CN1646453A - 烯烃的低聚方法 - Google Patents
烯烃的低聚方法 Download PDFInfo
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- CN1646453A CN1646453A CNA038080486A CN03808048A CN1646453A CN 1646453 A CN1646453 A CN 1646453A CN A038080486 A CNA038080486 A CN A038080486A CN 03808048 A CN03808048 A CN 03808048A CN 1646453 A CN1646453 A CN 1646453A
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- transition metal
- alkylaluminoxane
- metal complex
- described method
- oligomerization
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- 150000003624 transition metals Chemical class 0.000 claims abstract description 36
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- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/24—Catalytic processes with metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及使烯烃低聚的方法，根据该方法将烯烃与一种催化剂体系接触，该催化剂体系包含：a)至少一种具有一个多齿配体的过渡金属配合物，和b)烷基铝氧烷，其用量使得铝和过渡金属的摩尔比大于10，在该方法中至少部分用量的过渡金属配合物是在低聚反应期间连续或分批加入的。使用给定用量的烷基铝氧烷，该方法可以制备更高产量的烯烃低聚物。
Description
本发明涉及烯烃的低聚方法，其中将烯烃与一种催化剂体系接触，该催化剂体系包含至少一种具有多齿配体的过渡金属配合物和烷基铝氧烷。
具有多达30个碳原子的烯烃低聚物作为塑料的共聚单体或作为羰基合成醇的前体具有显著的经济重要意义，羰基合成醇进而又是用于塑料的表面活性剂和增塑剂的组分之一。因此，在例如蒸汽裂化室中进行低级烯烃的低聚反应的方法在日用品的制备中具有重要的中心地位。
WO 00/58319描述了一种使用低聚催化剂制备烯烃低聚物的方法，其中所述低聚催化剂可以由铬化合物和1，3，5-三氮杂环己烷以及活化添加剂例如烷基铝氧烷获得。
EP-A-0 537 609描述了乙烯在催化剂存在下的低聚反应，所述催化剂含有一种具有多齿配体的铬配合物和烷基铝氧烷。
虽然对于在过渡金属配合物上进行的烯烃低聚反应的机理还没有充分阐述清楚，但是据认定，过渡金属配合物被烷基铝氧烷“活化”涉及到配合物的可被夺取的配体与烷基铝氧烷的烷基之间的配体交换反应。这样生成一种催化活性物质，其以多步的方式加到烯烃分子上。烯烃分子在过渡金属配合物的配位层反应生成低聚物。低聚物的释放使催化活性物质获得再生。但是，即使是基本上除去杂质，催化剂体系的催化活性在经过一段时间后也会被耗尽。通常这样的催化剂体系随后就被废弃。
为了获得令人满意的活化作用，所用烷基铝氧烷通常相对于过渡金属配合物而言是明显过量的。因此，在上述烯烃低聚反应方法中，与此相关的烷基铝氧烷的高消耗意味着非常高的成本因素。
本发明目的在于提供一种烯烃的低聚方法，其中将烯烃与一种催化剂体系接触，该催化剂体系包含过渡金属配合物和烷基铝氧烷，这种方法可以使烷基铝氧烷得到最佳利用。
我们已经发现，上述目的可以通过烯烃的低聚方法得以实现，在该方法中将烯烃与一种催化剂体系接触，该催化剂体系包含
a)至少一种具有多齿配体的过渡金属配合物，和
b)烷基铝氧烷，其用量使得铝∶过渡金属的摩尔比大于10，其中至少部分用量的过渡金属配合物是在低聚反应期间连续或分批加入的。
适宜的烷基铝氧烷例如是由DE-A-3 007 725中已知的那些烷基铝氧烷，其结构并没有被阐明清楚。烷基铝氧烷是小心将烷基铝部分水解后的产物。这些产物显然不是纯化合物的形式，而是类型Ia和Ib的开链和环状结构的混合物，认为它们彼此处于动态平衡中。
