CN115400800B - 一种乙烯选择性三聚催化剂组合物及其应用 - Google Patents
一种乙烯选择性三聚催化剂组合物及其应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000005977 Ethylene Substances 0.000 title claims abstract description 38
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 40
- -1 1, 10-phenanthroline compound Chemical class 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 13
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- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 150000001845 chromium compounds Chemical class 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 abstract description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract description 3
- 150000005045 1,10-phenanthrolines Chemical class 0.000 abstract description 2
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical group ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 19
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
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- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
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- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 235000007831 chromium(III) chloride Nutrition 0.000 description 2
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
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- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 2
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- 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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- 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
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Abstract
本发明公开了一种乙烯选择性三聚催化剂组合物,由铬化物、1,10‑邻菲咯啉化合物、烷基铝和无机含磷卤化物解聚剂共同组成,各成分的摩尔比为1:0.1~100:1~1000:1~1000,其中铬化物为异辛酸铬、乙酰丙酮铬或四氢呋喃氯化铬,烷基铝助剂为三乙基铝、甲基铝氧烷(MAO)、三甲基铝或异丁基铝;给电子体为四氯乙烷或六氯乙烷;本发明要求保护的一种上述含磷卤化物作为解聚剂和1,10‑邻菲咯啉化合物作为配体的乙烯三聚催化剂体系催化乙烯三聚反应时,具有催化剂活性高、1‑己烯选择性高、产物中聚乙烯副产物少,且在产业化中能降低成本等优点。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种乙烯选择性三聚催化剂组合物及其应用。
背景技术
1-己烯和1-辛烯等高碳α-烯烃是聚乙烯的重要共聚单体,也是应用广泛的有机化工原料。1-己烯作为重要的有机原料和化学中间体,主要用于生产高端聚乙烯(PE)。目前,我国PE基本上还都是采用1-丁烯作为共聚单体,但是,1-己烯等高碳α-烯烃共聚树脂具有的优异性能是1-丁烯共聚物树脂难以比拟的,1-丁烯共聚物已是走向淘汰的产品。由1-己烯与乙烯共聚生产的线性低密度聚乙烯(LLDPE)及高密度聚乙烯(HDPE)在聚乙烯的机械加工、耐热性、柔韧性和透明性等方面具有明显优势。特别适合于生产包装膜和农用覆盖膜。世界大多数国家已经采用1-己烯和1-辛烯替代1-丁烯生产LLDPE和HDPE。在气相PE生产工艺中,采用凝聚方法还能以最小的投入实现20%以上的生产增长。世界许多厂家利用这种方法来提高生产效益。
