CN113814001B - 一种乙烯低聚催化剂及其制备方法与应用 - Google Patents
一种乙烯低聚催化剂及其制备方法与应用 Download PDFInfo
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- CN113814001B CN113814001B CN202111120295.2A CN202111120295A CN113814001B CN 113814001 B CN113814001 B CN 113814001B CN 202111120295 A CN202111120295 A CN 202111120295A CN 113814001 B CN113814001 B CN 113814001B
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- dichromium
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- organic acid
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- oligomerization catalyst
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 53
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 62
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 diacetate chromite Chemical compound 0.000 claims abstract description 33
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 9
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- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 claims description 5
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- PMUMWUZNNMTLHF-UHFFFAOYSA-K chromium(3+) acetate dichloride Chemical compound [Cl-].C(C)(=O)O[Cr+2].[Cl-] PMUMWUZNNMTLHF-UHFFFAOYSA-K 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明提供了一种乙烯低聚催化剂及其制备方法与应用,制备所述乙烯低聚催化剂的原料包括二铬有机酸盐、配体、给电子体和助催化剂。本发明使用比较廉价易得的具有金属‑金属四重键结构的二铬盐二乙酸亚铬作为合成有机二铬酸盐的原料。本发明的低聚催化剂优选使用比较容易配位的2,5‑二甲基吡咯作为催化剂配体,保证催化剂形成合理的空间结构,同时为了调配1‑己烯和1‑辛烯生产的比例采用多齿型PNP化合物作为催化剂选择性调配配体,能够有效提升催化剂的性能。
Description
技术领域
本发明涉及一种催化剂体系,尤其是涉及一种乙烯低聚催化剂及其制备方法与应用。
背景技术
线性α-烯烃是近年来迅速发展的重要化工原料,其中1-己烯和1-辛烯主要作为共聚单体用于生产高性能的高密度聚乙烯和线性低密度聚乙烯。以1-己烯、1-辛烯为共聚单体制得的聚乙烯树脂具有极好的拉伸强度及抗撕裂强度,可以极大的提高聚乙烯树脂的品质,国外欧美等国主要使用1-己烯、1-辛烯作为聚乙烯的共聚单体。相较传统的全分布生产方式,乙烯选择性三聚和四聚生产1-己烯和1-辛烯具有很高的原子利用率,更符合绿色化学的要求。