在式Ia和Ib中，基团R是相同或不同的并且彼此独立地是C1-C12-烷基，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1，2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、异庚基、正辛基、正壬基、正癸基和正十二烷基；优选C1-C6-烷基例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1，2-二甲基丙基、异戊基、正己基、异己基。甲基铝氧烷是特别优选的。m是0-40的整数，优选为0-25的整数，特别优选为0-22的整数。
类似笼结构的铝氧烷也已经在文献(参见Organometallics 1996，15，第2213-26页；Makromol.Symp.1995，97，第15-25页)中论及。
无论它们的结构性质如何，烷基铝氧烷适合用于本发明的目的。
过渡金属配合物可以是在活化之后能使烯烃低聚的任意配合物。这种类型的适宜催化剂描述在“Frontiers in metal-catalyzed Polymerization”，Chem.Rev.2000年4月，第100卷，第4期，第1167-1645页中。在优选的配合物中，过渡金属选自铬、钒、钽和钛。
适宜的过渡金属配合物可以用通式LMeXk表示，其中Me是过渡金属，优选Cr、V或Ti，L是多齿配体，X是相同或不同的阴离子，k是2或3。
在八面体配位金属原子中，多齿配体优选占据三个相邻的配位位置。含氮多齿配体是优选的。特别优选的是环状多胺配体，特别是具有1，3，5-三氮杂环己烷或1，4，7-三氮杂环壬烷骨架的那些环状多胺配体。
具有1，3，5-三氮杂环己烷骨架的适宜配体描述在WO 00/58319中，其内容在此引入作为参考。在这些配体中，优选的是其中各氮原子彼此独立地被取代或未取代的C1-C12-烷基、C6-C15-芳基或C7-C15-芳烷基所取代的1，3，5-三氮杂环己烷，这些取代基是例如甲基、乙基、N，N-二甲基氨基乙基、正丙基、正丁基、叔丁基、己基、辛基、十二烷基、1，1-二甲基十二烷基或1-苯基乙基。
优选的1，3，5-三氮杂环己烷是1，3，5-三叔丁基-1，3，5-三氮杂环己烷、1，3，5-三乙基-1，3，5-三氮杂环己烷、1，3，5-三[(1-苯基乙基)]-1，3，5-三氮杂环己烷、1，3，5-三[(1，1-二-甲基)十二烷基]-1，3，5-三氮杂环己烷和1，3-二-正十二烷基-5-[2-(N，N-二甲基氨基)乙基]-1，3，5三氮杂环己烷，特别优选的是1，3，5-三正辛基-1，3，5-三氮杂环己烷、1，3，5-三正十二烷基-1，3，5-三氮杂环己烷、1，3，5-三苄基-1，3，5-三氮杂环己烷、1，3，5-三(2-乙基己基)-1，3，5-三氮杂环己烷、1，3，5-三(2-正丙基庚基)-1，3，5-三氮杂环己烷。
适宜的1，4，7-三氮杂环壬烷在氮原子上可以被上述取代基所取代。1，4，7-三甲基-1，4，7-三氮杂环壬烷是商业上可得到的。
可替代使用的多齿配体是式C5H(5-u)Ru的环戊二烯基阴离子及其苯并稠合衍生物，其中n是0-5的整数，R是C1-C6-烷基、C2-C6-链烯基、C6-C10-芳基、C7-C14-芳烷基、R1 2p-X-或R1 2N-X-，其中R1是C1-C6-烷基、C5-C6-环烷基或C6-C10-芳基，X是C1-C6-亚烷基。n优选是1。适宜的环戊二烯基配体例如是2-二(C1-C6-烷基)膦基乙基环戊二烯基、3-二(C1-C6-烷基)膦基丙基环戊二烯基、2-二(C1-C6-烷基)氨基乙基环戊二烯基、叔丁基环戊二烯基或2-苯基丙-2-基环戊二烯基。
其它可替代使用的多齿配体是下式的二(N-甲基咪唑-2-基)化合物
其中R2是氢、C1-C6-烷基或C1-C6-烷氧基，Y是N-甲基咪唑-2-基、R1 2P-X-或R1 2N-X-，其中R1是C1-C6-烷基、C5-C6-环烷基或C6-C10-芳基，X是C1-C6-亚烷基。
适宜的阴离子X特别是卤离子，例如氟离子、溴离子、碘离子，特别是氯离子；甲苯磺酸根、三氟甲苯磺酸根、四氟硼酸根、六氟磷酸根、六氟锑酸根、四苯基硼酸根；C1-C18-羧酸根例如乙酸根、丁酸根、新戊酸根、月桂酸盐、硬脂酸根或2-乙基己酸根。
过渡金属配合物可以通过本领域熟练技术人员已知的方法或者通过类似于这些的方法(例如W.A.Herrmann，A.Salzer：“Synthetic Methods ofOrganometallic and Inorganic Chemistry”，Thieme Verlag，Stuttgart 1996)获得。适宜的配合物描述在WO 00/58319、EP-A-0 537 609、Rüther，T.等人，Organometallic 2001，20，第1247-1250页；Dhring A.等人，Organometallic 2001，20，第2234-2245页和Deckers P.J.W.等人，Angew.Chem.2001，113，第13期，第2584-2587页。