除此之外乙烯齐聚或三聚的1-己烯等高碳α-烯烃等都是很有价值的有机化工原料,不仅可用作聚合物的共聚单体、高档润滑油基础油,还可用作洗涤剂、表面活性剂、增塑剂、杀菌剂、乳化剂等精细化工的原料,市场前景广泛。要提高我国PE产品的竞争力,必须开发生产1-己烯等高碳α-烯烃替代1-丁烯作为共聚单体生产共聚物已成为我国PE工业发展的必然趋势。
在乙烯三聚的催化剂体系中、普遍采用的基本组成为铬化合物、吡咯、烷基铝和卤素化合物。催化剂组成较为复杂,深入进行催化剂组分的研究,将提高人们对催化剂活性、选择性的认识。实验表明,在传统催化剂中加入卤素化合物后会使催化剂的活性和选择性大大提高。
在乙烯选择性三聚方面,已有大量的专利。
1999年,Phillips申请专利US5856257采用铬系催化剂催化乙烯发生选择性三聚反应生成选择性高达95%的1-己烯,该装置工艺是目前世界上最先进的1-己烯工艺技术。中国石油化工股份有限公司在专利CN102558107A中通过微波辐射快速高效的制备CrCl3(THF)3,以此为基础制备的铬系催化剂生产1-己烯选择性高于92%,纯度高达99.2%,并且该工艺于2007年在北京燕山石化公司建成5万吨/年的1-己烯生产工艺。
EP0608447A1中报道了一种铬系催化剂组合物,作为乙烯齐聚和共聚的催化剂,其中使用一种含铬的化合物作为催化剂组合物之一,包含吡咯化合物以及一种路易斯酸和/或金属烷基铝化合物。该催化剂指出,催化剂体系中可任选一种卤素源作为该催化剂组合物中的组分之一,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-己烯的选择性有提高,但其催化活性不高。
专利JP 08134131中探讨了以末端相邻两个碳原子上含有三个以上卤素原子为特征的饱和卤代烃作为异辛酸铬、2,5-二甲基吡咯和三乙基铝催化剂的促进剂,该四元催化体系在乙烯选择性三聚制备1-己烯时,催化活性明显提高。
中国石油天然气股份有限公司申请的专利CN1490291中催化剂体系包含异辛酸铬、2,4-二甲基吡咯、三乙基铝、1,2,3,4,5,6-六氯环己烷γ体等,1-己烯的选择性高达99.3%,利用该三聚技术中石油分别于2007年和2014年在大庆石化公司和独山子石化公司实现1-己烯的产业化。
USP5910619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,该催化剂的活性虽然有所提高,但选择性不是很高
中石化在专利CN 1108193C中披露了一种能够促进乙烯选择性三聚反应的含卤促进剂,该促进剂是一种芳环上至少含有一个被至少二个卤素原子在α-位取代的C1-2-烷基的卤代烷基取代的芳烃或卤代芳烃化合物,促进剂的加入,能显著提高催化剂的活性和1-己烯的选择性。
由上述可见,在乙烯选择性三聚催化剂中,除铬源、烷基铝和配体外,第四组份是影响催化剂活性和选择性的关键因素,开发出优良的第四组份,不但能提高催化活性和目标产物的选择性,还能有效降低聚合物的生成,从而简化工艺流程。
发明内容
为解决上述问题,本发明提供了一种乙烯选择性三聚催化剂组合物,由铬化物、1,10-邻菲咯啉化合物、烷基铝和无机含磷卤化物解聚剂共同组成,其催化乙烯三聚反应时,具有催化剂活性高、1-己烯选择性高、产物中聚乙烯副产物少,且在产业化中能降低成本等优点。
为实现上述目的,本发明的技术方案为:
一种乙烯选择性三聚催化剂组合物,包括以下组分:
(1)铬化物:异辛酸铬、乙酰丙酮铬或四氢呋喃氯化铬;
(2)配体:1,10-邻菲咯啉化合物,结构式如下:,其中R1、R2、R3、R4、R5、R6、R7和R8相同或不同,选自氢、烷基、烷氧基、环烷基或卤素;
(3)烷基铝助剂:三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝;
(4)解聚剂:PCl3、PCl5、PBr5或PBr3。
进一步地,所述铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和解聚剂的摩尔比为:1:0.1~100:1~1000:1~1000;优选为1:0.1~10:1~500:1~50;更优选为1: 1~8:1~100:1~10。
上述乙烯选择性三聚催化剂组合物的应用:将乙烯选择性三聚催化剂组合物中各成分分别溶于惰性溶剂中,以均相催化剂形式依次注入或提前混合均匀注入乙烯三聚反应体系中,随后提高乙烯压力,与催化剂充分接触,进行乙烯三聚反应,得到1-己烯。
进一步地,乙烯三聚反应的条件为:温度为30~250℃,压力为0.5~20MPa,时间为0.1~2h;所述惰性溶剂包括苯、甲苯、环己烷、甲基环己烷、正庚烷或正己烷。
进一步地,本发明的乙烯选择性三聚催化剂组合物在催化乙烯三聚反应中的应用具体包括以下步骤:
(1)乙烯选择性三聚催化剂组合物制备:将乙烯选择性三聚催化剂组合物中各成分分别溶于经除水处理的惰性溶剂中制备成铬化物、1,10-邻菲咯啉化合物、烷基铝助剂和解聚剂四种溶液备用;