传统的生产方法中,乙烯非选择性齐聚工艺中的产物呈Schulz-Flory分布,特定组分选择性差,需要通过高耗能的分离过程才能获得相应的高纯度线性α-烯烃,这无法满足工业上对特定α-烯烃日益增长的需求。近些年,乙烯选择性齐聚技术的研究获得很大的发展。2003年,Phillips公司在卡塔尔实现了乙烯三聚生产1-己烯的工业化生产。
目前在乙烯选择性齐聚催化剂中,铬系、钛系、钽系等催化剂都具有良好的性能,其中Cr系催化剂的活性和选择性表现更佳,受到研究者越来越多的关注。
EP699648中报道了一种铬系催化剂,催化剂由一种铬盐A、一种有机铝化物B、一种吡咯化合物C和一种D(IIIB)氯化物或一种E(VIB)氯化物组成。最好的铬盐有2-乙基己酸铬和环烷酸铬、乙酰丙酮铬。A、B、D影响催化活性;C影响1-己烯选择性。1-己烯选择性80%、纯度98-99%。特点是用1-己烯作催化剂制备和乙烯三聚的溶剂,省去了1-己烯与溶剂分离的装置和费用。
EP 0608447A中报道了一种铬系催化剂组合物,作为乙烯齐聚和/或共聚的催化剂,其中使用一种含铬的化合物作为催化剂组合物的组分之一;使用吡咯化合物作为铬系催化剂组合物的组分之二;采用了一种以路易士酸和/或金属烷基化合物为活化剂作为该催化剂组合物的组分之三;同时还指出,催化剂体系中还可任选一种卤素源作为该催化剂组合物中的组分之四,该卤素源既可为无机卤化物,也可为众多类型的有机卤化物,该催化剂对1-己烯的选择性较高,但其催化活性不高。
JP 0832519中使用了Sn(OSO2F3)2化合物代替EP 0608447A中第四组分的卤素源,形成了一种新的四元铬系催化剂组合物,该四元铬系催化剂的活性和选择性未得到明显的改进。
USP 5,910,619中报道了采用1,2,3,4,5,6-六氯环己烷作为改进剂,组成四元催化剂组合物,该催化剂的活性虽有所提高;中国专利“一种乙烯齐聚制1-己烯的催化剂及其应用”(CN1294109A)使用了新型催化体系,催化活性有了明显提高。但仍不能满足要求,人们希望进一步改进催化剂的性能,以提高催化活性。
因此,针对目前聚烯烃装置生产高性能聚烯烃产品所需要的的巨大需求,通过优化低聚催化剂金属结构,开发出同时低聚生产1-己烯和1-辛烯的催化剂具有经济实用价值和科学意义。
发明内容
本发明的目的在于提供一种乙烯低聚催化剂及其制备方法与应用,能够有效提升催化剂的活性。
为了实现上述目的,本发明实施例提供如下技术方案:
根据本发明实施例的第一方面,提供一种乙烯低聚催化剂,制备所述乙烯低聚催化剂的原料包括二铬有机酸盐、配体、给电子体和助催化剂,
所述二铬有机酸盐的通式为
所述配体包括2,5-二甲基吡咯和多齿型PNP化合物,所述多齿型PNP化合物的通式为
其中,R1、R2、R3、R4分别选自苯基、苯甲基、萘基中的任意一种;R5为异丙基、丁基、环丙基、环戊基、环己基、芴基中的任意一种。
进一步的,所述给电子体为1,4-二氯苯、1,1,2-三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、氯苯、1,2-二氯苯,1,3-二氯苯中的任意一种或两种以上的组合。
进一步的,所述给电子体为四氯乙烷、五氯乙烷、六氯乙烷中的任意一种或两种以上的组合。
进一步的,所述助催化剂为三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氯二乙基铝、二氯乙基铝、倍半氯化乙基铝、甲基铝氧烷、改性甲基铝氧烷、乙基铝氧烷中的至少一种。
进一步的,所述助催化剂为三乙基铝、一氯二乙基铝中的至少一种。
进一步的,所述二铬有机酸盐与2,5-二甲基吡咯的摩尔比为1:(0~5),所述助催化剂与二铬有机酸盐的摩尔比为(50~300):1;所述二铬有机酸盐与给电子体的摩尔比1:(0.8~5)。
进一步的,所述助催化剂与二铬有机酸盐的摩尔比为(50~80):1。
根据本发明实施例的第二方面,提供一种乙烯低聚催化剂的制备方法,所述二铬有机酸盐的制备方法包括:氮气保护条件下,二乙酸铬和氯气加成反应生成二氯化乙酸铬,然后与有机酸进行复分解反应,生成所述二铬有机酸盐。
根据本发明实施例的第三方面,提供一种1-己烯的制备方法,包括将所述乙烯低聚催化剂放入到反应釜中,之后通入乙烯,反应结束后制得所述的1-己烯和1-辛烯,反应釜的反应温度为30-80℃,反应釜的反应时间为0.1-4h,反应釜的反应压力为0.5~10.0Mpa;反应釜中还填充有惰性溶剂,所述惰性溶剂包括烷烃、芳烃、卤代烃、烯烃中的任意一种或两种以上的组合。通过调节氮配体和多齿PNP配体比例生产不同产量的1-己烯和1-辛烯。
