CN1094389C - 新的含镍催化组合物和烯烃二聚和齐聚的方法 - Google Patents
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Abstract
本发明涉及催化组合物和烯烃的二聚、共二聚或齐聚的方法,所述组合物由至少一种含两个叔膦分子的二价镍复合物、至少一种既不含水也不含膦的镍复合物、和至少一种烷基铝卤化物的混合物组成。这种混合物特别是以溶于离子型非水液态组合物中的形式得以使用,如那些通过季铵卤化物和/或季鏻卤化物和卤化铝和/或烷基铝卤化物形成的组合物。
Description
本发明涉及新的催化组合物和烯烃(特别是丙烯)的二聚、共二聚或齐聚的方法。这种组合物包括至少一种含二分子叔膦的二价镍复合物、和至少一种不含膦的二价镍复合物的混合物。这些混合物特别是以溶于离子型液态组合物的形式得以使用,如通过季胺卤化物和/或季鏻卤化物和卤化铝和/或烷基铝卤化物和任选的芳烃形成的组合物。
大家知道,正如G.Wilke等在“Ind.Eng.Chem,1970,62,No12p.34”和英国专利GB-A-1410430中所述的那样,在催化二聚时与镍键合的膦的磷原子上的取代基的性质对烯烃分子、特别是对丙烯的链增长具有相当大的影响。G.Wilke使用了含一个单膦的镍的仲烯丙基复合物来催化二聚过程。这些复合物很难制备,且相当不稳定,对水和湿度敏感。因此,该发明从未付诸于实际应用。
已通过各种方法将膦导入催化剂中。特别是由二价镍盐和二当量的叔膦形成的复合物和烷基铝卤化物一起被用作烯烃特别是丙烯的二聚催化剂。这些复合物的优点是易于制备、在空气中稳定、而且也易于使用。这些化合物的问题是每个镍原子要用二分子的膦,而实际上单分子就足以达到所需的效果。更成问题的是烷基膦很昂贵,而且过量膦对反应速率有不利影响。
现在我们发现,(最好一当量的)至少一种含二分子叔膦的二价镍复合物与(最好一当量的)至少一种既不含水也不含膦的镍化合物和至少一种烷基铝卤化物的混合物能制备得到更具活性的稳定的催化剂,它对具更多支链的异构体的选择性高,可等同于单个含二分子膦的复合物获得的选择性。所述的催化剂还便宜得多。
更确切地说,本发明提供了一种专门用于烯烃二聚成齐聚的催化组合物,它包括至少一种烷基铝卤化物、至少一种含二分子叔膦的二价镍复合物和至少一种既不含水也不含膦的二价镍化合物。
本发明还提供烯烃的二聚、共二聚或齐聚的方法,其中至少有一种烯与上述的催化组合物接触。这种混合物最好至少部分溶解于离子型非水介质中。
两种类型的镍化合物的混合物必须和烷基铝卤化物一起使用。这种混合物可以按常规使用,即在没有溶剂的情况下使用,或者在卤代烃或非卤代烃的存在下使用。它可溶解于称为“熔融盐”的离子型非水液态组合物中使用,例如来自于季铵卤化物和/或季鏻卤化物与通过诸如烷基铝二卤化物等卤化铝和烷基铝卤化物同诸如在美国专利US-A-5104840所述的任一种三卤化铝形成的一组化合物中选出的一种铝化合物的接触得到的组合物。
按照本发明的含两个膦分子的镍复合物的通式为NiX2,2(叔膦),这里X代表氯、溴、碘、硝酸根或醋酸根阴离子,X2代表硫酸根阴离子。本发明的膦的通式为PR1R2R3或R1R2P-R1-PR1R2,这里R1、R2和R3可相同也可不同,代表含1至10个碳原子的烷基、环烷基、芳基或芳烷基、R1代表含1至6个碳原子的二价脂族其余部分。
可以举出下列例子:
三异丙基膦,
三环己基膦,
三苄基膦,
二环己基苯基膦,
四环己基亚甲基二膦、
二异丙基叔丁基膦。
按照本发明可用的含两个膦分子的镍复合物的实例有NiCl2,2P(异丙基)3和NiCl2,2P(环己基)3。
不含膦的镍化合物是溶剂化或非溶剂化的不含水的二价镍盐,通式为NiX2Lx,这里X代表氯、溴、碘、硝酸根或羧酸根阴离子,X2代表硫酸根阴离子,L代表含氧或含氮的化合物,如醚、酯、氨、伯、仲或叔胺、或含一个或多个相同或不同杂原子的杂环,x值为0、2或4。
不含膦的镍化合物的例子有NiCl2;NiCl22吡啶,NiCl2,二甲氧基乙烷;NiCl2,4NH3;醋酸镍;和辛酸镍等复合物。
按照本发明的铝的有机衍生物的通式为AlRxX3-x,这里R是含2至8个碳原子的直链或支链烷基,X代表氯或溴,x为值1、2或3。其例子有二氯乙基铝,乙基铝倍半氯化物,异丁基铝倍半氯化物,二氯异丁基铝和氯二乙基铝。所用的铝化合物量为使铝∶镍摩尔比达到2∶1至100∶1,最好是达到5∶1至50∶1。
含两个叔膦分子的二价镍复合物和既不含水也不含膦的二价镍化合物的比值(以Ni当量计)为0.1至10,最好为0.8至2。该比值以0.8至1.2为佳,等于成近于1则更有利。
在本发明的组合物中所含的化合物可在烃类或诸如氯苯或二氯甲烷卤代烃类溶剂、在烯烃二聚或齐聚产物中,或最好在离子型非水液态媒介物中以任意顺序混合。
通过简单接触并紧接着搅拌成均匀液体就可制成混合物。该过程在无空气的情况下进行,最好是在一种烯烃的存在下进行。
可在其中进行反应的离子型非水液态媒介物的例子有:
a)季铵和/或季鏻卤化物,特别是氯化物和溴化物;
b)卤化铝和/或烷基铝卤化物(三氯化物或三溴化物),
c)可选地并最好有一种简单的、缩合的或取代的芳烃存在
d)一种可选的有机铝衍生物。