(2)反应前先将反应釜釜体和内衬置于烘箱中120 ℃烘干过夜,安装到反应釜上后密封,抽真空条件下加热至105℃恒温1 h,除去残留的水、氧和含氧杂质,然后温度设置为反应温度,使其自然降温,同时氮气填充,随后抽真空,重复三次,确保空气被置换干净,然后用真空泵抽走氮气,用乙烯填充,重复三次,保证釜体充满乙烯;
(3)在搅拌条件下使用注射器注入步骤(1)制得的烷基铝助剂溶液,待温度稳定至反应温度后,用注射器依次注入铬化物溶液、1,10-邻菲咯啉化合物溶液、解聚试剂溶液,关闭尾气阀,调节减压阀,待压力升至预定压力值后开始计时,并记录质量流量计数据,反应结束后关闭乙烯气体,反应停止,关闭进气口阀门,卸下反应釜体,浸泡至冰水浴中使反应釜冷却至10℃以下。
开启尾气阀泄压后在搅拌条件下注入一定量5 ml 10%HCl/乙醇溶液,使烷基铝助剂淬灭,随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤,滤纸提前称量记录质量,随后搅拌桨上的聚合物用勺子刮下来,用溶剂清洗至烧杯里,将所得的聚合物置于真空烘箱中60℃干燥过夜,分别称重,计算获得聚合物的质量。根据MS可标定组分种类,根据GC结果结合液相产物质量和聚合物质量,可计算获得各产物的选择性以及催化剂活性。
本发明与现有技术相比:本发明在铬系催化剂和烷基铝助催化剂两种主要成分保持不变的情况下,首次采用了无机含磷卤化物作为解聚剂,同时本发明使用1,10-邻菲咯啉化合物代替吡咯化合物作为配体,即本发明由铬金属盐、1,10-邻菲咯啉化合物、烷基铝和无机含磷卤化物解聚剂共同组成乙烯三聚组合物。无机含磷卤化物解聚剂具有适当的给电子能力,可与烷基铝试剂结合,阻止其聚集,但又不影响其还原能力,最终该催化剂组合物具有优异的乙烯三聚催化性能,还能减少环境污染以及对操作人员的身体伤害。此外无机含磷卤化物作为路易斯酸与有机卤化物相比价格低廉,有利于工业化推广。此外,本发明中1,10-邻菲咯啉化合物中苯环和旁边的两个含氮六元环形成共轭,构成了大π键,三个六元环具有较强的刚性,在配位过程中结构稳定,不易转动,可以较为稳定的和金属中心形成单一活性中心,可以和活性中心发生较好的作用。与金属铬、烷基铝以及无机卤素给电子体共同作用,可以更加灵活地调节给单子性能,高效的催化乙烯分子与金属形成七元环,经β脱氢后释放一个1-己烯分子,且与吡咯化合物相比,1,10-邻菲咯啉化合物具有较大的空间位阻,可以有效降低聚合物的生成,有利于长周期运行。
具体实施方式
下面结合具体实施例对本发明进一步说明,但本发明不限于此。
实施例1
乙烯齐聚反应在高压不锈钢反应釜中进行。反应前高压反应釜在抽真空条件下加热至100℃恒温1 h,然后将温度设置为80℃,使其自然降温,同时氮气置换数次,然后用乙烯置换数次,保证釜体充满乙烯。随后依次向其中加入溶剂环己烷和催化剂,催化剂中中乙酰丙酮铬:1,10-邻菲咯啉:三乙基铝:三氯化磷=1: 1:100: 10。控制反应压力为3MPa,反应1h后后停止反应,关闭进气口阀门,卸下反应釜体,浸泡至冰水浴中使反应釜冷却至10℃以下。开启尾气阀泄压后在搅拌条件下注入5 mL 10% HCl/乙醇溶液,使烷基铝淬灭,随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤,滤纸提前称量记录质量,随后搅拌桨上的聚合物用勺子刮下来,用溶剂清洗至烧杯里,将所得的聚合物置于真空烘箱中60℃干燥过夜,分别称重,计算获得聚合物的质量。根据MS可标定组分种类,根据GC结果结合液相产物质量和聚合物质量,可计算获得各产物的选择性以及催化剂活性。数据结果见表1。
实施例2
同实施例1,不同之处在于将乙酰丙酮铬和1,10-邻菲咯啉化合物比例改为1:5,数据结果见表1。
实施例3
同实施例1,不同之处在于将三氯化磷改为五氯化磷,数据结果见表1。
实施例4
同实施例1,不同之处在于将三氯化磷改为三溴化磷,数据结果见表1。
实施例5
同实施例1,不同之处在于将三氯化磷改为五溴化磷,数据结果见表1。
对比例1
同实施例1,不同之处在于将1,10-邻菲咯啉改为吡咯,数据结果见表1。
对比例2
同实施例1,不同之处在于将三氯化磷改为六氯乙烷,数据结果见表1。
对比例3
同实施例1,不同之处在于将三氯化磷改为六氯乙烷,将1,10-邻菲咯啉化合物改为吡咯,数据结果见表1。
表1 本发明的实施例和对比例反应条件及反应性能汇总表
以上实施例仅为了清楚的说明本发明内容,本发明的实施方式并不限制于此。凡在本发明的精神与原则之内,所做的任何修改、替换、改进等均应包含在本发明的保护范围之内。
Claims (1)
1.一种乙烯选择性三聚催化剂组合物,其特征在于:所述催化剂组合物由乙酰丙酮铬、1,10-邻菲咯啉、三乙基铝、三溴化磷按摩尔比1:1:100:10组成。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0170311A2 (en) * | 1984-07-30 | 1986-02-05 | Shell Internationale Researchmaatschappij B.V. | Process for the dimerization of olefins |