过渡金属配合物和烷基铝氧烷的用量使得铝∶过渡金属的摩尔比大于10，例如在10-10000之间，优选在10-500之间。根据本发明，所使用的至少部分用量的过渡金属配合物是在低聚反应期间连续加入或分批加入的，也就是说，在烯烃、烷基铝氧烷和部分用量的配合物已经在发生烯烃低聚反应的条件下进行过接触后加入。通常，在使用低聚反应之前将全部用量的烷基铝氧烷与部分用量的配合物迅速就地混和。要进行低聚的烯烃可以相似地在开始的时候加入和/或连续或分批地加入至混合的催化剂组分中。作为替代方式，还可以在开始时将铝氧烷和烯烃引入，同时加入第一部分用量的过渡金属配合物。
在低聚反应期间，有利地是，当催化剂体系的活性被显著破坏时，例如至少30分钟或1小时后，可以加入另一部分用量的过渡金属配合物至聚合体系中。该步骤通常可以按照需要重复进行，只要过渡金属配合物的总量(也就是最初引入的和随后加入的部分用量之和)和存在于催化剂体系中的烷基铝氧烷用量所对应的铝∶过渡金属的摩尔比大于10即可。
在优选实施方案中，部分用量的过渡金属配合物最初与烷基铝氧烷一起引入，并且通过在低聚反应期间加入至少另一部分用量的过渡金属配合物，使铝∶过渡金属的摩尔比降低至小于初始值的一半。铝∶过渡金属的最初摩尔比大于100是有利的，优选大于200，特别是大于300。例如为了在相对长的时间段内获得高的催化剂活性，代替分批加入铬配合物，在低聚反应期间该过渡金属配合物还可以连续计量地加入。
当使用给定用量的铝氧烷时，使用本发明的方法使得能够获得显著更高收率的烯烃低聚物。
本发明的方法通常在液相中在溶剂中进行。适宜的溶剂是非质子溶剂，例如脂肪族饱和烃例如丁烷、戊烷、3-甲基戊烷、己烷、庚烷、2-甲基己烷、辛烷、环己烷、甲基环己烷、2，2，4-三甲基戊烷、十氢萘；卤代烃例如二氯乙烷；芳香族烃例如苯、甲苯、二甲苯、乙苯、均三甲苯、四氢萘或者在反应条件下为液体的低聚反应产物，例如1-己烯。这些溶剂可以单独使用或者混合使用。
本发明的方法适合乙烯的低聚的反应，特别适合乙烯的选择性三聚反应。本发明的方法还适合具有至少3个碳原子、例如3-12个碳原子的α-烯烃例如1-丙烯、1-丁烯、1-己烯、1-癸烯的聚合反应，特别适合这些烯烃的选择性三聚反应。特别有用的烯烃是1-丁烯，如果需要的话，可以是与其存在于例如残液II中的异构体的混合物。
由于烷基铝氧烷容易水解，本发明的方法通常在基本上无水分的环境中进行。优选在保护性气体中进行。可以使用的保护性气体是在反应条件下呈化学惰性的任意气体，例如氮气或氩气。另外，如果要反应的烯烃在反应条件下具有足够高的蒸汽压，则它本身就可以起到保护性气体的作用。
低聚反应优选在0-120℃下进行，特别是在25-110℃下进行。该反应在大气压至120巴的压力下进行。
反应完成后，通常将催化剂体系钝化。适宜的钝化剂例如是水(其可以被酸化)和低级醇。低聚反应的产物有利地通过蒸馏进行纯化。未反应的起始原料可以回收并将其返回至反应中。
通过下面的实施例对本发明进行阐述。
实施例
在40℃下，在氩气氛下，将42.1μmol(1，3，5-三-正十二烷基-1，3，5-三氮杂环己烷)CrCl3与250ml甲苯投入至安装有接触式温度计、搅拌器、加热套和气体入口管的1升四颈烧瓶中。溶液用丁烯饱和。然后，以1.6M的甲苯溶液形式加入14.74mmol甲基铝氧烷(MAO)，所对应的铝∶铬摩尔比为350。使1-丁烯从加入MAO后获得的浅绿/黄色溶液中通过。1小时后，再加入40.2μmol铬配合物，这样此时的铝∶铬摩尔比达到180。再过1小时后，再次加入40.5μmol铬配合物，此时的铝∶铬摩尔比达到120。总共3小时后，通过加入15ml溶于50ml甲醇中的浓盐酸，停止反应，反应混合物再搅拌15分钟。然后，加入250ml甲醇，再将混合物搅拌15分钟。产物用水洗涤三次并在硫酸钠中干燥。通过气相色谱分析所得到的溶液，测定十二碳烯的收率。总共生成25.8g十二碳烯。
比较实施例
在40℃下，将40.9μmol(1，3，5-三-正十二烷基-1，3，5-三氮杂环己烷)CrCl3与250ml甲苯投入至安装有接触式温度计、搅拌器、加热套和气体入口管的1升四颈烧瓶中。溶液用丁烯饱和。然后，以1.6M的甲苯溶液形式加入14.32mmol甲基铝氧烷(MAO)，所对应的铝∶铬摩尔比为350。使1-丁烯通过该溶液。1小时后，十二碳烯产量显著降低。如前面实施例所述那样进行后处理。得到10.2g十二碳烯。
Claims (7)
