CN115385965A - Asymmetric six-membered ring pyridine imine complex containing large steric hindrance substituent and preparation method and application thereof - Google Patents
Asymmetric six-membered ring pyridine imine complex containing large steric hindrance substituent and preparation method and application thereof Download PDFInfo
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- CN115385965A CN115385965A CN202110561418.XA CN202110561418A CN115385965A CN 115385965 A CN115385965 A CN 115385965A CN 202110561418 A CN202110561418 A CN 202110561418A CN 115385965 A CN115385965 A CN 115385965A
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- benzhydryl
- radical
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- -1 pyridine imine Chemical class 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title abstract description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 78
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000005977 Ethylene Substances 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 17
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 125000006714 (C3-C10) heterocyclyl group Chemical group 0.000 claims description 8
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
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- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
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- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 119
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- 239000002244 precipitate Substances 0.000 description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 53
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- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 18
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
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- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 2
- LYGYRPBKAOHABC-UHFFFAOYSA-N 2,4-dibenzhydryl-6-methylaniline Chemical compound CC1=C(N)C(=CC(=C1)C(C1=CC=CC=C1)C1=CC=CC=C1)C(C1=CC=CC=C1)C1=CC=CC=C1 LYGYRPBKAOHABC-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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Abstract
Description
技术领域technical field
本发明属于聚烯烃催化剂技术领域，具体涉及一类新型含大位阻环烷烃和二苯甲基取代基的不对称六元环吡啶亚胺基金属配合物及其制备方法和应用。The invention belongs to the technical field of polyolefin catalysts, and in particular relates to a new type of asymmetric six-membered ring pyridine imine-based metal complex containing large sterically hindered cycloalkane and benzhydryl substituents and its preparation method and application.
背景技术Background technique
聚乙烯(PE)由于具有力学性能优良、加工性能好、化学性能稳定以及价格低廉等优点，已成为通用合成树脂中产量最大的品种，在日常生活、包装行业、汽车、建筑、农业及军事等领域得到广泛的应用。目前我国已成为世界上最大的PE进口国和第二大消费国。聚乙烯材料的性能和工业化用途在很大程度上取决于其链的大小和拓扑结构，可从半结晶塑料到高度支化弹性体再到聚乙烯蜡。其中包括线性聚乙烯，指大分子主链上不带长侧链，只含短侧链的一类聚乙烯。通常有高密度聚乙烯，超高分子量聚乙烯，线性低密度聚乙烯，极低密度聚乙烯等。如高密度聚乙烯，可用作薄膜、纤维和各类管材等。而超高分子量聚乙烯在航空航天、加工管材等方面展现出广阔的应用前景。Due to its excellent mechanical properties, good processing properties, stable chemical properties and low price, polyethylene (PE) has become the variety with the largest output in general synthetic resins. It is widely used in daily life, packaging industry, automobile, construction, agriculture and military, etc. fields are widely used. At present, my country has become the world's largest importer of PE and the second largest consumer. The properties and industrial uses of polyethylene materials are largely determined by their chain size and topology, which can range from semi-crystalline plastics to highly branched elastomers to polyethylene waxes. These include linear polyethylene, which refers to a type of polyethylene that does not have long side chains on the main chain of the macromolecule and only contains short side chains. Usually there are high-density polyethylene, ultra-high molecular weight polyethylene, linear low-density polyethylene, very low-density polyethylene, etc. Such as high-density polyethylene, which can be used as film, fiber and various pipes. UHMWPE shows broad application prospects in aerospace and pipe processing.
其中，聚乙烯蜡(PEW)是一种摩尔质量在500～5000g/mol的低摩尔质量聚乙烯，熔点高于90℃，相对密度在0.92～0.936g/cm3之间。因其具有毒性小、无腐蚀性、硬度较大、软化点高、熔融黏度低、耐磨、耐热以及良好的润滑性、分散性和流动性等优点，其可作为润滑剂、低粘度的分散剂等广泛应用于各领域，也可有效改善管材、薄膜、线缆及其他塑料橡胶的加工效率，开发利用前景广阔。Among them, polyethylene wax (PEW) is a low molar mass polyethylene with a molar mass of 500-5000 g/mol, a melting point higher than 90°C, and a relative density of 0.92-0.936 g/cm 3 . Because of its low toxicity, non-corrosiveness, high hardness, high softening point, low melt viscosity, wear resistance, heat resistance, good lubricity, dispersibility and fluidity, it can be used as a lubricant, low viscosity Dispersants are widely used in various fields, and can also effectively improve the processing efficiency of pipes, films, cables and other plastics and rubbers, and have broad prospects for development and utilization.
传统合成线性聚乙烯的方法包括使用Ziegler-Natta催化剂(Chem.Rev.,2000,100,1169)和Phillips催化剂(Chem.Rev.,1996，96，3327)等，如1939年采用高压聚合技术生产出了聚乙烯蜡；1953年之后则可采用低压齐格勒法制备；自20世纪90年代初开始，采用最新一代茂金属催化剂引发合成的方法生产。这也说明了烯烃聚合催化剂的设计和开发，是进一步发展聚乙烯产品的关键。但因受到合成工艺的限制，所得聚乙烯主链往往带有一些支链，且聚合物的相关分子量分布达不到很窄的需求。因此，研究者们将目光投向后过渡金属铁钴配合物催化剂，因其优异的性能和所得聚合物高度线性的特性备受关注。Traditional methods of synthesizing linear polyethylene include the use of Ziegler-Natta catalysts (Chem.Rev., 2000, 100, 1169) and Phillips catalysts (Chem.Rev., 1996, 96, 3327), etc., such as the production of high-pressure polymerization technology in 1939 Polyethylene wax was produced; after 1953, it could be prepared by the low-pressure Ziegler method; since the early 1990s, it was produced by the latest generation of metallocene catalyst-induced synthesis. This also shows that the design and development of olefin polymerization catalysts is the key to the further development of polyethylene products. However, due to the limitation of the synthesis process, the obtained polyethylene main chain often has some branches, and the relevant molecular weight distribution of the polymer cannot meet the very narrow requirement. Therefore, researchers have turned their attention to late-transition metal iron-cobalt complex catalysts, which have attracted much attention because of their excellent performance and highly linear characteristics of the resulting polymers.
一直以来，发明人课题组通过使用更简单、便宜和高效的合成策略，对配合物骨架结构上位阻和电子效应的调控，和聚合物的分子量和微观结构等进行合理的调控和剪裁。具体来讲，发明人课题组在研究中发现以后过渡金属铁和钴为中心的金属配合物可以高活性地催化乙烯聚合(如式1中的A–E)，获得低分子量的乙烯齐聚产物或者较窄分布的高度线性聚乙烯。如铁配合物A(R1＝R2＝H)显示出极高的乙烯齐聚活性(达4.91×106g·mol-1(Fe)·h-1)，且生成的α-烯烃具有高选择性(>94％)并符合Schulz-Flory分布(Organometallics 2006,25,666-677)。该催化剂已用于每年500吨的制备α-烯烃的中式反应中。For a long time, the inventor's research group has used simpler, cheaper and more efficient synthetic strategies to reasonably regulate and tailor the regulation of steric hindrance and electronic effects on the skeleton structure of the complex, as well as the molecular weight and microstructure of the polymer. Specifically, the inventors’ research group found that metal complexes centered on post-transition metal iron and cobalt can catalyze ethylene polymerization (such as A–E in formula 1) with high activity and obtain low molecular weight ethylene oligomerization products Or a narrower distribution of highly linear polyethylene. For example, iron complex A (R 1 ＝R 2 ＝H) shows extremely high ethylene oligomerization activity (up to 4.91×10 6 g·mol -1 (Fe)·h -1 ), and the generated α-olefin has High selectivity (>94%) and fits the Schulz-Flory distribution (Organometallics 2006, 25, 666-677). The catalyst has been used in the Chinese reaction of 500 tons per year for the preparation of α-olefins.
发明人课题组报道的不同数目烷基稠环吡啶二亚胺类铁、钴配合物(如式1中的B–E)。其中带有双边并七元环结构(式1，B，Eur.J.Inorg.Chem.,2016,2016,1748-1755；Polymer,2018,149,45；Appl.Organomet.Chem.,2020,34)在以MAO或者MMAO为助催化剂时，催化体系可以在70℃或者80℃条件下催化乙烯聚合得到一系列不同分子量的、较窄分布的不饱和线性聚乙烯，活性几乎都能达到107g·mol-1(Fe/Co)·h-1。吡啶并六元环结构的2,8-二芳基亚胺-5,6,7-三氢喹啉类铁配合物(式1，C，n＝1，Organometallics,2012,31,5039-5048)，其最高活性在50℃时可达2.4×107g·mol-1(Fe)·h-1，分子量在1–10kg mol-1之间；其钴配合物(Appl.Catal.,A.2012,447-448,67-73)也表现出很高的催化乙烯聚合活性，该体系的最高活性在60℃时可达到1.09×107g·mol-1(Co)·h-1，聚合产物为窄分子量分布的聚乙烯蜡。带有七元环稠环吡啶衍生物的2,9-二亚胺芳基-5,6,7,8-四氢环庚烯并吡啶类铁配合物C(n＝2)，当R为甲基时(Dalton Trans.,2014,43,16818-16829)，其对乙烯聚合表现出最高可达1.56×107g·mol-1(Fe)·h-1的催化活性，得到的聚乙烯产品具有窄分子量分布(PDI～7)的特点。当R为苯基时(J.Polym.Sci.Part A.Polym.Chem.2017,55,830-842)显示出高的热稳定性和较长的使用寿命，在80℃这种工业应用的操作温度，活性依然可以达到6.87×106g·mol-1(Fe)·h-1。所得的产物是低分子量的聚乙烯蜡。而其钴配合物，无论R式甲基还是苯基均表现为高度线性、具有端基双键的聚乙烯蜡。Different numbers of alkyl fused ring pyridine diimine iron and cobalt complexes (such as B-E in formula 1) reported by the inventor's research group. Which has a double-sided and seven-membered ring structure (
在N-芳基上引入邻环烷基后也表现出了高效催化乙烯聚合生成高度线性聚乙烯的能力。其中，基于单边含柔性七元环的二芳基亚胺吡啶骨架的钴配合物E，当用MAO或MMAO作为助催化剂时，其最佳实验温度为50℃，最佳活性为4.09×106g·mol-1(Co)·h-1，最终产生高度线性(Tm>130℃)、具有窄分散性(Mw/Mn范围：2.0–3.9)、含端基双键的线性聚乙烯(分子量范围：9.78–25.6kg mol–1)(Molecules,2019,24,1176)。而单边并六元环吡啶类钴配合物D表现出高达1.71×106g·mol-1(Co)·h-1的催化活性，生成高度线性、低分子量(～1.50kg mol-1)和窄分散性(Mw/Mn范围：1.1–2.4)的聚乙烯蜡；即使在90℃的反应温度下，其催化活性仍可达6.75×106g·mol-1(Co)·h-1(Polymer,2021,213,123294)。The introduction of o-cycloalkyl groups on the N-aryl group also showed the ability to efficiently catalyze the polymerization of ethylene to produce highly linear polyethylene. Among them, the cobalt complex E based on a diarylimine pyridine skeleton containing a flexible seven-membered ring on one side, when MAO or MMAO is used as a cocatalyst, its optimal experimental temperature is 50 °C, and its optimal activity is 4.09×10 6 g·mol -1 (Co)·h -1 , resulting in highly linear (T m >130°C), narrow dispersion (M w /M n range: 2.0–3.9), and terminal double bond-containing linear Polyethylene (molecular weight range: 9.78–25.6 kg mol –1 ) (Molecules, 2019, 24, 1176). On the other hand, the unilateral six-membered ring pyridine cobalt complex D exhibits a catalytic activity as high as 1.71×10 6 g·mol -1 (Co)·h -1 , forming a highly linear, low molecular weight (~1.50kg mol -1 ) Polyethylene wax with narrow dispersion (M w /M n range: 1.1–2.4); even at a reaction temperature of 90 °C, its catalytic activity can still reach 6.75×10 6 g·mol -1 (Co)·h -1 (Polymer, 2021, 213, 123294).
纵观烯烃聚合催化剂的发展，后过渡金属配合物催化剂作为新型乙烯聚合催化剂体系，仍然存在一些基础研究的难点和推进工业化的制约因素。目前，如何获得热稳定性较好的高活性乙烯聚合催化剂以适应工业化生产成为学者研究的核心内容，亦是能否尽快推进工业化的关键。在课题组已有的环烷基稠环吡啶类铁、钴等配合物的研究基础上，开发新的高效乙烯聚合催化剂具有推进研究进展、适应工业化需求的研究价值。Throughout the development of olefin polymerization catalysts, late transition metal complex catalysts, as a new type of ethylene polymerization catalyst system, still have some difficulties in basic research and constraints to promote industrialization. At present, how to obtain a highly active ethylene polymerization catalyst with better thermal stability to adapt to industrial production has become the core content of scholars' research, and it is also the key to advancing industrialization as soon as possible. On the basis of the research group's existing research on cycloalkyl fused ring pyridine complexes such as iron and cobalt, the development of new high-efficiency ethylene polymerization catalysts has the research value of advancing research progress and meeting the needs of industrialization.
发明内容Contents of the invention
为了改善现有技术问题，本发明提供了一种含大位阻取代基的不对称六元环吡啶亚胺过渡金属配合物及其制备方法与应用。In order to improve the problems in the prior art, the present invention provides an asymmetric six-membered ring pyridine imine transition metal complex containing large steric hindrance substituents, its preparation method and application.