所用的季铵卤化物和季鏻卤化物,最好其通式为NR1R2R3R4X和PR1R2R3R4X,这里X代表Cl或Br,R1、R2、R3和R4可相同或不同,代表氢或含1至12个碳原子的脂链(饱和或不饱和)或芳烷基。卤化铵或/和卤化鏻也可以是含1,2或3个氮和/或磷原子的含氮或磷的杂环衍生物。其例子有氯化四丁基鏻,氯化N-丁基吡啶鎓,溴化乙基吡啶鎓,氯化3-丁基-1-甲基咪唑鎓,氯化二乙基吡唑鎓,盐酸吡啶和氯化三甲苯铵。
可以通过本发明的催化组合物进行二聚、共二聚或齐聚的烯烃一般含2至10个碳原子。最好它们是诸如乙烯、丙烯、正丁烯和正戊烯等α-烯烃。这种烯烃可以单独存在或者存在于混合物中,可以是纯烯烃或者是含例如烷烃等稀释物,正象在诸如催化裂化或蒸汽裂化等炼油过程中的“馏分”中所发现那样。
烯烃的催化二聚、共二聚或齐聚可以采用含一个或多个反应阶段的封闭式、半封闭式或连续式方法进行。反应温度为-40℃至+70℃,最好是在-20℃和+50℃之间。反应产生的热可用本领域技术人员所熟知的方法消除。压力可以从常压或负压至20MPa,最好是在常压和5MPa之间。反应产物和未反应的反应物和催化系统分离开。最好反应过程在离子型非水介质中进行,反应产物和剩余反应物通过简单的滗析然后分馏而分离。
下面的实施例用来说明本发明的情况,但并不限定本发明的范围。
实施例1
将带有温度测量装置、保证足够搅拌的磁力棒和冷却液循环的双夹层的100ml玻璃反应器中的空气和水分清除掉,充之以99%纯丙烯并维持在常压下。加入22mg(0.05mmol)的NiCl2,2P(异丙基)3复合物和14mg(0.05mmol)的NiCl2·2吡啶化合物,将温度降至-15℃。用注射器加入3.5ml由0.1mol氯化丁基甲基咪唑翁,0.122mol升华的氯化铝,0.002mole二氯乙基铝和0.03mole异杜烯构成的液态组合物。开始进行搅拌,同时可观察到丙烯立即被吸收。当反应器的四分之三被充满时,停止搅拌,让“熔融盐”沉降下来,提取出烃相的主要部分。重复该操作六次。届时消耗掉总数为300g的丙烯。不同馏分的分析表明它们包含75%的二聚体、22%的三聚体和3%的四聚体。在所有馏分中的二聚体组成实际上均是一样的,包括81%的2,3-二甲基丁烯,2%的正己烯和17%的2-甲基戊烯。
实施例1′(比较)
除了用0.1mmol的NiCl2,2P(异丙基)3复合物,同时不用NiCl2,2吡啶化合物外,一切同于实施例1。除了异丙烯的被转化量只有240g外,其它所获结果均一致。
实施例2
除了液态组合物中的异杜烯用甲苯代替外,一切同于实施例1。进行了六次提取,相当于导入了325g丙烯。每次提取后加入0.2ml甲苯。六次提取物均由78%的二聚体、19%的三聚体和3%的四聚体构成。二聚体包括83%的2,3-二甲基丁烯,20%的正己烯和15%的2-甲基戊烯。
实施例3
除了用同量的NiCl2,2P(丁基)3复合物代替NiCl2,2P(异丙基)3复合物并将反应温度设在+5℃外,一切同于实施例1。当反应器的四分之三充满液体时,停止搅拌,让“熔融盐”沉降并提取出大部分的烃相组分。重复该操作七次。届时共导入了408g丙烯。不同馏分的分析表明每次提取的物质均由89%的二聚体、8%的三聚体和30%的四聚体组成。所有提取物(馏分)中的二聚体组成实际上是一致的,均含31%的2,3-二甲基丁烯,5%的正己烯和64%的2-甲基戊烯。
Claims (19)
1.一种催化组合物,它由至少一种烷基铝卤化物、至少一种含二分子叔膦的二价镍复合物和至少一种既不含水也不含膦的二价镍化合物的混合物组成。
2.按照权利要求1的催化组合物,其中铝∶镍摩尔比是2∶1至100∶1之间。
3.按照权利要求2的催化组合物,其中铝∶镍摩尔比是5∶1至50∶1之间。
4.按照权利要求1的催化组合物,其中含两个膦分子的镍复合物的通式为:NiX2,2(叔膦),这里X代表氯、溴、碘、硝酸根或醋酸根阴离子,X2代表硫酸根阴离子。
5.按照权利要求1的催化组合物,其中叔膦选自三异丙基膦、三环己基膦、三苄基膦、二环己基苯基膦、四环己基亚甲基二膦和二异丙基叔丁基膦。
6.按照权利要求1的催化组合物,其中含膦的复合物选自NiCl2,2P(异丙基)3和NiCl2,2P(环己基)3。
7.按照权利要求1的催化组合物,其中不含膦的镍化合物的通式为NiX2Lx,这里X代表氯、溴、碘、硝酸根或羧酸根阴离子,X2代表硫酸根阴离子,L代表含氧或含氮的化合物,如醚、酯、氨、伯胺、仲胺或叔胺,或含一个或多个相同或不同杂原子的杂环,值为0、2或4。
8.按照权利要求7的催化组合物,其中不含膦的镍化物选自NiCl2;NiCl2,2吡啶;NiCl2,二甲氧基乙烷;NiCl2,4NH3,醋酸镍和辛酸镍。
9.按照权利要求1的催化剂组合物,其中有机铝化合物选自二氯乙基铝、二氯异丁基铝、氯二乙基铝、乙基铝倍半氯化物和二异丁基铝倍半氯化物。
10.按照权利要求1的催化组合物,其中含两个叔膦分子的二价镍复合物与既不含水也不含膦的二价镍化合物的以镍的当量计的比值在0.1和10之间。
11.按照权利要求10的催化组合物,其中含两个叔膦分子的二价镍复合物与既不含水也不含膦的二价镍化合物的以Ni的当量计的比值在0.8和2之间。
12.按照权利要求11的催化组合物,其中含两个叔膦分子的二价镍复合物与既不含水也不含膦的二价镍化合物的以Ni的当量计的比值在0.8至1.2之间。