根据本发明实施例的第四方面,提供一种乙烯低聚催化剂于乙烯低聚合成1-己烯、1-辛烯中的应用。
进一步的,所述多齿型PNP配体的制备方法和配置比例包括:
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二氯甲烷,三乙胺,二苯基氯化磷烷基化合物,降温至0℃,缓慢加入环丙胺。搅拌反应30min后升至室温继续反应12小时后获得多齿型PNP配体。
所述二铬有机酸盐与2,5-二甲基吡咯、多齿型PNP配体的摩尔比为1:(0~5):(0~5),所述助催化剂与二铬有机酸盐的摩尔比为(50~300):1;所述二铬有机酸盐与给电子体的摩尔比1:(0.8~5)。
本发明实施例具有如下优点:本发明实施例提供一种乙烯低聚催化剂及其制备方法与应用,本发明使用比较廉价易得的具有金属-金属四重键结构的二铬盐二乙酸亚铬作为合成有机二铬酸盐的原料。本发明的低聚催化剂优选使用比较容易配位的2,5-二甲基吡咯作为催化剂配体,保证催化剂形成合理的空间结构,同时为了调配1-己烯和1-辛烯生产的比例采用多齿型PNP化合物作为催化剂选择性调配配体,能够有效提升催化剂的性能。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明背景技术部分涉及的Manyie机理模型;
图2为本发明背景技术部分涉及的Phillips机理模型。
具体实施方式
下面将结合实施例对本发明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
1、二氯异辛酸二铬制备
无水无氧条件下,采用脱水后的二乙酸铬和氯气加成反应生成二氯化乙酸铬,然后与异辛酸进行复分解反应,生成二氯异辛酸二铬。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的经脱水处理的甲苯(10mL),步骤1合成的二氯异辛酸二铬(0.03mmol),2,5-二甲基吡咯(29mg),三乙基铝(10mL),1,1,2,2-四氯乙烷(7mL,0.54mmol),室温反应10min后备用。
3、乙烯低聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的环己烷(200mL)及上述催化剂。在90℃、5.0MPa的压力下进行齐聚反应,反应40min后用冰浴降温、卸压,用质量分数为10%的酸化乙醇终止反应。结果见附表1。
实施例2
1、二氯异辛酸二铬制备
详见实施例1。
2、制备(二苯基)磷氮(环丙基)磷(二苯基)配体
(1)制备N,N-二异丙基二氯磷酰胺
在经N2充分置换的带搅拌的250mL反应器中加入经脱水处理的甲苯(100mL),加入PCl3(21.87mL,0.25mol),并降温到-20℃。室温下边搅拌边缓慢地加入二异丙胺(70mL,0.5mol),搅拌3小时后升至室温再继续反应2小时,然后过滤,干燥得产物38.1g(0.19mol,74%)。
(2)制备苯基溴化镁格试剂
在经N2充分置换的带搅拌的250mL反应器中加入经脱水处理的THF(100mL),镁粉(9.11g,0.375mol),冰浴降温并缓慢滴加溴苯(11.775g,0.075mol)。2小时后,加热回流继续反应2小时得到格试剂。
(3)制备氯化二苯基磷
在经N2充分置换的带搅拌的250mL反应器中加入经脱水处理的THF(100mL),降温至0℃,缓慢加入N,N-二异丙基二氯化磷酰胺(6.64mL,36mmol)。升至室温反应12小时。然后反应混合物用环己烷稀释,并用干燥的HCl气体鼓泡1小时,过滤,干燥得到氯化二苯基磷。
(4)制备(二苯基)磷氮(环丙基)磷(二苯基)