本发明的技术方案为：一种含大位阻取代基的不对称六元环吡啶亚胺配合物，其结构式如下式(I)所示：The technical scheme of the present invention is: an asymmetric six-membered ring pyridine imine complex containing large sterically hindered substituents, the structural formula of which is shown in the following formula (I):
式(I)中，M选自金属，优选为过渡金属，例如Fe、Co、Ni；In formula (I), M is selected from metals, preferably transition metals, such as Fe, Co, Ni;
R5、R6、R7相同或不同，各自独立地选自H、F、Cl、Br、I、NO2、无取代或者任选被一个或多个Ra取代的下列基团：C1-6烷基、C1-6烷氧基、C3-10环烷基、3-10元杂环基、C3-10环烷基氧基、C6-20芳基、C6-20芳基氧基、C6-20芳基C1-6烷基、或二C6-20芳基C1-6烷基；R 5 , R 6 , and R 7 are the same or different, each independently selected from the following groups: H, F, Cl, Br, I, NO 2 , unsubstituted or optionally substituted by one or more R a : C 1 -6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, 3-10 membered heterocyclyl, C 3-10 cycloalkyloxy, C 6-20 aryl, C 6-20 Aryloxy, C 6-20 aryl C 1-6 alkyl, or two C 6-20 aryl C 1-6 alkyl;
R、R1、R4相同或不同，各自独立地选自H、F、Cl、Br、I、NO2、无取代或任选被一个或多个Rb取代的下列基团：C1-6烷基、C1-6烷氧基、C3-10环烷基、3-10元杂环基、C6-20芳基、C6-20芳基氧基、C6-20芳基C1-6烷基、或二C6-20芳基C1-6烷基；且R、R1、R4中至少两个基团为无取代或任选被一个或多个Rb取代的下列基团：C3-10环烷基、3-10元杂环基、C6-20芳基、C6-20芳基氧基、C6-20芳基C1-6烷基、或二C6-20芳基C1-6烷基；R, R 1 , R 4 are the same or different, each independently selected from H, F, Cl, Br, I, NO 2 , the following groups that are unsubstituted or optionally substituted by one or more R b : C 1- 6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, 3-10 membered heterocyclyl, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, or diC 6-20 aryl C 1-6 alkyl; and at least two of R, R 1 , R 4 are unsubstituted or optionally substituted by one or more R b The following groups: C 3-10 cycloalkyl, 3-10 membered heterocyclic group, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, Or two C 6-20 aryl C 1-6 alkyl;
R2、R3相同或不同，各自独立地选自H、F、Cl、Br、I、NO2、无取代或者任选被一个或多个Rc取代的下列基团：C1-6烷基、C1-6烷氧基、C3-10环烷基、3-10元杂环基、C3-10环烷基氧基；R 2 and R 3 are the same or different, each independently selected from the following groups: H, F, Cl, Br, I, NO 2 , unsubstituted or optionally substituted by one or more R c : C 1-6 alkane Base, C 1-6 alkoxy, C 3-10 cycloalkyl, 3-10 membered heterocyclyl, C 3-10 cycloalkyloxy;
每一个X相同或不同，各自独立地选自F、Cl、Br、I；Each X is the same or different, each independently selected from F, Cl, Br, I;
Ra、Rb、Rc相同或不同，各自独立的选自H、F、Cl、Br、I、C1-6烷基、C1-6烷氧基、C3-10环烷基、C3-10环烷氧基、C6-20芳基、C6-20芳基氧基或C6-20芳基C1-6烷基。R a , R b , and R c are the same or different, each independently selected from H, F, Cl, Br, I, C 1-6 alkyl, C 1-6 alkoxy, C 3-10 cycloalkyl, C 3-10 cycloalkoxy, C 6-20 aryl, C 6-20 aryloxy or C 6-20 aryl C 1-6 alkyl.
根据本发明的实施方案，R2、R3相同或不同，彼此独立地选自H、F、Cl、Br、I或C1-3烷基；更优选均为H。According to an embodiment of the present invention, R 2 and R 3 are the same or different, and are independently selected from H, F, Cl, Br, I or C 1-3 alkyl; more preferably both are H.
根据本发明的实施方案，R、R1、R4中至少两个基团为无取代或任选被一个或多个Rb取代的下列基团：C3-10环烷基、C6-20芳基、C6-20芳基C1-6烷基、或二C6-20芳基C1-6烷基。According to an embodiment of the present invention, at least two of R, R 1 , and R 4 are the following groups that are unsubstituted or optionally substituted by one or more R b : C 3-10 cycloalkyl, C 6- 20 aryl, C 6-20 aryl C 1-6 alkyl, or diC 6-20 aryl C 1-6 alkyl.
根据本发明的实施方案，R、R1、R4相同或不同，各自独立地为无取代或任选被一个或多个Rb取代的下列基团：C3-10环烷基、3-10元杂环基、C6-20芳基、C6-20芳基氧基、C6-20芳基C1-6烷基、或二C6-20芳基C1-6烷基。According to an embodiment of the present invention, R, R 1 , and R 4 are the same or different, and each independently represents the following groups that are unsubstituted or optionally substituted by one or more R b : C 3-10 cycloalkyl, 3- 10-membered heterocyclic group, C 6-20 aryl, C 6-20 aryloxy, C 6-20 aryl C 1-6 alkyl, or diC 6-20 aryl C 1-6 alkyl.
根据本发明的实施方案，R、R1、R4相同或不同，各自独立地为无取代或任选被一个或多个Rb取代的下列基团：C3-10环烷基、C6-20芳基、C6-20芳基C1-6烷基、或二C6-20芳基C1-6烷基。According to an embodiment of the present invention, R, R 1 , and R 4 are the same or different, and each independently represents the following groups that are unsubstituted or optionally substituted by one or more R b : C 3-10 cycloalkyl, C 6 -20 aryl, C 6-20 aryl C 1-6 alkyl, or di-C 6-20 aryl C 1-6 alkyl.
根据本发明的实施方案，R、R1、R4相同或不同，彼此独立地选自F、Cl、Br、I、NO2、OMe、CF3、C1-6烷基、C3-10环烷基、C6-20芳基C1-6烷基、二C6-20芳基C1-6烷基(如二C6-20芳基C1-3烷基)；According to an embodiment of the present invention, R, R 1 , and R 4 are the same or different, and are independently selected from F, Cl, Br, I, NO 2 , OMe, CF 3 , C 1-6 alkyl, C 3-10 Cycloalkyl, C 6-20 aryl C 1-6 alkyl, di-C 6-20 aryl C 1-6 alkyl (such as di-C 6-20 aryl C 1-3 alkyl);
根据本发明的实施方案，R、R1、R4相同或不同，彼此独立地选自F、Cl、甲基、环戊基、环己基、环辛基、二苯甲基。According to an embodiment of the present invention, R, R 1 , and R 4 are the same or different, and are independently selected from F, Cl, methyl, cyclopentyl, cyclohexyl, cyclooctyl, and benzhydryl.
根据本发明的实施方案，每一个X可以独立地选自Cl或Br，具体可选自Cl。According to an embodiment of the present invention, each X may be independently selected from Cl or Br, specifically Cl.
根据本发明的实施方案，R5、R6、R7相同或不同，彼此独立地选自H、F、Cl、Br、I、或C1-6烷基；具体可选自H或Cl。According to an embodiment of the present invention, R 5 , R 6 , and R 7 are the same or different, and are independently selected from H, F, Cl, Br, I, or C 1-6 alkyl; specifically, they can be selected from H or Cl.
Ra、Rb、Rc相同或不同，各自独立的选自H、F、Cl、C1-3烷基、C3-10环烷基、C6-12芳基。R a , R b , and R c are the same or different, each independently selected from H, F, Cl, C 1-3 alkyl, C 3-10 cycloalkyl, and C 6-12 aryl.
本发明具体实例中，所述式(I)所示的配合物为如下配合物：In the specific example of the present invention, the complex shown in the formula (I) is the following complex:
配合物Co-1：其中M为Co，R＝环戊基(C5H9)，R1＝甲基，R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-1: where M is Co, R = cyclopentyl (C 5 H 9 ), R 1 = methyl, R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 and R 7 are H;
配合物Co-2：其中，M为Co，R＝二苯甲基(CHPh2)，R1＝甲基，R4＝环戊基(C5H9)，R2、R3、R5、R6、R7为H；Complex Co-2: where, M is Co, R = benzhydryl (CHPh 2 ), R 1 = methyl, R 4 = cyclopentyl (C 5 H 9 ), R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Co-3：其中，M为Co，R＝环戊基(C5H9)，R1＝二苯甲基(CHPh2)，R4＝甲基，R2、R3、R5、R6、R7为H；Complex Co-3: where M is Co, R = cyclopentyl (C 5 H 9 ), R 1 = benzhydryl (CHPh 2 ), R 4 = methyl, R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Co-4：其中，M为Co，R＝环戊基(C5H9)，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-4: where M is Co, R = cyclopentyl (C 5 H 9 ), R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 is H;
配合物Co-5：其中，M为Co，R＝环己基(C6H11)，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-5: wherein, M is Co, R = cyclohexyl (C 6 H 11 ), R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R7 is H;
配合物Co-6：其中，M为Co，R＝环辛基(C8H15)，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-6: where M is Co, R = cyclooctyl (C 8 H 15 ), R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 is H;
配合物Co-7：其中，M为Co，R＝甲基，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-7: where M is Co, R = methyl, R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Co-8：其中，M为Co，R＝F，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-8: wherein, M is Co, R=F, R 1 =R 4 =benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , and R 7 are H;
配合物Co-9：其中，M为Co，R＝Cl，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Co-9: wherein, M is Co, R=Cl, R 1 =R 4 =benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , and R 7 are H;
配合物Fe-1：其中，M为Fe，R＝环戊基(C5H9)，R1＝甲基，R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Fe-1: where M is Fe, R = cyclopentyl (C 5 H 9 ), R 1 = methyl, R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Fe-2：其中，M为Fe，R＝二苯甲基(CHPh2)，R1＝甲基，R4＝环戊基(C5H9)，R2、R3、R5、R6、R7为H；Complex Fe-2: where, M is Fe, R = benzhydryl (CHPh 2 ), R 1 = methyl, R 4 = cyclopentyl (C 5 H 9 ), R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Fe-3：其中，M为Fe，R＝环戊基(C5H9)，R1＝二苯甲基(CHPh2)，R4＝甲基，R2、R3、R5、R6、R7为H；Complex Fe-3: where M is Fe, R = cyclopentyl (C 5 H 9 ), R 1 = benzhydryl (CHPh 2 ), R 4 = methyl, R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Fe-4：其中，M为Fe，R＝环戊基(C5H9)，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Fe-4: where M is Fe, R = cyclopentyl (C 5 H 9 ), R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 is H;
配合物Fe-5：其中，M为Fe，R＝环己基(C6H11)，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Fe-5: where M is Fe, R = cyclohexyl (C 6 H 11 ), R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R7 is H;
配合物Fe-6：其中，M为Fe，R＝环辛基(C8H15)，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Fe-6: where M is Fe, R = cyclooctyl (C 8 H 15 ), R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 is H;
配合物Fe-7：其中，M为Fe，R＝甲基，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Fe-7: wherein, M is Fe, R = methyl, R 1 = R 4 = benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , R 7 are H;
配合物Fe-8：其中，M为Fe，R＝F，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H；Complex Fe-8: wherein, M is Fe, R=F, R 1 =R 4 =benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , and R 7 are H;
配合物Fe-9：其中，M为Fe，R＝Cl，R1＝R4＝二苯甲基(CHPh2)，R2、R3、R5、R6、R7为H。Complex Fe-9: wherein, M is Fe, R=Cl, R 1 =R 4 =benzhydryl (CHPh 2 ), R 2 , R 3 , R 5 , R 6 , and R 7 are H.
本发明还提供上述式(I)所示配合物的制备方法，包括：将式(II)所示化合物、MX2及式(III)所示的苯胺化合物进行反应，得到式(I)所示化合物，The present invention also provides a preparation method for the compound represented by the above formula (I), comprising: reacting the compound represented by the formula (II), MX2 and the aniline compound represented by the formula (III) to obtain the compound represented by the formula (I) compound,
其中，R、R1、R2、R3、R4、R5、R6、R7、M、X具有上文所述定义。Wherein, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , M, and X have the above-mentioned definitions.
根据本发明，所述反应可以为模板反应；According to the present invention, the reaction may be a template reaction;
根据本发明的制备方法，所述MX2选自含铁或钻的卤化物、所述卤化物的水合物或其他溶剂合物中的一种或多种，例如可以为FeCl2、FeCl2·4H2O或CoCl2·6H2O中的一种或多种。According to the preparation method of the present invention, the MX 2 is selected from one or more of iron or cobalt-containing halides, hydrates or other solvates of the halides, for example, FeCl 2 , FeCl 2 . One or more of 4H 2 O or CoCl 2 ·6H 2 O.
根据本发明的制备方法，所述式(III)所示的苯胺化合物还可以采用其盐酸盐。According to the preparation method of the present invention, the aniline compound represented by the formula (III) can also use its hydrochloride.
根据本发明，所述式(II)化合物、MX2或其水合物及式(III)所示的苯胺化合物或其盐酸盐的投料摩尔比为1.0:(0.5～4.0):(0.9～2.5)，例如为1:1:2.2。According to the present invention, the molar ratio of the compound of formula (II), MX2 or its hydrate and the aniline compound represented by formula (III) or its hydrochloride is 1.0:(0.5～4.0):(0.9～2.5 ), for example 1:1:2.2.
根据本发明，所述反应的温度为100～160℃，例如为130℃；时间为6～12小时，例如为8小时。According to the present invention, the temperature of the reaction is 100-160°C, such as 130°C; the time is 6-12 hours, such as 8 hours.
根据本发明，所述反应可以在有机溶剂中进行；例如，所述有机溶剂可以为乙酸。According to the present invention, the reaction may be carried out in an organic solvent; for example, the organic solvent may be acetic acid.
根据本发明，所述反应优选在惰性气体氛围中进行，例如在氮气氛围下进行。According to the invention, the reaction is preferably carried out under an inert gas atmosphere, for example under a nitrogen atmosphere.
优选地，所得式(I)所示的化合物可以进一步纯化，所述纯化方法可以包括如下步骤：Preferably, the compound shown in the gained formula (I) can be further purified, and the purification method can include the following steps:
a)将含式(I)所示化合物的反应产物浓缩，然后加入溶剂，产生沉淀；a) Concentrating the reaction product containing the compound represented by formula (I), and then adding a solvent to produce a precipitate;
b)将步骤a)的产物固液分离(例如过滤)，取固相，用溶剂洗涤，干燥。b) separating the solid and liquid of the product in step a) (for example, filtering), taking the solid phase, washing with a solvent, and drying.
根据本发明，所述溶剂可以为无水乙醚。According to the present invention, the solvent may be anhydrous diethyl ether.
本发明还提供了上述式(I)所示的配合物的用途，应用于催化烯烃聚合反应。The present invention also provides the use of the complex represented by the above formula (I) for catalyzing olefin polymerization.
本发明中，上述式(I)所示的配合物具体可应用于催化乙烯聚合反应中。In the present invention, the complex represented by the above formula (I) can be specifically applied to catalyze ethylene polymerization.
本发明还提供一种催化剂组合物，其包括主催化剂以及任选存在或不存在的助催化剂，其中，所述主催化剂选自本发明所述的式(I)所示的配合物。The present invention also provides a catalyst composition, which includes a main catalyst and an optional or non-existing co-catalyst, wherein the main catalyst is selected from the complexes represented by the formula (I) described in the present invention.
根据本发明，所述催化剂组合物，包括主催化剂和助催化剂。According to the present invention, the catalyst composition includes a main catalyst and a co-catalyst.
根据本发明，当存在助催化剂时，所述助催化剂可以选自铝氧烷、烷基铝、氯化烷基铝中的一种或多种。具体的，所述烷基铝和氯化烷基铝中烷基选自碳原子数1～3的烷基。According to the present invention, when there is a co-catalyst, the co-catalyst may be selected from one or more of aluminoxane, alkylaluminum, and alkylaluminum chloride. Specifically, the alkyl group in the alkylaluminum and alkylaluminum chloride is selected from alkyl groups with 1 to 3 carbon atoms.
根据本发明，所述铝氧烷可以选自甲基铝氧烷(MAO)或三异丁基铝改性的甲基铝氧烷(MMAO)中的一种或两种；所述氯化烷基铝可以选自氯化二乙基铝(Et2AlCl)、氯化二甲基铝(Me2AlCl)中的一种或两种。According to the present invention, the aluminoxane can be selected from one or both of methylalumoxane (MAO) or triisobutylaluminum-modified methylalumoxane (MMAO); Aluminum can be selected from one or both of diethylaluminum chloride (Et 2 AlCl) and dimethylaluminum chloride (Me 2 AlCl).