13.按照权利要求12的催化组合物,其中含两个叔膦分子的二价镍复合物与既不含水也不含膦的二价镍化合物的以Ni的当量计的比值为1。
14.按照权利要求1的催化组合物,其中所述混合物至少部分溶解在离子性非水介质中。
15.按照权利要求1的催化组合物,其中所述混合物至少部分溶解在包含至少一种季铵卤化物和/或一种季鏻卤化物和至少一种选自烷基铝卤化物和卤化铝的铝化合物的离子性非水溶剂中。
16.按照权利要求1-15中任一项的催化组合物,它是通过将至少一种含两个叔膦分子的二价镍复合物与至少一种既不含水也不含膦的二价镍化合物混合,然后再与至少一种烷基铝卤化物混合而得到的。
17.按照权利要求16的催化组合物,它含有芳香烃。
18.烯烃的二聚、共二聚或齐聚的方法,其中使至少一种烯烃与权利要求1-7中任一种催化组合物接触。
19.按照权利要求18的方法,其中至少一种α-烯烃与催化组合物接触。
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CN (1) | CN1094389C (zh) |
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FR2804622B1 (fr) * | 2000-02-04 | 2002-04-05 | Inst Francais Du Petrole | Composition catalytique pour la dimerisation, la codimerisation et l'oligomerisation des olefines |
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FR2806644B1 (fr) * | 2000-03-23 | 2002-05-10 | Inst Francais Du Petrole | Composition catalytique et procede pour la catalyse de dimerisation, de codimerisation et d'oligomerisation des olefines |
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US7259284B2 (en) * | 2000-05-31 | 2007-08-21 | Chevron Phillips Chemical Company, Lp | Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts |
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WO2003040264A1 (en) * | 2001-11-06 | 2003-05-15 | Extractica, Llc | Method for extraction of organosulfur compounds from hydrocarbons using ionic liquids |
FR2835521B1 (fr) * | 2002-02-04 | 2004-04-09 | Inst Francais Du Petrole | Composition catalytique contenant un aluminoxane pour la dimerisation, la co-dimerisation et l'oligomerisation des olefines |
RU2004133895A (ru) * | 2002-04-22 | 2005-06-10 | Шеврон Филлипс Кемикал Компани Лп (Us) | Способ получения поли-альфа-олефинов с использованием ионных жидких катализаторов |
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FR2880018B1 (fr) | 2004-12-27 | 2007-02-23 | Inst Francais Du Petrole | Production de propylene mettant en oeuvre la dimerisation de l'ethylene en butene-1, l'hydro-isomerisation en butene-2 et la metathese par l'ethylene |
US7732651B2 (en) * | 2006-06-01 | 2010-06-08 | Chevron Oronite Company, Llc | Method of making an alkylated aromoatic using acidic ionic liquid catalyst |
US8779228B2 (en) | 2008-11-19 | 2014-07-15 | Basf Se | Oligomerisation of olefins |