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二氯甲烷(20mL),三乙胺(3.75mL),氯化二苯基磷(1.326mL,7.2mmol),降温至0℃,缓慢加入环丙胺(3.6mmol)。搅拌反应30min后升至室温继续反应12小时。过滤、干燥得到产物(0.87g,56.6%)。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL),(二苯基)磷氮(环丙基)磷(二苯基)(29mg),三乙基铝(10mL),异辛酸二铬(0.03mmol),1,1,2,2-四氯乙烷(7mL,0.54mmol),SiO2(0.03mmol)室温反应10min后备用。
3、乙烯低聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的甲苯(200mL)及上述催化剂。在90℃、5.0MPa的压力下进行齐聚反应,反应40min后用冰浴降温、卸压,用质量分数为10%的酸化乙醇终止反应。结果见附表1。
实施例3
1、异辛酸二铬制备
详见实施例1。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL),步骤1合成的二氯异辛酸二铬,2,5-二甲基吡咯(29mg),实施例2步骤2制备的(二苯基)磷氮(环丙基)磷(二苯基),三乙基铝(10mL),1,1,2,2四氯乙烷(0.069mmol)室温反应5min后备用。
3、乙烯低聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的环己烷(200mL)及上述催化剂。在20℃、5.0MPa的压力下进行齐聚反应,反应20min后用冰浴降温、卸压,用质量分数为10%的酸化乙醇终止反应。结果见附表1。
附表1
本发明的设计原理在于:
Manyie提出了著名的Metallocycle-based模型解释Cr(III)催化剂的乙烯三聚机理。Manyie机理认为:亚铬配位活性中心与两分子乙烯碰撞,形成“亚铬金属五元环”结构,该结构十分稳定,一般不会发生分解。它能与一分子乙烯继续反应生成不稳定的“丁烯基-亚铬-乙基”结构,然后金属阳离子发生自身还原消去反应释放出一分子1-己烯,如图1所示。
Phillips公司的Briggs等提出了另一种机理模型:与Manyie机理一样,亚铬配位活性中心首先与两分子乙烯碰撞形成稳定的“亚铬金属五元环”结构,该中间产物继续与一分子乙烯反应形成不稳定“金属七元环”结构,最终该七元环通过β-H消去反应生成一分子1-己烯,如图2所示。
本专利根据Manyie提出了著名的Metallocycle-based乙烯三聚机理模型,并受菲利普公司M.P.McDaniel有机多铬聚烯烃催化剂的启发,创新开发出采用二铬有机金属化合物作为主催化剂组分的催化剂,用于生产1-己烯和1-辛烯。传统乙烯三聚催化剂通过特殊配体的空间位阻,使铬配位活性中心与两分子乙烯碰撞,形成“亚铬金属五元环”结构,该中间产物继续与一分子乙烯反应形成不稳定“金属七元环”结构,而乙烯四聚催化剂合成1-辛烯的催化剂是与乙烯分子反应形成不稳定“金属九元环”结构,然后金属阳离子发生自身还原消去反应释放出一分子1-己烯或1-辛烯。二重铬结构的低聚催化剂,由于是双金属二重键结构,有四电子轨道处于平面,天然有利金属七元环或九元环的形成,可以在生产1-己烯的同时联产1-辛烯。
本发明采用二铬有机酸盐作为低聚催化剂作为主催化剂组份,为了达到合成目的,本发明使用比较廉价易得的具有金属-金属四重键结构的二铬盐二乙酸亚铬作为合成有机二铬酸盐的原料。二乙酸亚铬是深红色晶体,反磁性。通过真空条件加热转变为棕色无水物,后者倾向于通过氧桥聚合成无限长链。含金属-金属四重键,包括一个σ键、两个π键和一个δ键,Cr—Cr距离2.36埃。配体为双齿的桥式乙酸根。在该分子中,两个Cr2+的配位数均为6,结构为变形八面体结构。化合物的反磁性及两个Cr之间具有较短的键长(235pm,与Cr-Cr单键长328pm相比),表明Cr与Cr之间除了形成σ键和π键之外,还形成了δ键。合成有机二铬酸盐方法为首先将无水的二乙酸铬,氯化加成将Cr与Cr之间π键饱和,然后在氮气保护下与有机酸进行复分解反应合成有机酸二铬,生成有机酸二铬盐结构如图所示:
