CO混合气,80℃下搅拌2h,制备得到催化剂;
降温,加入1ml、浓度为3mol/L的1,3-丁二烯甲苯溶液,加压至4MPa,在80℃下搅拌反应12h,反应完成后,冷却到室温,释放未反应的气体,取出液体产物,通过气相色谱内标法测得1,3-丁二烯的转化率为99.2%,1,6-己二醛的选择性为53.2%。
反应完全后,在氮气保护下减压蒸馏除去溶剂、反应产物、未反应的原料等,剩下的残余物全部转移到反应釜。重复上述操作,加入同样量的溶剂、 1,3-丁二烯、合成气,在温度为80℃,搅拌反应12h。反应完成后分析产物, 1,3-丁二烯的转化率为99.0%,1,6-己二醛的选择性为53.1%。
重复上述操作,第二次循环,反应完成后分析产物,1,3-丁二烯的转化率为98.5%,1,6-己二醛的选择性为52.3%。
第三次循环,反应完成后分析产物,1,3-丁二烯的转化率为97.8%,1,6- 己二醛的选择性为51.8%。
第四次循环,反应完成后分析产物,1,3-丁二烯的转化率为96.8%,1,6- 己二醛的选择性为51.4%。
第五次循环,反应完成后分析产物,1,3-丁二烯的转化率为95.6%,1,6- 己二醛的选择性为50.7%。
本发明提供的铑基有机聚合物催化剂实现非均相催化1,3-丁二烯的氢甲酰化反应,从而有效解决催化剂回收、循环和污染等问题。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
3.根据权利要求1或2所述的方法,其特征在于,所述二齿膦配体单体与含有乙烯基的单体的摩尔比为1:(1-10)。
4.根据权利要求1-3任一项所述的方法,其特征在于,所述聚合反应的温度为60-100℃,时间为2-6h。
5.根据权利要求1-4任一项所述的方法,其特征在于,所述金属铑前驱体选自Rh(CO)2(acac)、Rh(AcO)2、RhCl3、Rh(NO3)3、RhH(CO)(PPh3)3、[Rh(CO)2Cl]2、RhH(CO)(PPh3)3、[Rh2(m-Cl)2(cod)2]、[Rh(cod)2]BF4中的一种或多种。
6.根据权利要求1或5所述的方法,其特征在于,所述金属铑前驱体与所述有机膦配体共聚物的质量比为(1:1)-(1:50)。
7.根据权利要求1或5所述的方法,其特征在于,所述金属铑前驱体与所述有机膦配体共聚物的质量比为(1:5)-(1:20)。
8.根据权利要求1-7任一项所述的方法,其特征在于,所述H2与CO的混合气的压力为1-10MPa,H2与CO的体积比为(1:10)-(10:1)。
9.根据权利要求1-8任一项所述的方法,其特征在于,所述金属铑前驱体与所述1,3-丁二烯的摩尔比为(1:50)-(1:50000)。
10.根据权利要求1-9任一项所述的方法,其特征在于,所述氢甲酰化反应的温度为50-150℃,时间为1-24h。
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