本发明中，所述所述助催化剂中的金属Al与主催化剂的中心金属M的摩尔比为500～4000:1。例如可以为500:1、1000:1、2000:1、3000:1、4000:1。In the present invention, the molar ratio of the metal Al in the co-catalyst to the central metal M of the main catalyst is 500-4000:1. For example, it can be 500:1, 1000:1, 2000:1, 3000:1, 4000:1.
本发明中，所述助催化剂中的金属Al与式(I)所示的配合物的中心金属(具体如Co)的摩尔比为(500～4000):1，优选摩尔比为(1000～3000):1，具体可为1000:1、1250:1、1500:1、1750:1、2000:1、2250:1、2500:1、2750:1、3000:1。In the present invention, the molar ratio of the metal Al in the cocatalyst to the center metal (specifically as Co) of the complex represented by formula (I) is (500～4000):1, preferably the molar ratio is (1000～3000 ):1, specifically 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1.
优选地，当所述助催化剂为甲基铝氧烷(MAO)时，甲基铝氧烷(MAO)中的金属Al与式(I)所示的配合物的中心金属(具体如Co)的摩尔比可为(1000～3000):1，更优选摩尔比为1750:1。例如可以为1000:1、1250:1、1500:1、1750:1、2000:1、2250:1、2500:1、2750:1、3000:1。Preferably, when the cocatalyst is methylaluminoxane (MAO), the metal Al in methylaluminoxane (MAO) and the central metal (specifically as Co) of the complex shown in formula (I) The molar ratio may be (1000-3000):1, more preferably 1750:1. For example, it can be 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1.
优选地，当所述助催化剂为三异丁基铝改性的甲基铝氧烷(MMAO)时，三异丁基铝改性的甲基铝氧烷(MMAO)中的金属Al与式(I)所示的配合物的中心金属(具体如Co)的摩尔比为(1000～3000):1，例如可以为1000:1、1250:1、1500:1、1750:1、2000:1、2250:1、2500:1、2750:1、3000:1；更优选摩尔比为2250:1。Preferably, when the cocatalyst is triisobutylaluminum modified methylalumoxane (MMAO), the metal Al in the triisobutylaluminum modified methylalumoxane (MMAO) and the formula ( The molar ratio of the central metal (such as Co) of the complex shown in I) is (1000-3000):1, for example, it can be 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1; more preferably the molar ratio is 2250:1.
本发明进一步提供了一种烯烃聚合物的制备方法，包括如下步骤：在上述式(I)所示的配合物或上述的催化剂组合物的作用下，催化烯烃进行聚合反应，得到烯烃聚合物。优选的，所述聚合反应的温度为30～100℃，具体可为30℃、40℃、50℃、60℃、70℃、80℃、90℃；优选为40～90℃；The present invention further provides a method for preparing an olefin polymer, comprising the following steps: under the action of the complex represented by the above formula (I) or the above catalyst composition, catalyzing the polymerization reaction of olefin to obtain an olefin polymer. Preferably, the temperature of the polymerization reaction is 30-100°C, specifically 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C; preferably 40-90°C;
根据本发明，所述聚合反应的时间为5～60min，具体可为30min；According to the present invention, the time for the polymerization reaction is 5 to 60 minutes, specifically 30 minutes;
根据本发明，所述聚合反应的压力为0.5～10atm，具体可为10atm。According to the present invention, the pressure of the polymerization reaction is 0.5-10 atm, specifically 10 atm.
根据本发明，所述烯烃可为乙烯，即所述聚合反应在乙烯气氛下进行。According to the present invention, the olefin may be ethylene, ie the polymerization reaction is carried out under an ethylene atmosphere.
有益效果Beneficial effect
1、本发明提供了一类可用于制备高度线性聚乙烯的高热稳定的含大位阻环烷基和二苯甲基的不对称六元环吡啶亚胺基过渡金属配合物的制备方法。该类化合物的制备过程具有反应条件温和、周期短、操作条件简单等优点。1. The present invention provides a method for preparing a kind of highly thermally stable asymmetric six-membered ring pyridine imine transition metal complex containing bulky cycloalkyl group and benzhydryl group, which can be used to prepare highly linear polyethylene. The preparation process of this type of compound has the advantages of mild reaction conditions, short cycle time, simple operation conditions and the like.
2、本发明提供了含大位阻环烷基和二苯甲基的不对称六元环吡啶亚胺基过渡金属配合物的用途；可作为催化剂应用于乙烯聚合反应，其反应活性高，且对聚乙烯分子量具有极强的调控性能，可用于制备高度线性聚乙烯。本发明配合物的结构有利地稳定了中心金属更强的正电特点，更强的路易斯酸性，提高了乙烯插入的几率，使该体系具有更高的催化活性及稳定性。该类催化剂制备所得的聚乙烯重均分子量Mw在1.1–101.6kg·mol-1之间波动，分子量分布介于2–19.8之间，可用做制备特种高端商业用聚乙烯产品。同时改变取代基的取代位置、位阻及电子效应，能极大范围调控所得聚乙烯的分子量。2. The present invention provides the use of an asymmetric six-membered ring pyridine imine-based transition metal complex containing a large sterically hindered cycloalkyl group and a benzhydryl group; it can be used as a catalyst for ethylene polymerization, with high reactivity and It has a strong ability to regulate the molecular weight of polyethylene and can be used to prepare highly linear polyethylene. The structure of the complex of the present invention advantageously stabilizes the stronger electropositive characteristics of the central metal, stronger Lewis acidity, increases the probability of ethylene insertion, and makes the system have higher catalytic activity and stability. The weight-average molecular weight M w of polyethylene prepared by this type of catalyst fluctuates between 1.1-101.6kg·mol -1 , and the molecular weight distribution is between 2-19.8, which can be used to prepare special high-end commercial polyethylene products. At the same time, changing the substitution position, steric hindrance and electronic effect of the substituent can regulate the molecular weight of the obtained polyethylene in a large range.
3、本发明提供的不对称六元环吡啶亚胺基过渡金属配合物在催化乙烯聚合中，表现出极高的热稳定性。该类配合物催化剂在较高温度下(80℃至100℃)仍可以保持较高的持久的活性，符合工业生产的操作温度，具有广泛的工业应用前景。3. The asymmetric six-membered ring pyridine imine transition metal complex provided by the present invention exhibits extremely high thermal stability in catalyzing ethylene polymerization. The catalyst of this kind of complex can still maintain high and persistent activity at relatively high temperature (80° C. to 100° C.), conforms to the operating temperature of industrial production, and has wide industrial application prospects.
4、本发明提供的制备聚乙烯的方法操作简单，反应条件易于控制，得到的产品具有可调控的分子量和熔点(熔点均大于120℃)。尤其是对于部分大位阻铁配合物催化剂，其催化乙烯聚合可得窄分子量分布(PDI值<2.0)的低分子量聚乙烯蜡，分子量在一千上下，最底可至550g·mol-1，分子量远低于以往合成的聚合物。同时其表现出含有端基双键的高度线性聚乙烯的特征，可用作薄膜、纤维和各类管材等，在生产长链共聚物、功能性聚合物和涂层材料方面显示出潜在应用。4. The method for preparing polyethylene provided by the present invention is simple to operate, the reaction conditions are easy to control, and the obtained product has adjustable molecular weight and melting point (both melting points are greater than 120° C.). Especially for some large steric hindrance iron complex catalysts , it can catalyze ethylene polymerization to obtain low molecular weight polyethylene wax with narrow molecular weight distribution (PDI value<2.0). The molecular weight is much lower than that of previously synthesized polymers. At the same time, it shows the characteristics of highly linear polyethylene containing terminal double bonds, which can be used as films, fibers and various pipes, etc., and shows potential applications in the production of long-chain copolymers, functional polymers and coating materials.
5、在本发明的配合物结构中，含有大位阻环烷烃和二苯甲基取代基，是一类新型的柔性六元环吡啶亚胺催化剂。由于邻位大体积取代基的空间位阻效应，使得芳基亚胺平面与配位平面形成的二面角接近90°，基本处于垂直位置，可以对金属活性中心形成有效保护；因此，本发明中所述配合物活性高，且性质稳定、催化寿命长。5. In the complex structure of the present invention, it contains large sterically hindered cycloalkane and benzhydryl substituents, and is a new type of flexible six-membered ring pyridine imine catalyst. Due to the steric hindrance effect of the bulky substituent at the adjacent position, the dihedral angle formed by the aryl imine plane and the coordination plane is close to 90°, which is basically in a vertical position, and can effectively protect the metal active center; therefore, the present invention The complex described in has high activity, stable properties and long catalytic life.
术语定义与说明Definition and Explanation of Terms
本发明中，术语“C1-6烷基”指具有1-6个碳原子的直链或支链烷基，所述烷基例如为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基。In the present invention, the term "C 1-6 alkyl" refers to a straight chain or branched chain alkyl having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl Base, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl.
术语“C1-6烷氧基”应当理解为意指式-O-烷基的直链或者支链的饱和一价烃基，其中术语“C1-6烷基”具有上述定义，例如为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基或其异构体。特别地，“烷氧基”为“C1-4烷氧基”、“C1-3烷氧基”，优选为甲氧基、乙氧基或丙氧基。进一步优选为“C1-2烷氧基”，特别是甲氧基或乙氧基。The term "C 1-6 alkoxy" should be understood as meaning a linear or branched saturated monovalent hydrocarbon group of the formula -O-alkyl, wherein the term "C 1-6 alkyl" has the above definition, for example, methyl oxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy or its isomers. In particular, "alkoxy" is "C 1-4 alkoxy", "C 1-3 alkoxy", preferably methoxy, ethoxy or propoxy. Further preferred is "C 1-2 alkoxy", especially methoxy or ethoxy.
术语“C3-10环烷基”应当理解为意指直链或者支链的饱和一价单环烃环，其含有例如3、4、5、6、7、8、9或10个碳原子。C3-8环烷基例如为单环烃环，例如环丙基、环丁基、环戊基、环己基、环庚基或环辛基。特别地，所述环烷基为C4-6环烷基、C5-6环烷基或环己基。例如，术语“C3-6环烷基”应理解为优选意指饱和一价单环烃环，其含有例如3、4、5或6个碳原子。具体而言，C3-6环烷基为单环烃环，例如环丙基、环丁基、环戊基或环己基。The term "C 3-10 cycloalkyl" is understood to mean a linear or branched saturated monovalent monocyclic hydrocarbon ring containing, for example, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms . C 3-8 cycloalkyl is, for example, a monocyclic hydrocarbon ring, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. In particular, the cycloalkyl is C 4-6 cycloalkyl, C 5-6 cycloalkyl or cyclohexyl. For example, the term "C 3-6 cycloalkyl" is understood to preferably mean a saturated monovalent monocyclic hydrocarbon ring containing, for example, 3, 4, 5 or 6 carbon atoms. Specifically, C 3-6 cycloalkyl is a monocyclic hydrocarbon ring, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
术语“C3-10环烷基氧基”应理解为意指式-O-环烷基的基团，其中术语“C3-10环烷基”具有如上所述的定义。The term "C 3-10 cycloalkyloxy" is understood to mean a group of the formula -O-cycloalkyl, wherein the term "C 3-10 cycloalkyl" has the meaning defined above.
术语“3-10元杂环基”意指饱和的一价单环或双环烃环，其包含1-5个，优选1-3个选自N、O和S的杂原子。所述杂环基可以通过所述碳原子中的任一个或氮原子(如果存在的话)与分子的其余部分连接。特别地，所述杂环基可以包括但不限于：4元环，如氮杂环丁烷基、氧杂环丁烷基；5元环，如四氢呋喃基、二氧杂环戊烯基、吡咯烷基、咪唑烷基、吡唑烷基、吡咯啉基；或6元环，如四氢吡喃基、哌啶基、吗啉基、二噻烷基、硫代吗啉基、哌嗪基或三噻烷基；或7元环，如二氮杂环庚烷基。任选地，所述杂环基可以是苯并稠合的。所述杂环基可以是双环的，例如但不限于5,5元环，如六氢环戊并[c]吡咯-2(1H)-基环，或者5,6元双环，如六氢吡咯并[1,2-a]吡嗪-2(1H)-基环。含氮原子的环可以是部分不饱和的，即它可以包含一个或多个双键，例如但不限于2,5-二氢-1H-吡咯基、4H-[1,3,4]噻二嗪基、4,5-二氢噁唑基或4H-[1,4]噻嗪基，或者，它可以是苯并稠合的，例如但不限于二氢异喹啉基。根据本发明，所述杂环基是无芳香性的。The term "3-10 membered heterocyclic group" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclyl group can be attached to the rest of the molecule through any of the carbon atoms or the nitrogen atom, if present. In particular, the heterocyclic group may include but not limited to: 4-membered rings, such as azetidinyl, oxetanyl; 5-membered rings, such as tetrahydrofuranyl, dioxolyl, pyrrole Alkyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or 6-membered rings such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl Or a trithianyl group; or a 7-membered ring, such as a diazepanyl group. Optionally, the heterocyclyl group may be benzo-fused. The heterocyclic group can be bicyclic, such as but not limited to 5,5-membered rings, such as hexahydrocyclopenta[c]pyrrol-2(1H)-yl rings, or 5,6-membered bicyclic rings, such as hexahydropyrrole And[1,2-a]pyrazin-2(1H)-yl ring. A ring containing a nitrogen atom may be partially unsaturated, i.e. it may contain one or more double bonds, such as but not limited to 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadi azinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, alternatively it may be benzo-fused such as but not limited to dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic.
术语“C6-20芳基”应理解为表示具有6～20个碳原子的一价芳香性或部分芳香性的单环、双环或三环烃环，优选“C6-14芳基”。术语“C6-14芳基”应理解为表示具有6、7、8、9、10、11、12、13或14个碳原子的一价芳香性或部分芳香性的单环、双环或三环烃环(“C6-14芳基”)，特别是具有6个碳原子的环(“C6芳基”)，例如苯基；或联苯基，或者是具有9个碳原子的环(“C9芳基”)，例如茚满基或茚基，或者是具有10个碳原子的环(“C10芳基”)，例如四氢化萘基、二氢萘基或萘基，或者是具有13个碳原子的环(“C13芳基”)，例如芴基，或者是具有14个碳原子的环(“C14芳基”)，例如蒽基。The term "C 6-20 aryl" should be understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably a "C 6-14 aryl". The term "C 6-14 aryl" should be understood as meaning a monovalent or partially aromatic monocyclic, bicyclic or tricyclic group having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms. Cyclohydrocarbon rings (“C 6-14 aryl”), especially rings having 6 carbon atoms (“C 6 aryl”), for example phenyl; or biphenyl, or rings having 9 carbon atoms ("C 9 aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or is a ring having 13 carbon atoms ("C 13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl"), such as anthracenyl.
术语“C6-20芳基氧基”应理解为意指式-O-芳基。The term "C 6-20 aryloxy" is understood to mean the formula -O-aryl.