本发明的低聚催化剂优选使用比较容易配位的2,5-二甲基吡咯作为催化剂配体,保证催化剂形成合理的空间结构,同时为了调配1-己烯和1-辛烯生产的比例采用多齿型PNP化合物作为催化剂选择性调配配体。配体结构对催化性能有显著影响,通过调节膦官能团上的取代基和配体中P-Cr-N角度可以调控C6或C8烯烃的选择性以及1-己烯和1-辛烯的纯度。含多齿型PNP配体的铬配合物能催化乙烯生成大量的齐聚物和少量聚乙烯,其液相产物中C6和C8、C10烯烃的总选择性高达99%,且1-己烯和1-辛烯的纯度很高。多齿型PNP合成方法具体可参考实例。
给电子体可以采用含氯的有机物,优选四氯乙烷,五氯乙烷,六氯乙烷,也可以使用1,4-二氯苯,1,1,2-三氯乙烷,氯苯,1,2-二氯苯,1,3-二氯苯和/或1,4-二氯苯,六氯环己烷等。
助催化剂优选廉价易得的三乙基铝,也可以使用其他的烷基铝或铝氧烷作为助催化剂。
所述二铬有机酸盐与2,5-二甲基吡咯、多齿型PNP化合物的摩尔比为1:(0~5):(0~5),所述助催化剂与二铬有机酸盐的摩尔比为(50~300):1,优选(50~80);所述二铬有机酸盐与给电子体的摩尔比1:(0.8~5)。
将以上四种组分在惰性环境下混合10分钟后,加入反应釜中,通入乙烯进行低聚反应;也可以将直接将以上四种组分加入反应釜中,通入乙烯进行低聚反应。反应温度通常为30~150℃。在使用烷基铝作为助催化剂时,优选为100~130℃,这样有利于取热和长期稳定运行;而使用铝氧烷时反应温度优选50~80℃,防止铝氧烷分解。反应压力为0.5~10.0MPa,优选为1~10MPa,更优选为2~6MPa;时间为0.1~4小时,优选为0.3~1小时,更优选为0.5~0.7小时,低停留时间有利于减少副反应发生。
乙烯低聚反应主要在惰性溶剂中进行,可选择的溶剂包括烷烃、芳烃、卤代烃、烯烃等。典型的溶剂包括,但不限于苯、甲苯、二甲苯、异丙苯、正庚烷、正己烷、甲基环己烷、环己烷、1-己烯、辛烯-1、离子液体等。通过改变反应条件(反应溶剂、助催化剂、催化剂浓度、配体/铬比例、反应温度和反应压力),可以调节液相产物中1-己烯/1-辛烯的比例。当使用脂肪族碳氢化合物为反应溶剂时,加入少量的甲苯能有效提高1-辛烯的选择性。
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 (9)
2.根据权利要求1所述的乙烯低聚催化剂,其特征在于:所述给电子体为1,4-二氯苯、1,1,2-三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、氯苯、1,2-二氯苯,1,3-二氯苯中的任意一种或两种以上的组合。
3.根据权利要求2所述的乙烯低聚催化剂,其特征在于:所述给电子体为四氯乙烷、五氯乙烷、六氯乙烷中的任意一种或两种以上的组合。
4.根据权利要求1所述的乙烯低聚催化剂,其特征在于:所述助催化剂为三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氯二乙基铝、二氯乙基铝、倍半氯化乙基铝、甲基铝氧烷、改性甲基铝氧烷、乙基铝氧烷中的至少一种。
5.根据权利要求4所述的乙烯低聚催化剂,其特征在于:所述助催化剂为三乙基铝、一氯二乙基铝中的至少一种。
6.根据权利要求4所述的乙烯低聚催化剂,其特征在于:所述二铬有机酸盐与2,5-二甲基吡咯、多齿型PNP化合物的摩尔比为1:(0~5):(0~5),所述助催化剂与二铬有机酸盐的摩尔比为(50~300):1;所述二铬有机酸盐与给电子体的摩尔比1:(0.8~5)。
7.根据权利要求6所述的乙烯低聚催化剂,其特征在于:所述助催化剂与二铬有机酸盐的摩尔比为(50~80):1。
8.一种1-己烯的制备方法,其特征在于:包括将权利要求1-7中任一项所述乙烯低聚催化剂加入到反应釜中,之后通入乙烯,反应结束后制得所述的1-己烯,反应釜的反应温度为30-150℃,反应釜的反应时间为0.1-4h,反应釜的反应压力为0.5~10.0Mpa;反应釜中还填充有惰性溶剂,所述惰性溶剂包括烷烃、芳烃、卤代烃、烯烃中的任意一种或两种以上的组合。
9.一种如权利要求1-7中任一项所述乙烯低聚催化剂于乙烯低聚合成1-己烯、1-辛烯中的应用。
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