1.一种使烯烃低聚的方法，其中将烯烃与一种催化剂体系接触，该催化剂体系包含
a)至少一种具有多齿配体的过渡金属配合物，和
b)烷基铝氧烷，其用量使得铝∶过渡金属的摩尔比大于10，
其中至少部分用量的过渡金属配合物是在低聚反应期间连续或分批加入的。
2.权利要求1所述的方法，其中部分用量的过渡金属配合物最初与烷基铝氧烷一起引入，并且通过加入至少另一部分用量的过渡金属配合物使铝∶过渡金属的摩尔比降低至小于初始值的一半。
3.权利要求2所述的方法，其中铝∶过渡金属的初始摩尔比大于100。
4.前述权利要求任意一项所述的方法，其中过渡金属是铬。
5.前述权利要求任意一项所述的方法，其中配体是多齿含氮配体。
6.权利要求5所述的方法，其中配体包含1，3，5-三氮杂环己烷或1，4，7-三氮杂环壬烷骨架。
7.前述权利要求任意一项所述的方法，其中所述烷基铝氧烷是甲基铝氧烷。
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| CN106565618A (zh) * | 2016-10-10 | 2017-04-19 | 常州大学 | 一种由α‑烯烃直接合成润滑油基础油的催化剂配体及其配合物以及制备方法和应用 |
| CN109563009A (zh) * | 2016-07-15 | 2019-04-02 | 公共型股份公司希布尔控股 | 烯烃低聚方法 |
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| EP1681279A4 (en) * | 2003-11-05 | 2009-04-22 | Sumitomo Chemical Co | PROCESS FOR THE PREPARATION OF 1-HEXES |
| JP2005152889A (ja) * | 2003-11-06 | 2005-06-16 | Sumitomo Chemical Co Ltd | オレフィンの三量化触媒およびその触媒を用いたオレフィンの三量化方法 |
| JP4991691B2 (ja) * | 2005-03-09 | 2012-08-01 | エクソンモービル・ケミカル・パテンツ・インク | オレフィンのオリゴマー化 |
| US7414006B2 (en) * | 2005-03-09 | 2008-08-19 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
| US7982085B2 (en) * | 2006-02-03 | 2011-07-19 | Exxonmobil Chemical Patents Inc. | In-line process for generating comonomer |
| US8003839B2 (en) * | 2006-02-03 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Process for generating linear apha olefin comonomers |
| WO2007092136A2 (en) * | 2006-02-03 | 2007-08-16 | Exxonmobil Chemical Patents, Inc. | Process for generating alpha olefin comonomers |
| US8404915B2 (en) * | 2006-08-30 | 2013-03-26 | Exxonmobil Chemical Patents Inc. | Phosphine ligand-metal compositions, complexes, and catalysts for ethylene trimerizations |
| US20110207977A1 (en) * | 2008-11-04 | 2011-08-25 | Idemitsu Kosan Co., Ltd. | Method for producing a-olefin oligomer, a-olefin oligomer, and lubricating oil composition |
| CN102030843B (zh) * | 2010-11-04 | 2012-05-30 | 中国石油天然气股份有限公司 | 烯烃聚合非茂金属催化剂体系及其制备与应用 |
