CN101041610B - 一种乙烯齐聚制备α-烯烃的方法 - Google Patents
一种乙烯齐聚制备α-烯烃的方法 Download PDFInfo
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- -1 phenyl pyridyl Chemical group 0.000 claims abstract description 12
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- 238000003756 stirring Methods 0.000 description 11
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- 239000012043 crude product Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明涉及一种用取代苯基吡啶基单亚胺和FeCl2·4H2O络合而成的催化剂催化乙烯齐聚制备线性α-烯烃的方法,特点是用取代苯基吡啶基单亚胺铁配合物与甲基铝氧烷混合做催化剂,Al/Fe摩尔比为500~3000,在40℃,4.5~5.0MPa,Fe浓度为1μmol/mL的条件下催化乙烯齐聚制备线性α-烯烃,催化活性大于3.0×106g乙烯·mol-1Fe·h-1,产物中C6~C10线性α-烯烃的质量百分含量>50%,线性α-烯烃的选择性>97%。
Description
技术领域
本发明涉及一种用取代苯基吡啶基单亚胺和FeCl2 4H2O络合而成的催化剂催化乙烯齐聚制备线性α-烯烃的方法。
技术背景
线性α-烯烃是指双键在分子术端的C4以上的直链烯烃。它在聚乙烯共聚单体、表面活性剂合成中间体、增塑剂用醇、合成润滑油和油品添加剂等领域有着广泛的应用。近年来,随着聚烯烃工业的不断发展,世界范围内对α-烯烃的需求量迅速增长。
工业上线性α-烯烃生产的方法主要有蜡裂解法、乙烯齐聚法、萃取分离法、脂肪醇脱氢法、内烯烃异构法、Alfene法等,其中,蜡裂解法、脂肪醇脱氢法已基本淘汰。内烯烃异构法、Alfene法以及Exxon公司的乙烯齐聚法也因技术、经济原因一直未工业化,萃取分离法用的也很少。1997年的资料统计表明:乙烯齐聚法生产的α-烯烃占整个α-烯烃生产总量的94.1%。可见,乙烯齐聚法是生产α-烯烃的一种非常重要的方法。目前生产线性α-烯烃比较典型的生产工艺有SHOP工艺(US patent 3686351,1972和US patent 3676523,1972)、Chevron工艺和Amoco工艺(Applied Homogeneous Catalysis with Organometallic Compounds.Vol.1,VCH Publishers,NewYork,1996:245~256)。
近年来,国外乙烯齐聚生产α-烯烃工艺催化剂的开发主要集中在镍系、锆系、铬系等催化剂上。Brookhart等人报道了阳离子Ni(II)-α,α′二胺络合物是有效的乙烯齐聚催化剂(Organometallics,1997,16:2005~2007)。专门用于乙烯三聚合成1-己烯的铬系催化剂也有很大的突破,已有多篇专利和文献报导(US5,523,507)。另外,UOP和Union Carbide两家公司于1992年联合进行Linear-1TM工艺开发,1997年完成中试验证。该工艺采用以特种配位体配合的均相催化体系,其中包括氯化镍、NaBH4及配位体2-二苯膦酰基1-萘磺酸,其直链α-烯烃收率几乎达100%。
1998年,Brookhart小组和Gibson小组几乎同时发现Fe(II)、Co(II)的三齿吡啶双亚配合物可催化乙烯齐聚,结构式如下:
这种催化剂催化乙烯齐聚的活性很高,而且线性α-烯烃的选择性也非常高(Brookhart,M等,J.Am.Chem.Soc.1998,120,7143;Gibson,V.C.等,J.Chem.Commun.1998,849)。这种三齿双亚胺配合物中,苯胺的一个邻位取代基一定为氢,其余的取代基可以为甲基、乙基、异丙基等供电子基团。