JP2013103218A (ja) * | 2011-11-17 | 2013-05-30 | Petroleo Brasileiro Sa | オリゴマー化反応用クロム及びニッケル触媒と前記触媒を使ったアルファ−オレフィンを得る方法 |
FR2984311B1 (fr) * | 2011-12-20 | 2015-01-30 | IFP Energies Nouvelles | Procede de production d'octenes mettant en oeuvre la dimerisation de l'ethylene en butenes et la dimerisation des butenes en octenes |
FR3007761B1 (fr) * | 2013-06-28 | 2016-02-05 | IFP Energies Nouvelles | Nouveau complexe a base de nickel et son utilisation dans un procede d'oligomerisation des olefines |
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FR3039431B1 (fr) * | 2015-07-29 | 2019-05-31 | IFP Energies Nouvelles | Nouvelle composition catalytique a base de nickel et d'un ligand de type phosphine complexe au nickel et son utilisation dans un procede d'oligomerisation des olefines |
FR3045414B1 (fr) * | 2015-12-18 | 2019-12-27 | IFP Energies Nouvelles | Nouvelle composition catalytique a base de nickel et de ligand de type phosphine et d'une base de lewis et son utilisation dans un procede d'oligomerisation des olefines |
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- 1994-09-13 EP EP94402045A patent/EP0646413B1/fr not_active Expired - Lifetime
- 1994-09-21 US US08/309,703 patent/US5502018A/en not_active Expired - Lifetime
- 1994-09-22 JP JP22748794A patent/JP4168099B2/ja not_active Expired - Lifetime
- 1994-09-22 CA CA002132700A patent/CA2132700A1/fr not_active Abandoned
- 1994-09-22 CN CN94116414A patent/CN1094389C/zh not_active Expired - Lifetime
- 1994-09-22 TW TW083108754A patent/TW287175B/zh active
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US5332708A (en) * | 1992-11-23 | 1994-07-26 | Phillips Petroleum Company | Catalyst compositions and catalytic processes |
CN1091999A (zh) * | 1992-11-23 | 1994-09-14 | 菲利浦石油公司 | 催化剂组合物和催化工艺 |
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DE69423165D1 (de) | 2000-04-06 |
TW287175B (zh) | 1996-10-01 |
KR950007942A (ko) | 1995-04-15 |
CA2132700A1 (fr) | 1995-03-23 |
JPH07171404A (ja) | 1995-07-11 |
US5550304A (en) | 1996-08-27 |
EP0646413A1 (fr) | 1995-04-05 |
US5502018A (en) | 1996-03-26 |
EP0646413B1 (fr) | 2000-03-01 |
JP4168099B2 (ja) | 2008-10-22 |
DE69423165T2 (de) | 2000-07-06 |
CN1109065A (zh) | 1995-09-27 |
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