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| DE3007725A1 (de) | 1980-02-29 | 1981-09-17 | Hansjörg Prof. Dr. 2000 Hamburg Sinn | Verfahren zur herstellung von polyethylen, polypropylen und copolymeren |
| JPH06254402A (ja) * | 1991-09-05 | 1994-09-13 | Mitsui Petrochem Ind Ltd | α−オレフィンのオリゴメリゼーション触媒およびα−オレフィンのオリゴメリゼーション法 |
| US5744677A (en) | 1991-10-16 | 1998-04-28 | Amoco Corporation | Ethylene oligomerization |
| SG99843A1 (en) | 1992-09-17 | 2003-11-27 | Mitsubishi Chem Corp | Method for oligomerizing an alpha-olefin |
| US5856612A (en) | 1996-02-02 | 1999-01-05 | Mitsubishi Chemical Corporation | Process for producing α-olefin oligomer |
| DE19943544A1 (de) * | 1999-09-11 | 2001-03-15 | Basf Ag | Oligomerisierungskatalysator |
| EP1305271B1 (en) | 2000-08-03 | 2009-03-04 | E.I. Du Pont De Nemours And Company | Continuous manufacturing process for alpha-olefins |
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- 2003-04-09 US US10/509,871 patent/US7214842B2/en not_active Expired - Fee Related
- 2003-04-09 WO PCT/EP2003/003691 patent/WO2003084902A1/de active Application Filing
- 2003-04-09 AU AU2003227586A patent/AU2003227586A1/en not_active Abandoned
- 2003-04-09 CN CNB038080486A patent/CN1263712C/zh not_active Expired - Fee Related
- 2003-04-09 JP JP2003582101A patent/JP4086159B2/ja not_active Expired - Fee Related
- 2003-04-09 EP EP03724987A patent/EP1497244A1/de not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109563009A (zh) * | 2016-07-15 | 2019-04-02 | 公共型股份公司希布尔控股 | 烯烃低聚方法 |
| CN106565618A (zh) * | 2016-10-10 | 2017-04-19 | 常州大学 | 一种由α‑烯烃直接合成润滑油基础油的催化剂配体及其配合物以及制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050165266A1 (en) | 2005-07-28 |
| CN1263712C (zh) | 2006-07-12 |
| AU2003227586A1 (en) | 2003-10-20 |
| US7214842B2 (en) | 2007-05-08 |
| KR20040097307A (ko) | 2004-11-17 |
| JP4086159B2 (ja) | 2008-05-14 |
| JP2005526823A (ja) | 2005-09-08 |
| WO2003084902A1 (de) | 2003-10-16 |
| DE10215754A1 (de) | 2003-10-30 |
| EP1497244A1 (de) | 2005-01-19 |
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