陈耀峰等(CN 1343664A,CN1142142C)发现上述结构的三齿配合物中,如果苯胺的一个邻位取代基为氢,而其它的取代基如果为卤素等吸电子基团,也可以同样催化乙烯齐聚,而且苯胺上带有吸电子基团的配合物催化乙烯齐聚同样具有很高的活性和线性α-烯烃的选择性。
WO0110875公开了一种包含2,6-二乙酰基吡啶配体的金属配合物及其在乙烯聚合反应中的应用。催化剂的结构式如下:
上述结构式中,R′和R″可以相同或不同,为氢、C1-10的烃基、卤素等。R1~R8可以相同或不同,为氢、卤素、C1-10的烃基,R1和R5为烃基,如甲基、乙基、异丙基等。该配体与Fe(II)、Fe(III)、Co(II)等金属络合,可用于催化乙烯均聚或共聚合。
但上述催化剂及工艺所合成的产物中,附加值低的丁烯-1选择性一般都很高(>15%),附加值高的己烯-1和辛烯-1选择性低,经济性不明显。
发明内容
本发明的目的是提供一种对附加值高的己烯-1,辛烯-1选择性高,而对附加值低的丁烯-1选择性低的乙烯齐聚制备α-烯烃的方法。
本发明所用的乙烯齐聚催化剂是一种结构式如下的取代苯基吡啶基单亚胺铁配合物:
上述结构式中,R1可为胺基、氰基、硝基、甲基、一氯代甲基。
本发明的催化剂,即上述结构的取代苯基吡啶基单亚胺铁配合物,是由取代苯基吡啶基单亚胺和FeCl2 4H2O在有机溶剂中或水中反应72小时得到,取代苯基吡啶基单亚胺配体与FeCl2 4H2O的摩尔比为1∶1,所用的有机溶剂是四氢呋喃。
齐聚反应是在高压反应釜中进行的,乙烯压力为:4.5~5.0MPa,齐聚反应温度为40℃,以甲苯为溶剂,以甲基铝氧烷为助催化剂,Fe浓度为1μmol/mL,Al/Fe摩尔比为500~3000,反应30分钟后,以10%的盐酸乙醇溶液终止反应。
发明人在研究中发现,本发明的催化剂用于乙烯齐聚,在指定的反应压力(4.5~5.0MPa)下,具有附加值高的己烯-1选择性高,辛烯-1选择性高,而附加值低的丁烯-1选择性低(<10%)的优点,而传统的乙烯齐聚催化剂丁烯-1选择性均高于15%。这主要是由于反应压力的增加(传统的乙烯齐聚反应压力为0~3.0MPa),乙烯在溶剂中的溶解能力有较明显的提高,同时链终止反应更容易在己烯-1和辛烯-1形成时发生,使丁烯-1选择性低,己烯-1选择性高,辛烯-1选择性高。
具体实施方式
实施例1
1.催化剂的制备
氮气保护下,在干燥的50mL三口烧瓶中加入2,6-二乙酰基吡啶(1.63g,10mmol)、缓慢滴加2-胺基苯胺(0.97g,9mmol),加入无水甲醇25mL,5滴无水甲酸,室温下搅拌反应48小时后,冷冻过滤,粗产物在甲醇中重结晶,得到浅黄色配体,产率69%。元素分析:C15H15N3O:计算值C,71.13;H,5.97,N,16.59。实测值C,71.31;H,6.07,N,16.49。
在氮气保护下,首先在反应器中加入0.21mmol上述配体与0.20mmolFeCl2·4H2O,开动搅拌。然后注入5mL四氢呋喃,在25℃下反应2h。反应结束后,将所得沉淀物过滤,用乙醚洗涤数次,得到深绿色固体催化剂(产率:60.2%)。
2.乙烯齐聚
500ml的高压釜加热到200℃抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,依次加入100mL的甲苯,11.43mL甲基铝氧烷(10%的甲苯溶液),搅拌2分钟后迅速加入100μmol主催化剂(Al/Fe摩尔比=500),在40℃和Fe浓度为1μmol/mL,5.0Mpa乙烯压力下进行齐聚反应,反应30min后用冰浴降温、卸压,用质量分数为10%的酸化乙醇终止反应。催化剂的活性通过产物的增重求得。
实施例2
1.催化剂的制备
氮气保护下,在干燥的50mL三口烧瓶中加入2,6-二乙酰基吡啶(1.63g,10mmol)、缓慢滴加2-甲基苯胺(0.96g,9mmol),加入无水甲醇25mL,5滴无水甲酸,室温下搅拌反应48小时后,冷冻过滤,粗产物在甲醇中重结晶,得到浅黄色配体,产率80%。1H-NMR(300M Hz,CDCl3):8.44(d,2H,Py-H);7.96(t,1H,Py-H);7.2(d,2H,Ar-H);7.1(t,2H,Ar-H);2.38(s,6H,N=CMe);2.07(s,3H,CH3)。元素分析:C16H16N2O:计算值C,76.16;H,6.39,N,11.10。