附图说明Description of drawings
图1为本发明实施例1-18制备配合物的反应流程图。Fig. 1 is a reaction flow diagram for preparing complexes in Examples 1-18 of the present invention.
图2为实施例14配合物Fe-5晶体结构示意图。Fig. 2 is a schematic diagram of the crystal structure of complex Fe-5 in Example 14.
图3为实施例19i)中所得聚合物升温核磁氢谱图和核磁碳谱图。Fig. 3 is the H NMR spectrum and the C NMR spectrum of the polymer obtained in Example 19i).
具体实施方式Detailed ways
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies realized based on the above contents of the present invention are covered within the scope of protection intended by the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.
下述实施例中的浓度如无特别说明，均为摩尔浓度。The concentrations in the following examples are molar concentrations unless otherwise specified.
实施例19-47中所用甲基铝氧烷(简称MAO)和三异丁基铝改性的甲基铝氧烷甲基铝氧烷(简称MMAO)均购自美国AkzoNobel公司。下述实施例中的Al/Fe以及Al/Co均指的是助催化剂MAO或MMAO中的金属Al与所加金属配合物催化剂中Fe或Co的摩尔比，而非铝元素与金属Fe或Co的摩尔比。Both methylalumoxane (MAO for short) and triisobutylaluminum-modified methylalumoxane methylalumoxane (MMAO for short) used in Examples 19-47 were purchased from AkzoNobel, USA. Al/Fe and Al/Co in the following examples all refer to the molar ratio of the metal Al in the promoter MAO or MMAO and the Fe or Co in the metal complex catalyst added, rather than the aluminum element and the metal Fe or Co molar ratio.
实施例19-47乙烯聚合实施例中所得聚合物的分子量(Mw)均按照常规的高温GPC方法测定而得，熔点(Tm)均按照常规的DSC方法测定而得，聚合物的聚合活性均按照如下公式计算而得：聚合活性＝聚合物产量/(催化剂用量*聚合时间)。Examples 19-47 The molecular weight (M w ) of the polymers obtained in the examples of ethylene polymerization are all measured by the conventional high-temperature GPC method, and the melting points (T m ) are all measured by the conventional DSC method. The polymerization activity of the polymer All are calculated according to the following formula: polymerization activity=polymer output/(catalyst dosage*polymerization time).
下述所有合成的化合物通过红外和元素分析得到了证实。All synthesized compounds described below were confirmed by infrared and elemental analysis.
实施例1、制备下式所示2-(1-(2-环戊基-4-二苯甲基-6-甲基苯基亚胺基)乙基)-8-(2-环戊基-4-二苯甲基-6-甲基苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为环戊基，R1为甲基，R4为二苯甲基，R2、R3为氢)，Co-1Example 1, preparation of 2-(1-(2-cyclopentyl-4-benzhydryl-6-methylphenylimino) ethyl)-8-(2-cyclopentyl) shown in the following formula -4-benzhydryl-6-methylphenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclopentyl, R 1 is methyl, R 4 is di Benzyl, R 2 , R 3 are hydrogen), Co-1
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.19g(0.55mmol)2-环戊基-4-二苯甲基-6-甲基苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,67％)，即为Co-1配合物。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.19g (0.55mmol) 2-cyclopentyl-4-diphenyl Methyl-6-methylaniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, under nitrogen atmosphere, stirred and refluxed at 130°C for 4h, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. After drying, a brown powder (0.16 g, 67%) was obtained, which was the Co-1 complex.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2949(w),2865(w),1618(υC＝N,w),1489(w),1449(w),1371(w),1263(w),1240(w),1139(w),1032(w),925(w),892(w),827(w),744(w),702(s).FT-IR(KBr cm -1 ): 2949(w), 2865(w), 1618(υ C=N ,w), 1489(w), 1449(w), 1371(w), 1263(w), 1240(w), 1139(w), 1032(w), 925(w), 892(w), 827(w), 744(w), 702(s).
元素分析：C61H61Cl2CoN3(966.0)理论值：C,75.84；H,6.37；N,4.35％；实验值:C,75.41；H,5.96；N,4.17％。Elemental analysis: C 61 H 61 Cl 2 CoN 3 (966.0) Theoretical: C, 75.84; H, 6.37; N, 4.35%; Experimental: C, 75.41; H, 5.96; N, 4.17%.
实施例2、制备下式所示2-(1-(2-二苯甲基-4-环戊基-6-甲基苯基亚胺基)乙基)-8-(2-二苯甲基-4-环戊基-6-甲基苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为二苯甲基，R1为甲基，R4为环戊基，R2、R3为氢)，Co-2Example 2, preparation of 2-(1-(2-benzhydryl-4-cyclopentyl-6-methylphenylimino)ethyl)-8-(2-benzhydryl) shown in the following formula Base-4-cyclopentyl-6-methylphenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is benzhydryl, R 1 is methyl, R 4 is Cyclopentyl, R 2 , R 3 are hydrogen), Co-2
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.19g(0.55mmol)2-二苯甲基-4-环戊基-6-甲基苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.15g,63％)，Co-2。0.05g (0.25mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.19g (0.55mmol) of 2-benzhydryl-4-ring Pentyl-6-methylaniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. Brown powder (0.15 g, 63%) was obtained after drying, Co-2.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2947(w),2865(w),1621(υC＝N,w),1574(w),1490(w),1448(w),1373(m),1242(w),1215(w),1032(w),925(w),868(w),825(w),748(w),703(s).FT-IR (KBr cm -1 ): 2947(w), 2865(w), 1621(υ C=N ,w), 1574(w), 1490(w), 1448(w), 1373(m), 1242(w), 1215(w), 1032(w), 925(w), 868(w), 825(w), 748(w), 703(s).
元素分析：C61H61Cl2CoN3(966.0)理论值：C,75.84；H,6.37；N,4.35％；实验值:C,75.38；H,6.14；N,4.00％。Elemental analysis: C 61 H 61 Cl 2 CoN 3 (966.0) Theoretical: C, 75.84; H, 6.37; N, 4.35%; Experimental: C, 75.38; H, 6.14; N, 4.00%.
实施例3、制备下式所示2-(1-(2-环戊基-4-甲基-6-二苯甲基苯基亚胺基)乙基)-8-(2-环戊基-4-甲基-6-二苯甲基苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为环戊基，R1为二苯甲基，R4为甲基，R2、R3为氢)，Co-3Example 3, preparation of 2-(1-(2-cyclopentyl-4-methyl-6-benzhydrylphenylimino)ethyl)-8-(2-cyclopentyl) shown in the following formula -4-methyl-6-benzhydrylphenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclopentyl, R 1 is benzhydryl, R 4 is methyl, R 2 , R 3 are hydrogen), Co-3
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.19g(0.55mmol)2-环戊基-4-甲基-6-二苯甲基苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,67％)，Co-3。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.19g (0.55mmol) 2-cyclopentyl-4-methyl -6-Benzhydrylaniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. Brown powder (0.16 g, 67%) was obtained after drying, Co-3.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2949(w),2863(w),1619(υC＝N,w),1575(w),1496(w),1450(w),1370(w),1267(w),1241(w),1203(w),1033(w),993(w),934(w),861(w),821(w),750(w),703(w).FT-IR (KBr cm -1 ): 2949(w), 2863(w), 1619(υ C=N ,w), 1575(w), 1496(w), 1450(w), 1370(w), 1267(w), 1241(w), 1203(w), 1033(w), 993(w), 934(w), 861(w), 821(w), 750(w), 703(w).
元素分析：C61H61Cl2CoN3(966.0)理论值：C,75.84；H,6.37；N,4.35％；实验值:C,75.94；H,6.14；N,4.04％.Elemental analysis: C 61 H 61 Cl 2 CoN 3 (966.0) Theoretical value: C, 75.84; H, 6.37; N, 4.35%; Experimental value: C, 75.94; H, 6.14; N, 4.04%.
实施例4、制备下式所示2-(1-(2-环戊基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-环戊基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为环戊基，R1＝R4为二苯甲基，R2为氢，R3为氢)，Co-4Example 4, preparation of 2-(1-(2-cyclopentyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-cyclopentyl) shown in the following formula -4,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclopentyl, R 1 =R 4 is benzhydryl , R2 is hydrogen, R3 is hydrogen), Co-4
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.27g(0.55mmol)2-环戊基-4,6-二(二苯甲基)苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.17g,54％)，Co-4。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.27g (0.55mmol) 2-cyclopentyl-4,6- Bis(benzhydryl)aniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. Brown powder (0.17 g, 54%) was obtained after drying, Co-4.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2955(w),2868(w),1606(υC＝N,w),1575(w),1494(w),1448(m),1370(w),1263(w),1241(w),1077(w),1031(w),928(w),920(w),861(w),823(w),748(w),700(s).FT-IR (KBr cm -1 ): 2955(w), 2868(w), 1606(υ C=N ,w), 1575(w), 1494(w), 1448(m), 1370(w), 1263(w), 1241(w), 1077(w), 1031(w), 928(w), 920(w), 861(w), 823(w), 748(w), 700(s).
元素分析：C85H77Cl2CoN3(1270.4)理论值：C,80.36；H,6.11；N,3.31％；实验值:C,79.79；H,5.78；N,3.25％。Elemental analysis: C 85 H 77 Cl 2 CoN 3 (1270.4) Theoretical: C, 80.36; H, 6.11; N, 3.31%; Experimental: C, 79.79; H, 5.78; N, 3.25%.
实施例5、制备下式所示2-(1-(2-环己基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-环己基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为环己基，R1＝R4为二苯甲基，R2为氢，R3为氢)，Co-5Example 5, preparation of 2-(1-(2-cyclohexyl-4,6-di(benzhydryl)phenylimino)ethyl)-8-(2-cyclohexyl-4 shown in the following formula ,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclohexyl, R 1 =R 4 is benzhydryl, R 2 is hydrogen, R 3 is hydrogen), Co-5
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.28g(0.55mmol)2-环己基-4,6-二(二苯甲基)苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,56％)，Co-5。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.28g (0.55mmol) 2-cyclohexyl-4,6-di (Diphenylmethyl)aniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, the precipitate After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, precipitated by adding a large amount of ether, and the precipitate was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.18 g, 56%), Co-5 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2930(w),2853(w),1626(υC＝N,w),1605(w),1575(w),1493(w),1446(m),1369(w),1295(w),1240(w),1076(w),1031(w),967(w),924(w),884(w),830(w),746(w),701(s).FT-IR(KBr cm -1 ): 2930(w), 2853(w), 1626(υ C=N ,w), 1605(w), 1575(w), 1493(w), 1446(m), 1369(w), 1295(w), 1240(w), 1076(w), 1031(w), 967(w), 924(w), 884(w), 830(w), 746(w), 701(s).
元素分析：C87H81Cl2CoN3(1298.5)理论值：C,80.48；H,6.29；N,3.24％；实验值:C,80.11；H,6.22；N,3.22％。Elemental analysis: C 87 H 81 Cl 2 CoN 3 (1298.5) Theoretical: C, 80.48; H, 6.29; N, 3.24%; Experimental: C, 80.11; H, 6.22; N, 3.22%.
实施例6、制备下式所示2-(1-(2-环辛基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-环辛基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为环辛基，R1＝R4为二苯甲基，R2、R3为氢)，Co-6Example 6, preparation of 2-(1-(2-cyclooctyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-cyclooctyl) shown in the following formula -4,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is cyclooctyl, R 1 =R 4 is benzhydryl , R 2 , R 3 are hydrogen), Co-6
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.29g(0.55mmol)2-环辛基-4,6-二(二苯甲基)苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,54％)，Co-6。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.29g (0.55mmol) 2-cyclooctyl-4,6- Bis(benzhydryl)aniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. Brown powder (0.18 g, 54%) was obtained after drying, Co-6.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2917(w),2859(w),1624(w),1602(w),1576(w),1492(w),1447(w),1371(w),1267(w),1241(w),1075(w),1033(w),927(w),903(w),870(w),828(w),747(w),702(s).FT-IR (KBr cm -1 ): 2917(w), 2859(w), 1624(w), 1602(w), 1576(w), 1492(w), 1447(w), 1371(w), 1267(w), 1241(w), 1075(w), 1033(w), 927(w), 903(w), 870(w), 828(w), 747(w), 702(s).
元素分析：C91H89Cl2CoN3(1354.57)理论值：C,80.69；H,6.62；N,3.10％；实验值:C,80.22；H,6.43；N,3.07％。Elemental analysis: C 91 H 89 Cl 2 CoN 3 (1354.57) Theoretical: C, 80.69; H, 6.62; N, 3.10%; Experimental: C, 80.22; H, 6.43; N, 3.07%.
实施例7、制备下式所示2-(1-(2-甲基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-甲基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为甲基，R1＝R4为二苯甲基，R2、R3为氢)，Co-7Example 7, preparation of 2-(1-(2-methyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-methyl-4 ,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is methyl, R 1 =R 4 is benzhydryl, R 2 , R 3 is hydrogen), Co-7
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.24g(0.55mmol)2-甲基-4,6-二(二苯甲基)苯胺和0.06g(0.25mmol)CoCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,55％)，Co-7。0.05g (0.25mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.24g (0.55mmol) of 2-methyl-4,6-di (Diphenylmethyl)aniline and 0.06g (0.25mmol) CoCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, the precipitate After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, precipitated by adding a large amount of ether, and the precipitate was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.16 g, 55%), Co-7 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2951(w),2871(w),1624(υC＝N,w),1593(w),1550(w),1494(w),1449(w),1263(w),1236(w),1121(w),1030(w),925(w),889(w),829(w),742(w),701(s).FT-IR (KBr cm -1 ): 2951(w), 2871(w), 1624(υ C=N ,w), 1593(w), 1550(w), 1494(w), 1449(w), 1263(w), 1236(w), 1121(w), 1030(w), 925(w), 889(w), 829(w), 742(w), 701(s).
元素分析：C77H65Cl2CoN3(1162.22)理论值：C,79.58；H,5.64；N,3.62％；实验值:C,79.21；H,5.51；N,3.78％。Elemental analysis: C 77 H 65 Cl 2 CoN 3 (1162.22) Theoretical: C, 79.58; H, 5.64; N, 3.62%; Experimental: C, 79.21; H, 5.51; N, 3.78%.
实施例8、制备下式所示2-(1-(2-氟-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-氟-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为氟，R1＝R4为二苯甲基，R2、R3为氢)，Co-8Example 8. Preparation of 2-(1-(2-fluoro-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-fluoro-4,6 -Bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is fluorine, R 1 =R 4 is benzhydryl, R 2 , R 3 for hydrogen), Co-8
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.24g(0.55mmol)2-氟-4,6-二(二苯甲基)苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,62％)，Co-8。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.24g (0.55mmol) 2-fluoro-4,6-bis( Diphenylmethyl)aniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, a large amount of ether was added to precipitate, and the precipitate passed through After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added for precipitation. The precipitate was collected by filtration and washed with a large amount of diethyl ether. After drying a brown powder (0.18 g, 62%), Co-8 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2950(w),2873(w),1628(w),1602(w),1576(w),1494(w),1427(w),1366(w),1297(w),1241(w),1131(w),1031(w),1000(w),925(w),830(w),745(w),701(s).FT-IR (KBr cm -1 ): 2950(w), 2873(w), 1628(w), 1602(w), 1576(w), 1494(w), 1427(w), 1366(w), 1297(w), 1241(w), 1131(w), 1031(w), 1000(w), 925(w), 830(w), 745(w), 701(s).
