CN115445667B - 一种乙烯齐聚用催化剂及其应用 - Google Patents
一种乙烯齐聚用催化剂及其应用 Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000005977 Ethylene Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 21
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 16
- -1 4-phenylimidazole compound Chemical class 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000005829 trimerization reaction Methods 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 150000001845 chromium compounds Chemical class 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 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 claims description 3
- 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 description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 150000004820 halides Chemical class 0.000 abstract description 12
- 229910052804 chromium Inorganic materials 0.000 abstract description 11
- 239000011651 chromium Substances 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
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- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 15
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- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
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- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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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
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-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
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 229910001868 water Inorganic materials 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
- FUEGFUSXEBMAGH-UHFFFAOYSA-N C1CCCC1.[Cr] Chemical compound C1CCCC1.[Cr] FUEGFUSXEBMAGH-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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齐聚用催化剂及其应用，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4‑苯基咪唑化合物代替吡咯化合物作为配体，即本发明由铬金属盐、4‑苯基咪唑化合物化合物、烷基铝和无机含磷卤化物解聚试剂共同组成乙烯三聚组合物，不仅能将聚合的烷基铝拆解为单分子结构，能保持有机氯化物的高选择性和活性，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。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种乙烯齐聚用催化剂及其应用。
背景技术
线性α-烯烃不仅是重要的乙烯共聚单体，还是制备增塑剂、洗涤剂、表面活性剂及润滑剂的重要化工原料。用作共聚单体的C4~C8部分所占比重最大，它们可以用来合成线性低密度聚乙烯（LLDPE）。在这些共聚单体中应用最广泛的是1-己烯，用它生产的线性低密度聚乙烯具有强度高、韧性好、刚性强、耐热、耐寒等优点，还具有良好的耐环境应力开裂、耐撕裂强度，并可耐酸、碱、有机溶剂等。因此生产高纯度的线性α-烯烃是至关重要的。
用乙烯非选择性齐聚得到的线性α-烯烃产品分布宽，分离效率低。19世纪70年代，高选择性的乙烯齐聚逐步成为可能并得到了发展，2003年Phillips公司率先实现了高选择性乙烯齐聚三聚的工业化。在Phillips乙烯聚合体系中发现1-己烯的生成后， Briggs推测在乙烯三聚过程中存在两个中间体，即金属五元环和七元环。第三分子乙烯与金属铬五元环配位后，会快速插入到金属五元环中形成金属七元环，而且此步必须快于1-丁烯从铬环戊烷上的消去速度。然后，金属七元环通过β-氢转移消去一分子1-己烯，并得到铬活性中心，这一步应快于乙烯继续插入生成更大的金属环状物的速率。
目前，乙烯高选择性齐聚催化剂已经有了很大程度的发展，新配体、新的催化剂体系不断涌现。但是总体而言还是不能满足要求，很多体系缺少具体的反应机理。配体、助催化剂、反应条件对乙烯齐聚选择性及活性的影响及配位方式还有待进一步考究。但经过多次实验证明，在不加卤素化合物的情况下，有机金属化合物/配体/助催化剂催化剂体系无论是活性还是选择性都及其低，可见催化剂中第四组分对整个反应体系的活性以及选择性都有明显的影响。
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。
Phillips申请专利的EP0608447A1 中披露了含卤化合物促进剂能较大程度提高催化剂的活性和选择性，该含卤化合物可为无机卤化物，也可为有机含卤化合物，但催化剂的活性和选择性仍未达到人们的要求。
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。
三菱化学公司申请了专利US08790479保护了一种含有铬基催化剂的反应溶液存在下使α-烯烃在反应区中进行齐聚来制备α-烯烃齐聚物的方法，催化剂组合物为铬源、吡咯衍生物、烷基铝和有机卤化物（四氯乙烷）。
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
根据大量披露的专利或报道，现有技术仍然存在催化剂活性低、原料成本高、1-己烯的选择性低、聚合过程中会生成少量聚合物，影响装置连续运行的问题，为了解决上述技术问题，本发明公开了一种乙烯齐聚用催化剂，其采用铬化物、配体、烷基铝助剂和无机含磷卤化物解聚剂。本发明将无机含磷卤化物作为解聚剂、4-苯基咪唑化合物作为配体的催化剂组合物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：
一种乙烯齐聚用催化剂，包括以下组分：铬化物、配体、烷基铝助剂和解聚助剂，其中配体为4-苯基咪唑化合物，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；所述解聚助剂为PCl3、PCl5、PBr5或PBr3。
进一步地，所述铬化物、配体、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。
进一步地，所述铬化物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种。
进一步地，所述烷基铝助剂为三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝。
上述的乙烯齐聚用催化剂在催化乙烯制备1-己烯中的应用：将乙烯齐聚用催化剂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，本发明的乙烯齐聚用催化剂的应用具体包括以下步骤：
（1）乙烯齐聚用催化剂制备：将乙烯齐聚用催化剂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溶液、配体溶液、烷基铝助剂溶液和解聚试剂溶液备用；
（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、配体溶液和解聚试剂溶液，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4-苯基咪唑化合物代替吡咯化合物作为配体，即本发明由铬金属盐、4-苯基咪唑化合物、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，不仅能将聚合的烷基铝拆解为单分子结构，能保持有机氯化物的高选择性和活性，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。该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。此外，本发明中4-苯基咪唑化合物中咪唑环和旁边的苯环为双环结构，且咪唑环上的杂原子有较强的给电子性能，整体构成了一个给电子能力适中的体系，且给电子能力可由两个共轭环协调，与金属铬、烷基铝以及无机含磷卤化物给电子体共同作用，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，4-苯基咪唑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95℃，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，催化剂中乙酰丙酮铬：4-苯基咪唑：三乙基铝：三氯化磷=1: 1:100: 10。控制反应压力为3.5MPa，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，不同之处在于反应温度为130℃，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4-苯基咪唑改为吡咯，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，将4-苯基咪唑改为吡咯，数据结果见表1。
对比例3
同对比例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。
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 (4)
1.一种乙烯齐聚用催化剂，其特征在于：包括以下组分：铬化物、配体、烷基铝助剂和解聚剂，其中配体为4-苯基咪唑化合物，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；所述解聚剂为PCl3、PCl5、PBr5或PBr3；
所述铬化物、配体、烷基铝助剂和解聚剂的摩尔比为：1:0.1~100:1~1000:1~1000。
2.根据权利要求1所述的乙烯齐聚用催化剂，其特征在于：所述铬化物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种。
3.根据权利要求1所述的乙烯齐聚用催化剂，其特征在于：所述烷基铝助剂为三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝。
4.一种如权利要求1-3任一项所述的乙烯齐聚用催化剂在催化乙烯三聚反应中的应用。
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