实测值C,75.81;H,6.47,N,11.09。
在氮气保护下,首先在反应器中加入0.21mmol上述配体与0.20mmolFeCl2·4H2O,开动搅拌。然后注入5mL四氢呋喃,在25℃下反应2h。反应结束后,将所得沉淀物过滤,用乙醚洗涤数次,得到深绿色固体催化剂。
2.乙烯齐聚
Al/Fe比为500,反应压力4.5MPa,其它条件同实施例1。
实施例3
1.催化剂的制备
氮气保护下,在干燥的50mL三口烧瓶中加入2,6-二乙酰基吡啶(1.63g,10mmol)、缓慢滴加2-氰基苯胺(1.06g,9mmol),加入无水甲醇25mL,5滴无水甲酸,室温下搅拌反应48小时后,冷冻过滤,粗产物在甲醇中重结晶,得到浅黄色配体,产率51%。
在氮气保护下,首先在反应器中加入0.21mmol上述配体与0.20mmolFeCl2·4H2O,开动搅拌。然后注入5mL四氢呋喃,在25℃下反应2h。反应结束后,将所得沉淀物过滤,用乙醚洗涤数次,得到深绿色固体催化剂。
2.乙烯齐聚
Al/Fe比为1000,反应压力4.5MPa,其它条件同实施例1。
实施例4
1.催化剂的制备
同实施例3。
2.乙烯齐聚
Al/Fe比为3000,其它条件同实施例1。
实施例5
1.催化剂的制备
氮气保护下,在干燥的50ml三口烧瓶中加入2,6-二乙酰基吡啶(1.63g,10mmol)、缓慢滴加2-氯甲基苯胺(1.27g,9mmol),加入无水甲醇25mL,5滴无水甲酸,室温下搅拌反应72小时后,冷冻过滤,粗产物在甲醇中重结晶,得到浅黄色配体,产率76%。
在氮气保护下,首先在反应器中加入0.21mmol上述配体与0.20mmolFeCl2·4H2O,开动搅拌。然后注入5mL四氢呋喃,在25℃下反应2h。反应结束后,将所得沉淀物过滤,用乙醚洗涤数次,得到深绿色固体催化剂。
2.乙烯齐聚
Al/Fe比为500,反应压力为4.5MPa,其它条件同实施例1。
实施例6
1.催化剂的制备
氮气保护下,在干燥的50ml三口烧瓶中加入2,6-二乙酰基吡啶(1.63g,10mmol)、缓慢滴加2-硝基苯胺(1.24g,9mmol),加入无水甲苯25mL,0.2gSilica-Aluminium catalyst support,室温下搅拌反应72小时后,过滤,滤液经减压蒸馏后得到粘稠状固体。粗产物在甲醇中重结晶,得到浅黄色配体,产率68%。
在氮气保护下,首先在反应器中加入0.21mmol上述配体与0.20mmolFeCl2·4H2O,开动搅拌。然后注入5mL四氢呋喃,在25℃下反应2h。反应结束后,将所得沉淀物过滤,用乙醚洗涤数次,得到深绿色固体催化剂(产率:71.2%)。
2.乙烯齐聚
Al/Fe比为500,反应压力为4.5MPa,其它条件同实施例1。
表1 乙烯齐聚结果汇总
R<sub>1</sub>基团 | 反应压力MPa | Al/Fe | 催化剂活性10<sup>7</sup>g/molcat.h | 丁烯-1选择性% | 己烯-1选择性% | 辛烯-1选择性% | α烯烃纯度% | |
实施例1 | NH<sub>2</sub> | 4.5 | 500 | 1.21 | 9.3 | 20.5 | 17.4 | 98.10 |
实施例2 | CH<sub>3</sub> | 5.0 | 2000 | 10.08 | 9.6 | 20.1 | 18.5 | 97.52 |
实施例3 | CN | 4.5 | 1000 | 0.81 | 10.7 | 19.2 | 19.2 | 98.66 |
实施例4 | CN | 5.0 | 3000 | 19.73 | 8.4 | 232 | 17.8 | 98.88 |
实施例5 | CH<sub>2</sub>Cl | 4.5 | 500 | 1.25 | 9.7 | 20.3 | 19.3 | 97.35 |
实施例6 | NO<sub>2</sub> | 4.5 | 500 | 0.92 | 7.7 | 24.3 | 17.8 | 98.21 |
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