元素分析：C75H59Cl2CoF2N3(1170.15)理论值：C,76.98；H,5.08；N,3.59％；实验值:C,76.49；H,4.89；N,3.65％。Elemental analysis: C 75 H 59 Cl 2 CoF 2 N 3 (1170.15) Theoretical: C, 76.98; H, 5.08; N, 3.59%; Experimental: C, 76.49; H, 4.89; N, 3.65%.
实施例9、制备下式所示2-(1-(2-氯-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-氯-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化钴(R为氯，R1＝R4为二苯甲基，R2、R3为氢)，Co-9Example 9, preparation of 2-(1-(2-chloro-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-chloro-4,6 -bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline cobalt chloride (R is chlorine, R 1 =R 4 is benzhydryl, R 2 , R 3 for hydrogen), Co-9
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.25g(0.55mmol)2-氯-4,6-二(二苯甲基)苯胺和0.06g(0.25mmol)CoCl2·6H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,53％)，Co-9。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.25g (0.55mmol) 2-chloro-4,6-bis( Diphenylmethyl)aniline and 0.06g (0.25mmol) CoCl 2 ·6H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, a large amount of ether was added to precipitate, and the precipitate passed through After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added for precipitation. The precipitate was collected by filtration and washed with a large amount of diethyl ether. After drying a brown powder (0.16 g, 53%), Co-9 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2951(w),2871(w),1624(υC＝N,w),1593(w),1550(w),1494(w),1449(w),1263(w),1236(w),1121(w),1030(w),925(w),889(w),829(w),742(w),701(s).FT-IR (KBr cm -1 ): 2951(w), 2871(w), 1624(υ C=N ,w), 1593(w), 1550(w), 1494(w), 1449(w), 1263(w), 1236(w), 1121(w), 1030(w), 925(w), 889(w), 829(w), 742(w), 701(s).
元素分析：C75H59Cl4CoN3(1203.05)理论值：C,74.88；H,4.94；N,3.49％；实验值:C,74.62；H,4.89；N,3.66％。Elemental analysis: C 75 H 59 Cl 4 CoN 3 (1203.05) Theoretical: C, 74.88; H, 4.94; N, 3.49%; Experimental: C, 74.62; H, 4.89; N, 3.66%.
实施例10、制备下式所示2-(1-(2-环戊基-4-二苯甲基-6-甲基苯基亚胺基)乙基)-8-(2-环戊基-4-二苯甲基-6-甲基苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为环戊基，R1为甲基，R4为二苯甲基，R2、R3为氢)，Fe-1Example 10, preparation of 2-(1-(2-cyclopentyl-4-benzhydryl-6-methylphenylimino)ethyl)-8-(2-cyclopentyl) shown in the following formula -4-benzhydryl-6-methylphenylimino)-5,6,7-trihydroquinoline ferric chloride (R is cyclopentyl, R 1 is methyl, R 4 is di Benzyl, R 2 , R 3 are hydrogen), Fe-1
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.19g(0.55mmol)2-环戊基-4-二苯甲基-6-甲基苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,75％)，Fe-1。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.19g (0.55mmol) 2-cyclopentyl-4-diphenyl Methyl-6-methylaniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, under nitrogen atmosphere, stirred and refluxed at 130°C for 4h, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.18 g, 75%), Fe-1 was obtained.
结构确证数据如下：The structural confirmation data are as follows:
FT-IR(KBr cm-1):2956.3(w),2867.6(w),1617.8(w),1598.6(w),1575.3(w),1493.6(m),1447.3(w),1365.7(w),1269.3(w),1241.2(m),1153.5(w),1074.7(w),1032.6(w),898.5(w),862.9(w),823.1(w),746.6(m),698.4(s).FT-IR (KBr cm -1 ): 2956.3(w), 2867.6(w), 1617.8(w), 1598.6(w), 1575.3(w), 1493.6(m), 1447.3(w), 1365.7(w), 1269.3(w), 1241.2(m), 1153.5(w), 1074.7(w), 1032.6(w), 898.5(w), 862.9(w), 823.1(w), 746.6(m), 698.4(s).
元素分析：C61H61Cl2FeN3(962.9)理论值：C,76.09；H,6.39；N,4.36％；实验值:C,76.13；H,5.93；N,4.11％。Elemental analysis: C 61 H 61 Cl 2 FeN 3 (962.9) Theoretical: C, 76.09; H, 6.39; N, 4.36%; Experimental: C, 76.13; H, 5.93; N, 4.11%.
实施例11、制备下式所示2-(1-(2-二苯甲基-4-环戊基-6-甲基苯基亚胺基)乙基)-8-(2-二苯甲基-4-环戊基-6-甲基苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为二苯甲基，R1为甲基，R4为环戊基，R2、R3为氢)，Fe-2Example 11, preparation of 2-(1-(2-benzhydryl-4-cyclopentyl-6-methylphenylimino)ethyl)-8-(2-benzhydryl) shown in the following formula Base-4-cyclopentyl-6-methylphenylimino)-5,6,7-trihydroquinoline ferric chloride (R is benzhydryl, R 1 is methyl, R 4 is Cyclopentyl, R 2 , R 3 are hydrogen), Fe-2
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.19g(0.55mmol)2-二苯甲基-4-环戊基-6-甲基苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,67％)，Fe-2。0.05g (0.25mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.19g (0.55mmol) of 2-benzhydryl-4-ring Pentyl-6-methylaniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, under nitrogen atmosphere, stirred and refluxed at 130°C for 4h, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.16 g, 67%), Fe-2 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2948.4(w),2865.8(w),1619.9(w),1574.6(w),1490.1(w),1449.8(w),1374.0(m),1266.9(w),1243.3(m),1214.2(w),1153.5(w),1078.7(w),1033.4(w),923.7(w),869.1(w),824.7(w),748.5(m),703.0(s).FT-IR (KBr cm -1 ): 2948.4(w), 2865.8(w), 1619.9(w), 1574.6(w), 1490.1(w), 1449.8(w), 1374.0(m), 1266.9(w), 1243.3(m), 1214.2(w), 1153.5(w), 1078.7(w), 1033.4(w), 923.7(w), 869.1(w), 824.7(w), 748.5(m), 703.0(s).
元素分析：C61H61Cl2FeN3(962.9)理论值：C,76.09；H,6.39；N,4.36％；实验值:C,75.72；H,6.28；N,4.20％。Elemental analysis: C 61 H 61 Cl 2 FeN 3 (962.9) Theoretical: C, 76.09; H, 6.39; N, 4.36%; Experimental: C, 75.72; H, 6.28; N, 4.20%.
实施例12、制备下式所示2-(1-(2-环戊基-4-甲基-6-二苯甲基苯基亚胺基)乙基)-8-(2-环戊基-4-甲基-6-二苯甲基苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为环戊基，R1为二苯甲基，R4为甲基，R2、R3为氢)，Fe-3Example 12, preparation of 2-(1-(2-cyclopentyl-4-methyl-6-benzhydrylphenylimino)ethyl)-8-(2-cyclopentyl) shown in the following formula -4-Methyl-6-benzhydrylphenylimino)-5,6,7-trihydroquinoline ferric chloride (R is cyclopentyl, R 1 is benzhydryl, R 4 is methyl, R 2 , R 3 are hydrogen), Fe-3
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.19g(0.55mmol)2-环戊基-4-甲基-6-二苯甲基苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,75％)，Fe-3。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.19g (0.55mmol) 2-cyclopentyl-4-methyl -6-Benzhydrylaniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, under nitrogen atmosphere, stirred and refluxed at 130°C for 4h, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.18 g, 75%), Fe-3 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2951.2(w),2866.1(w),1603.3(w),1574.5(w),1493.2(w),1449.8(w),1373.2(w),1270.4(w),1243.0(w),1206.5(w),1137.0(w),1074.5(w),1033.1(w),931.5(w),863.3(w),924.2(w),747.6(w),701.4(s).FT-IR (KBr cm -1 ): 2951.2(w), 2866.1(w), 1603.3(w), 1574.5(w), 1493.2(w), 1449.8(w), 1373.2(w), 1270.4(w), 1243.0(w), 1206.5(w), 1137.0(w), 1074.5(w), 1033.1(w), 931.5(w), 863.3(w), 924.2(w), 747.6(w), 701.4(s).
元素分析：C61H61Cl2FeN3(962.9)理论值：C,76.09；H,6.39；N,4.36％；实验值:C,75.88；H,6.21；N,4.29％。Elemental analysis: C 61 H 61 Cl 2 FeN 3 (962.9) Theoretical: C, 76.09; H, 6.39; N, 4.36%; Found: C, 75.88; H, 6.21; N, 4.29%.
实施例13、制备下式所示2-(1-(2-环戊基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-环戊基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为环戊基，R1＝R4为二苯甲基，R2为氢，R3为氢)，Fe-4Example 13, preparation of 2-(1-(2-cyclopentyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-cyclopentyl) shown in the following formula -4,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline ferric chloride (R is cyclopentyl, R 1 =R 4 is benzhydryl , R 2 is hydrogen, R 3 is hydrogen), Fe-4
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.27g(0.55mmol)2-环戊基-4,6-二(二苯甲基)苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.17g,54％)，Fe-4。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.27g (0.55mmol) 2-cyclopentyl-4,6- Bis(benzhydryl)aniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.17 g, 54%), Fe-4 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2956.3(w),2867.6(w),1617.8(w),1598.6(w),1575.3(w),1493.6(m),1447.3(w),1365.7(w),1269.3(w),1241.2(m),1153.5(w),1074.7(w),1032.6(w),898.5(w),862.9(w),823.1(w),746.6(m),698.4(s).FT-IR (KBr cm -1 ): 2956.3(w), 2867.6(w), 1617.8(w), 1598.6(w), 1575.3(w), 1493.6(m), 1447.3(w), 1365.7(w), 1269.3(w), 1241.2(m), 1153.5(w), 1074.7(w), 1032.6(w), 898.5(w), 862.9(w), 823.1(w), 746.6(m), 698.4(s).
元素分析：C85H77Cl2FeN3(1267.3)理论值：C,80.56；H,6.12；N,3.32％；实验值:C,80.08；H,5.89；N,3.36％.Elemental analysis: C 85 H 77 Cl 2 FeN 3 (1267.3) Theoretical value: C, 80.56; H, 6.12; N, 3.32%; Experimental value: C, 80.08; H, 5.89; N, 3.36%.
实施例14、制备下式所示2-(1-(2-环己基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-环己基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为环己基，R1＝R4为二苯甲基，R2为氢，R3为氢)，Fe-5Example 14. Preparation of 2-(1-(2-cyclohexyl-4,6-di(benzhydryl)phenylimino)ethyl)-8-(2-cyclohexyl-4 shown in the following formula ,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline ferric chloride (R is cyclohexyl, R 1 =R 4 is benzhydryl, R 2 is hydrogen, R 3 is hydrogen), Fe-5
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.28g(0.55mmol)2-环己基-4,6-二(二苯甲基)苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,56％)，Fe-5。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.28g (0.55mmol) 2-cyclohexyl-4,6-di (Diphenylmethyl)aniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, the precipitate After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, precipitated by adding a large amount of ether, and the precipitate was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.18 g, 56%), Fe-5 was obtained.
结构确证数据如下：The structural confirmation data are as follows:
FT-IR(KBr cm-1):2924.6(w),2857.7(w),1623.6(w),1599.3(w),1569.3(w),1493.8(w),1446.9(m),1368.7(w),1271.7(w),1241.3(w),1075.0(w),1032.5(w),907.9(w),865.4(w),824.7(w),744.8(m),698.7(s).FT-IR(KBr cm -1 ):2924.6(w), 2857.7(w), 1623.6(w), 1599.3(w), 1569.3(w), 1493.8(w), 1446.9(m), 1368.7(w), 1271.7(w), 1241.3(w), 1075.0(w), 1032.5(w), 907.9(w), 865.4(w), 824.7(w), 744.8(m), 698.7(s).
元素分析：C87H81Cl2FeN3(1295.4)理论值：C,80.67；H,6.30；N,3.24％；实验值:C,80.22；H,6.11；N,3.19％。Elemental analysis: C 87 H 81 Cl 2 FeN 3 (1295.4) Theoretical: C, 80.67; H, 6.30; N, 3.24%; Found: C, 80.22; H, 6.11; N, 3.19%.
Fe-5晶体结构示意图如图2所示。The schematic diagram of Fe-5 crystal structure is shown in Fig. 2.
实施例15、制备下式所示2-(1-(2-环辛基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-环辛基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为环辛基，R1＝R4为二苯甲基，R2、R3为氢)，Fe-6。Example 15. Preparation of 2-(1-(2-cyclooctyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-cyclooctyl) shown in the following formula -4,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline ferric chloride (R is cyclooctyl, R 1 =R 4 is benzhydryl , R 2 , R 3 are hydrogen), Fe-6.
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.29g(0.55mmol)2-环辛基-4,6-二(二苯甲基)苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.18g,53％)，Fe-6。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.29g (0.55mmol) 2-cyclooctyl-4,6- Bis(benzhydryl)aniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, and the precipitate The precipitate was collected by filtration, and then the precipitate was dissolved in dichloromethane, the solution was concentrated, and a large amount of ether was added to precipitate the precipitate, which was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.18 g, 53%), Fe-6 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2917.7(w),2852.0(w),1604.7(w),1574.8(w),1494.2(w),1446.3(w),1367.4(w),1269.3(w),1240.5(w),1135.4(w),1076.6(w),1030.7(w),924.4(w),865.4(w),826.5(w),745.5(w),700.8(s).FT-IR (KBr cm -1 ): 2917.7(w), 2852.0(w), 1604.7(w), 1574.8(w), 1494.2(w), 1446.3(w), 1367.4(w), 1269.3(w), 1240.5(w), 1135.4(w), 1076.6(w), 1030.7(w), 924.4(w), 865.4(w), 826.5(w), 745.5(w), 700.8(s).
元素分析：C91H89Cl2FeN3(1351.5)理论值：C,80.87；H,6.64；N,3.11％；实验值:C,C,80.39；H,6.21；N,3.14％。Elemental analysis: C 91 H 89 Cl 2 FeN 3 (1351.5) Theoretical: C, 80.87; H, 6.64; N, 3.11%; Experimental: C, C, 80.39; H, 6.21; N, 3.14%.