JPH107594A (ja) * | 1996-06-17 | 1998-01-13 | Tosoh Corp | 1−ヘキセンの製造方法 |
JP2000202299A (ja) * | 1999-01-20 | 2000-07-25 | Tosoh Corp | エチレンの三量化触媒及びこれを用いたエチレンの三量化方法 |
CN1850339A (zh) * | 2005-04-22 | 2006-10-25 | 中国科学院化学研究所 | 一种用于乙烯齐聚和聚合的催化剂及制备方法和用途 |
CN101348502A (zh) * | 2007-07-19 | 2009-01-21 | 中国科学院化学研究所 | 2-苯并咪唑-1,10-菲咯啉过渡金属配合物及其制备方法与应用 |
JP2010105977A (ja) * | 2008-10-31 | 2010-05-13 | Idemitsu Kosan Co Ltd | オレフィンオリゴマーの製造方法 |
CN104011089A (zh) * | 2011-12-27 | 2014-08-27 | 出光兴产株式会社 | α-烯烃的制造方法 |
JP2016188204A (ja) * | 2015-03-27 | 2016-11-04 | 三井化学株式会社 | 遷移金属化合物、該化合物を含むオレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法 |
WO2018125826A1 (en) * | 2016-12-29 | 2018-07-05 | Chevron Phillips Chemical Company Lp | Ethylene oligomerization processes |
EP3562799A1 (en) * | 2016-12-29 | 2019-11-06 | Chevron Phillips Chemical Company LP | Ethylene oligomerization processes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6689928B2 (en) * | 2000-04-04 | 2004-02-10 | Exxonmobil Research And Engineering Company | Transition metal complexes and oligomers therefrom |
-
2022
- 2022-09-22 CN CN202211158189.8A patent/CN115400800B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0170311A2 (en) * | 1984-07-30 | 1986-02-05 | Shell Internationale Researchmaatschappij B.V. | Process for the dimerization of olefins |
JPH107594A (ja) * | 1996-06-17 | 1998-01-13 | Tosoh Corp | 1−ヘキセンの製造方法 |
JP2000202299A (ja) * | 1999-01-20 | 2000-07-25 | Tosoh Corp | エチレンの三量化触媒及びこれを用いたエチレンの三量化方法 |
CN1850339A (zh) * | 2005-04-22 | 2006-10-25 | 中国科学院化学研究所 | 一种用于乙烯齐聚和聚合的催化剂及制备方法和用途 |
CN101348502A (zh) * | 2007-07-19 | 2009-01-21 | 中国科学院化学研究所 | 2-苯并咪唑-1,10-菲咯啉过渡金属配合物及其制备方法与应用 |
JP2010105977A (ja) * | 2008-10-31 | 2010-05-13 | Idemitsu Kosan Co Ltd | オレフィンオリゴマーの製造方法 |
CN104011089A (zh) * | 2011-12-27 | 2014-08-27 | 出光兴产株式会社 | α-烯烃的制造方法 |
JP2016188204A (ja) * | 2015-03-27 | 2016-11-04 | 三井化学株式会社 | 遷移金属化合物、該化合物を含むオレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法 |
WO2018125826A1 (en) * | 2016-12-29 | 2018-07-05 | Chevron Phillips Chemical Company Lp | Ethylene oligomerization processes |
EP3562799A1 (en) * | 2016-12-29 | 2019-11-06 | Chevron Phillips Chemical Company LP | Ethylene oligomerization processes |
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