实施例16、制备下式所示2-(1-(2-甲基-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-甲基-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为甲基，R1＝R4为二苯甲基，R2、R3为氢)，Fe-7Example 16. Preparation of 2-(1-(2-methyl-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-methyl-4 ,6-bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline ferric chloride (R is methyl, R 1 =R 4 is benzhydryl, R 2 , R 3 is hydrogen), Fe-7
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.24g(0.55mmol)2-甲基-4,6-二(二苯甲基)苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,55％)，Fe-7。0.05g (0.25mmol) of 2-acetyl-6,7-dihydroquinolin-8-one compound represented by formula (II-1), 0.24g (0.55mmol) of 2-methyl-4,6-di (Diphenylmethyl)aniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL of acetic acid, stirred and refluxed at 130°C for 4h under a nitrogen atmosphere, the reaction solution was concentrated, and a large amount of ether was added to precipitate, the precipitate After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, precipitated by adding a large amount of ether, and the precipitate was collected by filtration and washed with a large amount of ether. After drying a brown powder (0.16 g, 55%), Fe-7 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2951.0(w),2861.9(w),1622.1(w),1597.3(w),1491.0(w),1452.7(w),1363.3(w),1261.2(w),1244.8(w),1202.1(w),1139.9(w),1031.1(w),927.1(w),898.3(w),745.5(w),702.2(s).FT-IR (KBr cm -1 ): 2951.0(w), 2861.9(w), 1622.1(w), 1597.3(w), 1491.0(w), 1452.7(w), 1363.3(w), 1261.2(w), 1244.8(w), 1202.1(w), 1139.9(w), 1031.1(w), 927.1(w), 898.3(w), 745.5(w), 702.2(s).
元素分析：C77H65Cl2FeN3(1157.39)理论值：C,79.79；H,5.65；N,3.63％；实验值:C,79.51；H,5.47；N,3.82％。Elemental analysis: C 77 H 65 Cl 2 FeN 3 (1157.39) Theoretical: C, 79.79; H, 5.65; N, 3.63%; Experimental: C, 79.51; H, 5.47; N, 3.82%.
实施例17、制备下式所示2-(1-(2-氟-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-氟-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为氟，R1＝R4为二苯甲基，R2、R3为氢)，Fe-8Example 17. Preparation of 2-(1-(2-fluoro-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-fluoro-4,6 -Bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline ferric chloride (R is fluorine, R 1 =R 4 is benzhydryl, R 2 , R 3 for hydrogen), Fe-8
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.24g(0.55mmol)2-氟-4,6-二(二苯甲基)苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.20g,69％)，Fe-8。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.24g (0.55mmol) 2-fluoro-4,6-bis( Diphenylmethyl)aniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL acetic acid, under nitrogen atmosphere, stirred and refluxed at 130°C for 4h, the reaction solution was concentrated, a large amount of ether was added to precipitate, and the precipitate passed through After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added for precipitation. The precipitate was collected by filtration and washed with a large amount of diethyl ether. After drying a brown powder (0.20 g, 69%), Fe-8 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2974.8(w),2908.7(w),1623.6(w),1602.4(w),1573.8(w),1494.2(w),1427.1(w),1297.3(w),1243.4(w),1125.2(w),1031.8(w),919.7(w),829.9(w),744.5(w),700.1(s).FT-IR(KBr cm -1 ):2974.8(w), 2908.7(w), 1623.6(w), 1602.4(w), 1573.8(w), 1494.2(w), 1427.1(w), 1297.3(w), 1243.4(w), 1125.2(w), 1031.8(w), 919.7(w), 829.9(w), 744.5(w), 700.1(s).
元素分析：C75H59Cl2F2FeN3(1167.1)理论值：C,77.19；H,5.10；N,3.60％；实验值:C,74.63；H,4.55；N,3.52％。Elemental analysis: C 75 H 59 Cl 2 F 2 FeN 3 (1167.1) Theoretical: C, 77.19; H, 5.10; N, 3.60%; Found: C, 74.63; H, 4.55; N, 3.52%.
实施例18、制备下式所示2-(1-(2-氯-4,6-二(二苯甲基)苯基亚胺基)乙基)-8-(2-氯-4,6-二(二苯甲基)苯基亚胺基)-5,6,7-三氢喹啉合氯化铁(R为氯，R1＝R4为二苯甲基，R2、R3为氢)，Fe-9Example 18. Preparation of 2-(1-(2-chloro-4,6-bis(benzhydryl)phenylimino)ethyl)-8-(2-chloro-4,6 -Bis(benzhydryl)phenylimino)-5,6,7-trihydroquinoline ferric chloride (R is chlorine, R 1 =R 4 is benzhydryl, R 2 , R 3 for hydrogen), Fe-9
将0.05g(0.25mmol)式(II-1)所示2-乙酰基-6,7-二氢喹啉-8-酮化合物，0.25g(0.55mmol)2-氯-4,6-二(二苯甲基)苯胺和0.05g(0.25mmol)FeCl2·4H2O溶于10mL乙酸中，在氮气氛围下，于130℃下搅拌回流4h，反应液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，之后将沉底物溶于二氯甲烷中，溶液浓缩，加入大量乙醚沉淀，沉淀物通过过滤收集，并用大量乙醚洗涤。干燥后得到棕色粉末(0.16g,53％)，Fe-9。0.05g (0.25mmol) 2-acetyl-6,7-dihydroquinolin-8-one compound shown in formula (II-1), 0.25g (0.55mmol) 2-chloro-4,6-bis( Diphenylmethyl)aniline and 0.05g (0.25mmol) FeCl 2 ·4H 2 O were dissolved in 10mL acetic acid, under nitrogen atmosphere, stirred and refluxed at 130°C for 4h, the reaction solution was concentrated, a large amount of ether was added to precipitate, and the precipitate passed through After collecting by filtration, the precipitated substrate was dissolved in dichloromethane, the solution was concentrated, and a large amount of diethyl ether was added for precipitation. The precipitate was collected by filtration and washed with a large amount of diethyl ether. After drying a brown powder (0.16 g, 53%), Fe-9 was obtained.
结构数据如下：The structure data is as follows:
FT-IR(KBr cm-1):2970.3(w),2909.2(w),1604.7(w),1573.8(w),1491.3(w),1446.8(w),1406.3(w),1378.0(w),1241.3(w),1073.5(w),900.4(w),827.1(w),745.9(w),701.0(s).FT-IR (KBr cm -1 ): 2970.3(w), 2909.2(w), 1604.7(w), 1573.8(w), 1491.3(w), 1446.8(w), 1406.3(w), 1378.0(w), 1241.3(w), 1073.5(w), 900.4(w), 827.1(w), 745.9(w), 701.0(s).
元素分析：C75H59Cl4FeN3(1200.0)理论值：C,75.07；H,4.96；N,3.50％；实验值:C,74.63；H,4.55；N,3.52％。Elemental analysis: C 75 H 59 Cl 4 FeN 3 (1200.0) Theoretical: C, 75.07; H, 4.96; N, 3.50%; Experimental: C, 74.63; H, 4.55; N, 3.52%.
实施例19、利用配合物Co-1及助催化剂MAO高压下联合催化乙烯聚合Example 19. Using complex Co-1 and co-catalyst MAO to jointly catalyze ethylene polymerization under high pressure
a)在氮气氛围下，将30ml的催化剂Co-1(2μmol)的甲苯溶液注射到250ml装有机械搅拌的不锈钢高压釜中，接着加入30ml甲苯，加入所需量的3.1mL的助催化剂MAO(1.46mol/L在甲苯中)，继续加入甲苯，使反应液总体积为100mL。此时Al/Co＝2250:1。机械搅拌开始，保持400转/分，当聚合温度达30℃时，往反应釜中充入乙烯，聚合反应开始。在30℃下保持10atm的乙烯压强，搅拌进行聚合反应30min。用10％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇洗数次，真空50℃烘干至恒重，称重得4.75g聚合物，聚合活性：4.75×106g/mol(Co)h-1，聚合分子量Mw＝1.89kg mol-1，分子量分布Mw/Mn为2.7(Mw为聚合物的重均分子量，Mn为聚合物的数均分子量，均通过GPC测试所得)，聚合物Tm＝122.8℃(Tm为聚合物的熔融温度，通过DSC测试所得)。a) Under a nitrogen atmosphere, inject the toluene solution of 30ml of catalyst Co-1 (2μmol) into a 250ml stainless steel autoclave equipped with mechanical stirring, then add 30ml of toluene, and add the required amount of 3.1mL of cocatalyst MAO ( 1.46mol/L in toluene), continue to add toluene, so that the total volume of the reaction solution is 100mL. At this time, Al/Co=2250:1. Start the mechanical stirring and keep it at 400 rpm. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, and the polymerization reaction starts. At 30°C, the ethylene pressure was maintained at 10 atm, and the polymerization reaction was carried out with stirring for 30 minutes. Neutralize the reaction solution with ethanol solution acidified with 10% hydrochloric acid to obtain a polymer precipitate, wash with ethanol several times, dry in vacuum at 50°C to constant weight, weigh 4.75g polymer, polymerization activity: 4.75×10 6 g/ mol(Co)h -1 , polymer molecular weight M w =1.89kg mol -1 , molecular weight distribution M w /M n is 2.7 (M w is the weight average molecular weight of the polymer, M n is the number average molecular weight of the polymer, average Tested by GPC), polymer T m =122.8°C (T m is the melting temperature of the polymer, measured by DSC).
b)基本同本实施例中方法a)，区别在于：聚合温度为40℃。聚合活性：5.32×106g/mol(Co)h-1，聚合分子量Mw＝1.75kg mol-1，分子量分布Mw/Mn为3.6，聚合物Tm＝122.6℃。b) is basically the same as method a) in this example, except that the polymerization temperature is 40°C. Polymerization activity: 5.32×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.75 kg mol -1 , molecular weight distribution M w /M n 3.6, polymer T m =122.6°C.
c)基本同本实施例中方法a)，区别在于：聚合温度为50℃。聚合活性：8.93×106g/mol(Co)h-1，聚合分子量Mw＝1.61g mol-1，分子量分布Mw/Mn为3.4，聚合物Tm＝122.4℃。c) is basically the same as method a) in this example, except that the polymerization temperature is 50°C. Polymerization activity: 8.93×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.61 g mol -1 , molecular weight distribution M w /M n is 3.4, polymer T m =122.4°C.
d)基本同本实施例中方法a)，区别在于：聚合温度为60℃。聚合活性：9.18×106g/mol(Co)h-1，聚合分子量Mw＝1.56kg mol-1，分子量分布Mw/Mn为3.3，聚合物Tm＝122.3℃。d) is basically the same as method a) in this example, except that the polymerization temperature is 60°C. Polymerization activity: 9.18×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.56 kg mol -1 , molecular weight distribution M w /M n 3.3, polymer T m =122.3°C.
e)基本同本实施例中方法a)，区别在于：聚合温度为70℃。聚合活性：5.28×106g/mol(Co)h-1，聚合分子量Mw＝1.41kg mol-1，分子量分布Mw/Mn为3.1，聚合物Tm＝122.1℃。e) is basically the same as method a) in this example, except that the polymerization temperature is 70°C. Polymerization activity: 5.28×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.41 kg mol -1 , molecular weight distribution M w /M n 3.1, polymer T m =122.1°C.
f)基本同本实施例中方法a)，区别在于：聚合温度为80℃。聚合活性：2.89×106g/mol(Co)h-1，聚合分子量Mw＝1.37kg mol-1，分子量分布Mw/Mn为2.9，聚合物Tm＝121.8℃。f) is basically the same as method a) in this example, except that the polymerization temperature is 80°C. Polymerization activity: 2.89×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.37 kg mol -1 , molecular weight distribution M w /M n 2.9, polymer T m =121.8°C.
g)基本同本实施例中方法d)，区别在于：助催化剂MAO(1.46mol/L在甲苯中)用量为1.7mL，使Al/Co＝1250：1。聚合活性：5.37×106g/mol(Co)h-1，聚合分子量Mw＝1.56kgmol-1，分子量分布Mw/Mn为3.6，聚合物Tm＝123.6℃。g) is basically the same as method d) in this example, except that the amount of cocatalyst MAO (1.46 mol/L in toluene) is 1.7 mL, so that Al/Co=1250:1. Polymerization activity: 5.37×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.56 kgmol -1 , molecular weight distribution M w /M n 3.6, polymer T m =123.6°C.
h)基本同本实施例中方法d)，区别在于：助催化剂MAO(1.46mol/L在甲苯中)用量为2.1mL，使Al/Co＝1500：1。聚合活性：6.47×106g/mol(Co)h-1，聚合分子量Mw＝1.56kgmol-1，分子量分布Mw/Mn为2.9，聚合物Tm＝123.3℃。h) is basically the same as method d) in this example, the difference is that the amount of co-catalyst MAO (1.46 mol/L in toluene) is 2.1 mL, so that Al/Co=1500:1. Polymerization activity: 6.47×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.56 kgmol -1 , molecular weight distribution M w /M n 2.9, polymer T m =123.3°C.
i)基本同本实施例中方法d)，区别在于：助催化剂MAO(1.46mol/L在甲苯中)用量为2.4mL，使Al/Co＝1750：1。聚合活性：13.66×106g/mol(Co)h-1，聚合分子量Mw＝1.63kgmol-1，分子量分布Mw/Mn为3.2，聚合物Tm＝123.0℃。i) It is basically the same as the method d) in this example, except that the amount of co-catalyst MAO (1.46 mol/L in toluene) is 2.4 mL, so that Al/Co=1750:1. Polymerization activity: 13.66×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.63 kgmol -1 , molecular weight distribution M w /M n 3.2, polymer T m =123.0°C.
取所得聚合物20mg，溶于2ml氘代1,1,2,2-四氯乙烷，在100℃条件下，测试该聚合物的1H数据，如图3所示。信号累积64次，在位移5.90(ppm)和5.02(ppm)处得到两组多重信号峰，证明为乙烯基团(–CH＝CH2)。Take 20 mg of the obtained polymer, dissolve it in 2 ml of deuterated 1,1,2,2-tetrachloroethane, and test the 1 H data of the polymer at 100° C., as shown in FIG. 3 . The signal was accumulated 64 times, and two sets of multiple signal peaks were obtained at shifts of 5.90 (ppm) and 5.02 (ppm), which proved to be vinyl groups (–CH=CH 2 ).
取所得聚合物20mg，溶于2ml氘代1,1,2,2-四氯乙烷，在100℃条件下，测试该聚合物的13C数据，如图3所示的插图。信号累积1024次，在位移114.42(ppm)和139.57(ppm)处得到两组信号峰，表明为聚乙烯长链的乙烯端基，证明所得聚合物为高度线性聚乙烯，并在32.23，22.95和14.32(ppm)处，表明为对应的正丙基端基。Take 20 mg of the obtained polymer, dissolve it in 2 ml of deuterated 1,1,2,2-tetrachloroethane, and test the 13 C data of the polymer at 100° C., as shown in the inset of FIG. 3 . The signal was accumulated 1024 times, and two groups of signal peaks were obtained at displacements of 114.42 (ppm) and 139.57 (ppm), indicating that they were ethylene end groups of polyethylene long chains, proving that the obtained polymer was highly linear polyethylene, and at 32.23, 22.95 and 14.32 (ppm), indicated as the corresponding n-propyl end group.
j)基本同本实施例中方法d)，区别在于：助催化剂MAO(1.46mol/L在甲苯中)用量为2.7mL使Al/Co＝2000：1。聚合活性：10.54×106g/mol(Co)h-1，聚合分子量Mw＝1.58kgmol-1，分子量分布Mw/Mn为3.3，聚合物Tm＝123.1℃。j) is basically the same as method d) in this example, except that the amount of cocatalyst MAO (1.46 mol/L in toluene) is 2.7 mL so that Al/Co=2000:1. Polymerization activity: 10.54×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.58 kgmol -1 , molecular weight distribution M w /M n 3.3, polymer T m =123.1°C.
k)基本同本实施例中方法d)，区别在于：助催化剂MAO(1.46mol/L在甲苯中)用量为3.4mL使Al/Co＝2500：1。聚合活性：7.81×106g/mol(Co)h-1，聚合分子量Mw＝1.66kg mol-1，分子量分布Mw/Mn为3.4，聚合物Tm＝122.8℃。k) is basically the same as method d) in this example, the difference is that the amount of cocatalyst MAO (1.46 mol/L in toluene) is 3.4 mL so that Al/Co=2500:1. Polymerization activity: 7.81×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.66 kg mol -1 , molecular weight distribution M w /M n is 3.4, polymer T m =122.8°C.
实施例20、利用配合物Co-2及MAO联合催化加压下的乙烯聚合Example 20. Using complex Co-2 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-2。聚合活性：2.98×106g/mol(Co)h-1，聚合分子量Mw＝14.67kg mol-1，分子量分布Mw/Mn为5.9，聚合物Tm＝129.7℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-2. Polymerization activity: 2.98×10 6 g/mol(Co)h -1 , polymer molecular weight M w =14.67 kg mol -1 , molecular weight distribution M w /M n 5.9, polymer T m =129.7°C.
实施例21、利用配合物Co-3及MAO联合催化加压下的乙烯聚合Example 21. Using complex Co-3 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-3。聚合活性：3.61×106g/mol(Co)h-1，聚合分子量Mw＝101.63kg mol-1，分子量分布Mw/Mn为3.8，聚合物Tm＝134.6℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-3. Polymerization activity: 3.61×10 6 g/mol(Co)h -1 , polymer molecular weight M w =101.63 kg mol -1 , molecular weight distribution M w /M n 3.8, polymer T m =134.6°C.
实施例22、利用配合物Co-4及MAO联合催化加压下的乙烯聚合Example 22. Using complex Co-4 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-4。聚合活性：3.20×106g/mol(Co)h-1，聚合分子量Mw＝48.28kg mol-1，分子量分布Mw/Mn为3.8，聚合物Tm＝134.6℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-4. Polymerization activity: 3.20×10 6 g/mol(Co)h -1 , polymer molecular weight M w =48.28 kg mol -1 , molecular weight distribution M w /M n 3.8, polymer T m =134.6°C.
实施例23、利用配合物Co-5及MAO联合催化加压下的乙烯聚合Example 23. Using complex Co-5 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂Co-5。聚合活性：1.10×106g/mol(Co)h-1，聚合分子量Mw＝61.62g mol-1，分子量分布Mw/Mn为4.7，聚合物Tm＝135.5℃。Basically the same as Example 19i), the difference is: main catalyst Co-5. Polymerization activity: 1.10×10 6 g/mol(Co)h -1 , polymer molecular weight M w =61.62 g mol -1 , molecular weight distribution M w /M n 4.7, polymer T m =135.5°C.
实施例24、利用配合物Co-6及MAO联合催化加压下的乙烯聚合Example 24. Utilizing complex Co-6 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-6。聚合活性：0.81×106g/mol(Co)h-1，聚合分子量Mw＝92.16g mol-1，分子量分布Mw/Mn为6.4，聚合物Tm＝134.7℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-6. Polymerization activity: 0.81×10 6 g/mol(Co)h -1 , polymer molecular weight M w =92.16 g mol -1 , molecular weight distribution M w /M n is 6.4, polymer T m =134.7°C.
实施例25、利用配合物Co-7及MAO联合催化加压下的乙烯聚合Example 25. Utilizing complex Co-7 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-7。聚合活性：3.65×106g/mol(Co)h-1，聚合分子量Mw＝63.91g mol-1，分子量分布Mw/Mn为19.8，聚合物Tm＝134.3℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-7. Polymerization activity: 3.65×10 6 g/mol(Co)h -1 , polymer molecular weight M w =63.91 g mol -1 , molecular weight distribution M w /M n 19.8, polymer T m =134.3°C.
实施例26、利用配合物Co-8及MAO联合催化加压下的乙烯聚合Example 26. Utilizing complex Co-8 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-8。聚合活性：4.24×106g/mol(Co)h-1，聚合分子量Mw＝3.43g mol-1，分子量分布Mw/Mn为6.3，聚合物Tm＝122.8℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-8. Polymerization activity: 4.24×10 6 g/mol(Co)h -1 , polymer molecular weight M w =3.43 g mol -1 , molecular weight distribution M w /M n is 6.3, polymer T m =122.8°C.
实施例27、利用配合物Co-9及MAO联合催化加压下的乙烯聚合Example 27. Using complex Co-9 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例19i)，区别在于：主催化剂为Co-9。聚合活性：3.78×106g/mol(Co)h-1，聚合分子量Mw＝24.85g mol-1，分子量分布Mw/Mn为9.2，聚合物Tm＝131.0℃。Basically the same as Example 19i), the difference is that the main catalyst is Co-9. Polymerization activity: 3.78×10 6 g/mol(Co)h -1 , polymer molecular weight M w =24.85 g mol -1 , molecular weight distribution M w /M n 9.2, polymer T m =131.0°C.
实施例28、利用配合物Co-1及MMAO联合催化加压下的乙烯聚合Example 28. Using complex Co-1 and MMAO to jointly catalyze ethylene polymerization under pressure
a)在氮气氛围下，将30ml的催化剂Co-1(2.0μmol)的甲苯溶液注射到250ml装有机械搅拌的不锈钢高压釜中，接着加入30ml甲苯，加入所需量的2.0mL的助催化剂MMAO(2.0mol/L在甲苯中)，继续加入甲苯，使反应液总体积为100mL。此时Al/Co＝2000:1。机械搅拌开始，保持400转/分，当聚合温度达到30℃时，往反应釜中充入乙烯，聚合反应开始。在30℃下保持10atm的乙烯压强，搅拌进行聚合反应30min。用10％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇洗数次，真空50℃烘干至恒重，称重得2.96g聚合物，聚合活性：2.96×106g/mol(Co)h-1，聚合分子量Mw＝2.32kg mol-1，分子量分布Mw/Mn为4.9(Mw为聚合物的重均分子量，Mn为聚合物的数均分子量，均通过GPC测试所得)，聚合物Tm＝122.3℃(Tm为聚合物的熔融温度，通过DSC测试所得)。a) Under a nitrogen atmosphere, inject 30ml of the catalyst Co-1 (2.0μmol) toluene solution into a 250ml stainless steel autoclave equipped with mechanical stirring, then add 30ml of toluene, and add the required amount of 2.0mL of the cocatalyst MMAO (2.0mol/L in toluene), continue to add toluene to make the total volume of the reaction solution 100mL. At this time, Al/Co=2000:1. Start the mechanical stirring and keep it at 400 rpm. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, and the polymerization reaction starts. At 30°C, the ethylene pressure was maintained at 10 atm, and the polymerization reaction was carried out with stirring for 30 minutes. Neutralize the reaction solution with ethanol solution acidified with 10% hydrochloric acid to obtain a polymer precipitate, wash it several times with ethanol, dry it in vacuum at 50°C to constant weight, weigh 2.96g polymer, polymerization activity: 2.96×10 6 g/ mol(Co)h -1 , polymer molecular weight M w =2.32kg mol -1 , molecular weight distribution M w /M n is 4.9 (M w is the weight average molecular weight of the polymer, M n is the number average molecular weight of the polymer, average Tested by GPC), polymer T m =122.3°C (T m is the melting temperature of the polymer, measured by DSC).
b)基本同本实施例中方法a)，区别在于：聚合温度为40℃。聚合活性：3.64×106g/mol(Co)h-1，聚合分子量Mw＝1.62kg mol-1，分子量分布Mw/Mn为3.2，聚合物Tm＝122.3℃。b) is basically the same as method a) in this example, except that the polymerization temperature is 40°C. Polymerization activity: 3.64×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.62 kg mol -1 , molecular weight distribution M w /M n 3.2, polymer T m =122.3°C.
c)基本同本实施例中方法a)，区别在于：聚合温度为50℃。聚合活性：8.41×106g/mol(Co)h-1，聚合分子量Mw＝1.49kg mol-1，分子量分布Mw/Mn为3.1，聚合物Tm＝122.3℃。c) is basically the same as method a) in this example, except that the polymerization temperature is 50°C. Polymerization activity: 8.41×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.49 kg mol -1 , molecular weight distribution M w /M n is 3.1, polymer T m =122.3°C.
d)基本同本实施例中方法a)，区别在于：聚合温度为60℃。聚合活性：5.27×106g/mol(Co)h-1，聚合分子量Mw＝1.38kg mol-1，分子量分布Mw/Mn为3.1，聚合物Tm＝122.9℃。d) is basically the same as method a) in this example, except that the polymerization temperature is 60°C. Polymerization activity: 5.27×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.38 kg mol -1 , molecular weight distribution M w /M n 3.1, polymer T m =122.9°C.
e)基本同本实施例中方法a)，区别在于：聚合温度为70℃。聚合活性：2.39×106g/mol(Co)h-1，聚合分子量Mw＝5.84kg mol-1，分子量分布Mw/Mn为9.2，聚合物Tm＝125.3℃。e) is basically the same as method a) in this example, except that the polymerization temperature is 70°C. Polymerization activity: 2.39×10 6 g/mol(Co)h -1 , polymer molecular weight M w =5.84 kg mol -1 , molecular weight distribution M w /M n 9.2, polymer T m =125.3°C.
f)基本同本实施例中方法a)，区别在于：聚合温度为80℃。聚合活性：2.1539×106g/mol(Co)h-1，聚合分子量Mw＝5.54kg mol-1，分子量分布Mw/Mn为9.2，聚合物Tm＝124.7℃。f) is basically the same as method a) in this example, except that the polymerization temperature is 80°C. Polymerization activity: 2.1539×10 6 g/mol(Co)h -1 , polymer molecular weight M w =5.54 kg mol -1 , molecular weight distribution M w /M n 9.2, polymer T m =124.7°C.
g)基本同本实施例中方法c)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为1.5mL使Al/Co＝1500：1。聚合活性：6.20×106g/mol(Co)h-1，聚合分子量Mw＝2.50kg mol-1，分子量分布Mw/Mn为2.4，聚合物Tm＝122.3℃。g) is basically the same as method c) in this example, except that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 1.5 mL so that Al/Co=1500:1. Polymerization activity: 6.20×10 6 g/mol(Co)h -1 , polymer molecular weight M w =2.50 kg mol -1 , molecular weight distribution M w /M n 2.4, polymer T m =122.3°C.
h)基本同本实施例中方法c)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为2.3mL使Al/Co＝2250：1。聚合活性：11.78×106g/mol(Co)h-1，聚合分子量Mw＝1.49kgmol-1，分子量分布Mw/Mn为4.0，聚合物Tm＝121.9℃。h) is basically the same as method c) in this example, except that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 2.3 mL so that Al/Co=2250:1. Polymerization activity: 11.78×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.49 kgmol -1 , molecular weight distribution M w /M n 4.0, polymer T m =121.9°C.
i)基本同本实施例中方法c)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为2.5mL使Al/Co＝2500：1。聚合活性：11.46×106g/mol(Co)h-1，聚合分子量Mw＝1.30kgmol-1，分子量分布Mw/Mn为3.3，聚合物Tm＝121.8℃。i) It is basically the same as method c) in this example, except that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 2.5 mL so that Al/Co=2500:1. Polymerization activity: 11.46×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.30 kgmol -1 , molecular weight distribution M w /M n 3.3, polymer T m =121.8°C.
j)基本同本实施例中方法c)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为2.8mL使Al/Co＝2750：1。聚合活性：6.87×106g/mol(Co)h-1，聚合分子量Mw＝2.87kg mol-1，分子量分布Mw/Mn为3.2，聚合物Tm＝122.5℃。j) is basically the same as method c) in this example, except that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 2.8 mL so that Al/Co=2750:1. Polymerization activity: 6.87×10 6 g/mol(Co)h -1 , polymer molecular weight M w =2.87 kg mol -1 , molecular weight distribution M w /M n is 3.2, polymer T m =122.5°C.
k)基本同本实施例中方法c)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为3.0mL使Al/Co＝3000：1。聚合活性：5.82×106g/mol(Co)h-1，聚合分子量Mw＝2.75kg mol-1，分子量分布Mw/Mn为3.4，聚合物Tm＝122.3℃。k) is basically the same as method c) in this example, the difference is that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 3.0 mL so that Al/Co=3000:1. Polymerization activity: 5.82×10 6 g/mol(Co)h -1 , polymer molecular weight M w =2.75 kg mol -1 , molecular weight distribution M w /M n is 3.4, polymer T m =122.3°C.
实施例29、利用配合物Co-2及MMAO联合催化加压下的乙烯聚合Example 29. Using complex Co-2 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-2。聚合活性：2.80×106g/mol(Co)h-1，聚合分子量Mw＝14.06kg mol-1，分子量分布Mw/Mn为9.1，聚合物Tm＝130.8℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-2. Polymerization activity: 2.80×10 6 g/mol(Co)h -1 , polymer molecular weight M w =14.06 kg mol -1 , molecular weight distribution M w /M n 9.1, polymer T m =130.8°C.
实施例30、利用配合物Co-3及MMAO联合催化加压下的乙烯聚合Example 30: Utilizing complex Co-3 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-3。聚合活性：9.56×106g/mol(Co)h-1，聚合分子量Mw＝61.79kg mol-1，分子量分布Mw/Mn为2.9，聚合物Tm＝134.5℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-3. Polymerization activity: 9.56×10 6 g/mol(Co)h -1 , polymer molecular weight M w =61.79 kg mol -1 , molecular weight distribution M w /M n 2.9, polymer T m =134.5°C.
实施例31、利用配合物Co-4及MMAO联合催化加压下的乙烯聚合Example 31. Using complex Co-4 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-4。聚合活性：2.50×106g/mol(Co)h-1，聚合分子量Mw＝24.23kg mol-1，分子量分布Mw/Mn为6.2，聚合物Tm＝132.6℃。Basically the same as embodiment 28h), the difference is: the main catalyst is Co-4. Polymerization activity: 2.50×10 6 g/mol(Co)h -1 , polymer molecular weight M w =24.23 kg mol -1 , molecular weight distribution M w /M n is 6.2, polymer T m =132.6°C.
实施例32、利用配合物Co-5及MMAO联合催化加压下的乙烯聚合Example 32. Using complex Co-5 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-5。聚合活性：6.31×106g/mol(Co)h-1，聚合分子量Mw＝24.62kg mol-1，分子量分布Mw/Mn为3.0，聚合物Tm＝133.1℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-5. Polymerization activity: 6.31×10 6 g/mol(Co)h -1 , polymer molecular weight M w =24.62 kg mol -1 , molecular weight distribution M w /M n 3.0, polymer T m =133.1°C.
实施例33、利用配合物Co-6及MMAO联合催化加压下的乙烯聚合Example 33. Using complex Co-6 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-6。聚合活性：3.75×106g/mol(Co)h-1，聚合分子量Mw＝31.09kg mol-1，分子量分布Mw/Mn为5.3，聚合物Tm＝134.6℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-6. Polymerization activity: 3.75×10 6 g/mol(Co)h -1 , polymer molecular weight M w =31.09 kg mol -1 , molecular weight distribution M w /M n 5.3, polymer T m =134.6°C.
实施例34、利用配合物Co-7及MMAO联合催化加压下的乙烯聚合Example 34. Utilizing complex Co-7 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-7。聚合活性：1.80×106g/mol(Co)h-1，聚合分子量Mw＝9.01kg mol-1，分子量分布Mw/Mn为3.9，聚合物Tm＝132.1℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-7. Polymerization activity: 1.80×10 6 g/mol(Co)h -1 , polymer molecular weight M w =9.01 kg mol -1 , molecular weight distribution M w /M n 3.9, polymer T m =132.1°C.
实施例35、利用配合物Co-8及MMAO联合催化加压下的乙烯聚合Example 35. Using complex Co-8 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-8。聚合活性：4.95×106g/mol(Co)h-1，聚合分子量Mw＝1.11kg mol-1，分子量分布Mw/Mn为2.1，聚合物Tm＝119.5℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-8. Polymerization activity: 4.95×10 6 g/mol(Co)h -1 , polymer molecular weight M w =1.11 kg mol -1 , molecular weight distribution M w /M n 2.1, polymer T m =119.5°C.
实施例36、利用配合物Co-9及MMAO联合催化加压下的乙烯聚合Example 36. Utilizing complex Co-9 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例28h)，区别在于：主催化剂为Co-9。聚合活性：2.35×106g/mol(Co)h-1，聚合分子量Mw＝11.45kg mol-1，分子量分布Mw/Mn为9.9，聚合物Tm＝131.5℃。Basically the same as Example 28h), the difference is that the main catalyst is Co-9. Polymerization activity: 2.35×10 6 g/mol(Co)h -1 , polymer molecular weight M w =11.45 kg mol -1 , molecular weight distribution M w /M n 9.9, polymer T m =131.5°C.
实施例37、利用配合物Fe-5及MMAO联合催化加压下的乙烯聚合Example 37. Using complex Fe-5 and MMAO to jointly catalyze ethylene polymerization under pressure
a)在氮气氛围下，将30ml的催化剂Fe-5(2.0μmol)的甲苯溶液注射到250ml装有机械搅拌的不锈钢高压釜中，接着加入30ml甲苯，加入所需量的2.0mL的助催化剂MMAO(2.0mol/L在甲苯中)，继续加入甲苯使反应液总体积为100mL。此时Al/Fe＝2000:1。机械搅拌开始，保持400转/分，当聚合温度达到30℃时，往反应釜中充入乙烯，聚合反应开始。在30℃下保持10atm的乙烯压强，搅拌进行聚合反应30min。用10％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇洗数次，真空50℃烘干至恒重，称重得4.47g聚合物，聚合活性：4.47×106g/mol(Fe)h-1，聚合分子量Mw＝11.92kg mol-1，分子量分布Mw/Mn为2.2(Mw为聚合物的质均分子量，Mn为聚合物的数均分子量，均通过GPC测试所得)，聚合物Tm＝127.0℃(Tm为聚合物的熔融温度，通过DSC测试所得)。a) Under nitrogen atmosphere, inject 30ml of toluene solution of catalyst Fe-5 (2.0μmol) into a 250ml stainless steel autoclave equipped with mechanical stirring, then add 30ml of toluene, and add the required amount of 2.0mL of cocatalyst MMAO (2.0mol/L in toluene), continue to add toluene to make the total volume of the reaction solution be 100mL. At this time, Al/Fe=2000:1. Start the mechanical stirring and keep it at 400 rpm. When the polymerization temperature reaches 30°C, fill the reactor with ethylene, and the polymerization reaction starts. At 30°C, the ethylene pressure was maintained at 10 atm, and the polymerization reaction was carried out with stirring for 30 minutes. Neutralize the reaction solution with ethanol solution acidified with 10% hydrochloric acid to obtain a polymer precipitate, wash it several times with ethanol, dry it in vacuum at 50°C to constant weight, and weigh 4.47g polymer, polymerization activity: 4.47×10 6 g/ mol(Fe)h -1 , polymer molecular weight M w =11.92kg mol -1 , molecular weight distribution M w /M n is 2.2 (M w is the mass average molecular weight of the polymer, M n is the number average molecular weight of the polymer, average Tested by GPC), polymer T m =127.0°C (T m is the melting temperature of the polymer, measured by DSC).
b)基本同本实施例中方法a)，区别在于：聚合温度为40℃。聚合活性：6.25×106g/mol(Fe)h-1，聚合分子量Mw＝2.30kg mol-1，分子量分布Mw/Mn为2.0，聚合物Tm＝126.1℃。b) is basically the same as method a) in this example, except that the polymerization temperature is 40°C. Polymerization activity: 6.25×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =2.30 kg mol -1 , molecular weight distribution M w /M n 2.0, polymer T m =126.1°C.
c)基本同本实施例中方法a)，区别在于：聚合温度为50℃。聚合活性：7.76×106g/mol(Fe)h-1，聚合分子量Mw＝1.67kg mol-1，分子量分布Mw/Mn为1.7，聚合物Tm＝126.0℃。c) is basically the same as method a) in this example, except that the polymerization temperature is 50°C. Polymerization activity: 7.76×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.67 kg mol -1 , molecular weight distribution M w /M n is 1.7, polymer T m =126.0°C.
d)基本同本实施例中方法a)，区别在于：聚合温度为60℃。聚合活性：9.38×106g/mol(Fe)h-1，聚合分子量Mw＝1.47kg mol-1，分子量分布Mw/Mn为2.0，聚合物Tm＝125.0℃。d) is basically the same as method a) in this example, except that the polymerization temperature is 60°C. Polymerization activity: 9.38×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.47 kg mol -1 , molecular weight distribution M w /M n 2.0, polymer T m =125.0°C.
e)基本同本实施例中方法a)，区别在于：聚合温度为70℃。聚合活性：1.62×106g/mol(Fe)h-1，聚合分子量Mw＝0.98kg mol-1，分子量分布Mw/Mn为1.5，聚合物Tm＝123.2℃。e) is basically the same as method a) in this example, except that the polymerization temperature is 70°C. Polymerization activity: 1.62×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =0.98 kg mol -1 , molecular weight distribution M w /M n 1.5, polymer T m =123.2°C.
f)基本同本实施例中方法a)，区别在于：聚合温度为80℃。聚合活性：0.57×106g/mol(Fe)h-1，聚合分子量Mw＝0.55kg mol-1，分子量分布Mw/Mn为1.7，聚合物Tm＝122.5℃。f) is basically the same as method a) in this example, except that the polymerization temperature is 80°C. Polymerization activity: 0.57×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =0.55 kg mol -1 , molecular weight distribution M w /M n 1.7, polymer T m =122.5°C.
g)基本同本实施例中方法d)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为1.5mL使Al/Fe＝1500：1。聚合活性：1.39×106g/mol(Fe)h-1，聚合分子量Mw＝2.95kg mol-1，分子量分布Mw/Mn为1.5，聚合物Tm＝129.6℃。g) is basically the same as the method d) in this example, the difference is that the amount of co-catalyst MMAO (2.0 mol/L in toluene) is 1.5 mL so that Al/Fe=1500:1. Polymerization activity: 1.39×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =2.95 kg mol -1 , molecular weight distribution M w /M n 1.5, polymer T m =129.6°C.
h)基本同本实施例中方法d)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为1.8mL使Al/Fe＝1750：1。聚合活性：7.86×106g/mol(Fe)h-1，聚合分子量Mw＝1.78kg mol-1，分子量分布Mw/Mn为1.8，聚合物Tm＝128.6℃。h) is basically the same as method d) in this example, the difference is that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 1.8 mL so that Al/Fe=1750:1. Polymerization activity: 7.86×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.78 kg mol -1 , molecular weight distribution M w /M n is 1.8, polymer T m =128.6°C.
i)基本同本实施例中方法d)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为2.3mL使Al/Fe＝2250：1。聚合活性：5.30×106g/mol(Fe)h-1，聚合分子量Mw＝1.55kg mol-1，分子量分布Mw/Mn为1.8，聚合物Tm＝123.5℃。i) is basically the same as method d) in this example, except that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 2.3 mL so that Al/Fe=2250:1. Polymerization activity: 5.30×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.55 kg mol -1 , molecular weight distribution M w /M n 1.8, polymer T m =123.5°C.
j)基本同本实施例中方法d)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为2.5mL使Al/Fe＝2500：1。聚合活性：4.22×106g/mol(Fe)h-1，聚合分子量Mw＝1.39kg mol-1，分子量分布Mw/Mn为1.9，聚合物Tm＝124.1℃。j) is basically the same as method d) in this example, except that the amount of co-catalyst MMAO (2.0 mol/L in toluene) is 2.5 mL so that Al/Fe=2500:1. Polymerization activity: 4.22×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.39 kg mol -1 , molecular weight distribution M w /M n 1.9, polymer T m =124.1°C.
k)基本同本实施例中方法d)，区别在于：助催化剂MMAO(2.0mol/L在甲苯中)用量为3.0mL使Al/Fe＝3000：1。聚合活性：3.87×106g/mol(Fe)h-1，聚合分子量Mw＝1.15kg mol-1，分子量分布Mw/Mn为1.6，聚合物Tm＝123.9℃。k) is basically the same as method d) in this example, the difference is that the amount of cocatalyst MMAO (2.0 mol/L in toluene) is 3.0 mL so that Al/Fe=3000:1. Polymerization activity: 3.87×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.15 kg mol -1 , molecular weight distribution M w /M n 1.6, polymer T m =123.9°C.
实施例38、利用配合物Fe-1及MMAO联合催化加压下的乙烯聚合Example 38. Using complex Fe-1 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-1。聚合活性：24.55×106g/mol(Fe)h-1，聚合分子量Mw＝42.32kg mol-1，分子量分布Mw/Mn为11.9，聚合物Tm＝128.2℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-1. Polymerization activity: 24.55×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =42.32 kg mol -1 , molecular weight distribution M w /M n 11.9, polymer T m =128.2°C.
实施例39、利用配合物Fe-2及MMAO联合催化加压下的乙烯聚合Example 39. Using complex Fe-2 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-2。聚合活性：25.20×106g/mol(Fe)h-1，聚合分子量Mw＝62.41kg mol-1，分子量分布Mw/Mn为18.3，聚合物Tm＝129.0℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-2. Polymerization activity: 25.20×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =62.41 kg mol -1 , molecular weight distribution M w /M n 18.3, polymer T m =129.0°C.
实施例40、利用配合物Fe-3及MMAO联合催化加压下的乙烯聚合Example 40. Using complex Fe-3 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-3。聚合活性：13.46×106g/mol(Fe)h-1，聚合分子量Mw＝7.73kg mol-1，分子量分布Mw/Mn为2.7，聚合物Tm＝128.6℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-3. Polymerization activity: 13.46×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =7.73 kg mol -1 , molecular weight distribution M w /M n 2.7, polymer T m =128.6°C.
实施例41、利用配合物Fe-4及MMAO联合催化加压下的乙烯聚合Example 41. Using complex Fe-4 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-4。聚合活性：5.29×106g/mol(Fe)h-1，聚合分子量Mw＝1.36kg mol-1，分子量分布Mw/Mn为1.6，聚合物Tm＝121.6℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-4. Polymerization activity: 5.29×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.36 kg mol -1 , molecular weight distribution M w /M n is 1.6, polymer T m =121.6°C.
实施例42、利用配合物Fe-6及MMAO联合催化加压下的乙烯聚合Example 42. Using complex Fe-6 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-6。聚合活性：1.51×106g/mol(Fe)h-1，聚合分子量Mw＝2.59kg mol-1，分子量分布Mw/Mn为2.3，聚合物Tm＝126.5℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-6. Polymerization activity: 1.51×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =2.59 kg mol -1 , molecular weight distribution M w /M n 2.3, polymer T m =126.5°C.
实施例43、利用配合物Fe-7及MMAO联合催化加压下的乙烯聚合Example 43. Using complex Fe-7 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-7。聚合活性：11.78×106g/mol(Fe)h-1，聚合分子量Mw＝1.92kg mol-1，分子量分布Mw/Mn为2.1，聚合物Tm＝127.2℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-7. Polymerization activity: 11.78×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =1.92 kg mol -1 , molecular weight distribution M w /M n 2.1, polymer T m =127.2°C.
实施例44、利用配合物Fe-8及MMAO联合催化加压下的乙烯聚合Example 44. Using the complex Fe-8 and MMAO to jointly catalyze the polymerization of ethylene under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-8。聚合活性：21.35×106g/mol(Fe)h-1，聚合分子量Mw＝9.38kg mol-1，分子量分布Mw/Mn为7.1，聚合物Tm＝126.5℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-8. Polymerization activity: 21.35×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =9.38 kg mol -1 , molecular weight distribution M w /M n 7.1, polymer T m =126.5°C.
实施例45、利用配合物Fe-9及MMAO联合催化加压下的乙烯聚合Example 45. Using complex Fe-9 and MMAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-9。聚合活性：13.56×106g/mol(Fe)h-1，聚合分子量Mw＝25.51kg mol-1，分子量分布Mw/Mn为7.4，聚合物Tm＝130.3℃。Basically the same as Example 37d), the difference is that the main catalyst is Fe-9. Polymerization activity: 13.56×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =25.51 kg mol -1 , molecular weight distribution M w /M n 7.4, polymer T m =130.3°C.
实施例46、利用配合物Fe-8及MAO联合催化加压下的乙烯聚合Example 46. Utilizing complex Fe-8 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-8，助催化剂为MAO，聚合温度为80℃。聚合活性：8.54×106g/mol(Fe)h-1，聚合分子量Mw＝8.63kg mol-1，分子量分布Mw/Mn为6.8，聚合物Tm＝126.4℃。Basically the same as Example 37d), except that the main catalyst is Fe-8, the co-catalyst is MAO, and the polymerization temperature is 80°C. Polymerization activity: 8.54×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =8.63 kg mol -1 , molecular weight distribution M w /M n is 6.8, polymer T m =126.4°C.
实施例47、利用配合物Fe-8及MAO联合催化加压下的乙烯聚合Example 47. Utilizing complex Fe-8 and MAO to jointly catalyze ethylene polymerization under pressure
基本同实施例37d)，区别在于：主催化剂为Fe-8，助催化剂为MAO，聚合温度为100℃。聚合活性：3.92×106g/mol(Fe)h-1，聚合分子量Mw＝7.06kg mol-1，分子量分布Mw/Mn为6.8，聚合物Tm＝126.6℃。Basically the same as Example 37d), except that the main catalyst is Fe-8, the co-catalyst is MAO, and the polymerization temperature is 100°C. Polymerization activity: 3.92×10 6 g/mol(Fe)h -1 , polymer molecular weight M w =7.06 kg mol -1 , molecular weight distribution M w /M n is 6.8, polymer T m =126.6°C.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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