WO2017161466A1 - 新型线性α烯烃催化剂及其制备和应用 - Google Patents

新型线性α烯烃催化剂及其制备和应用 Download PDF

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WO2017161466A1
WO2017161466A1 PCT/CN2016/000184 CN2016000184W WO2017161466A1 WO 2017161466 A1 WO2017161466 A1 WO 2017161466A1 CN 2016000184 W CN2016000184 W CN 2016000184W WO 2017161466 A1 WO2017161466 A1 WO 2017161466A1
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catalyst
alkyl
carbon
butylphenyl
tert
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PCT/CN2016/000184
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English (en)
French (fr)
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魏东初
李兵
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亚培烯科技(嘉兴)有限公司
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Priority claimed from CN201610164561.4A external-priority patent/CN105728045B/zh
Priority claimed from CN201610165648.3A external-priority patent/CN105797773B/zh
Priority claimed from CN201610165991.8A external-priority patent/CN105797774B/zh
Application filed by 亚培烯科技(嘉兴)有限公司 filed Critical 亚培烯科技(嘉兴)有限公司
Priority to BR112018017060-7A priority Critical patent/BR112018017060B1/pt
Priority to KR1020187030161A priority patent/KR102222844B1/ko
Priority to US15/731,880 priority patent/US10441946B2/en
Publication of WO2017161466A1 publication Critical patent/WO2017161466A1/zh

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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • C07—ORGANIC CHEMISTRY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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Definitions

  • the invention relates to the field of industrial catalysts, in particular to novel linear alpha olefin catalysts and preparation methods and applications thereof.
  • Linear alpha-olefin refers to high-carbon linear olefins above C 4 -C 28 and is an important organic chemical raw material that has developed rapidly in the past 30 years.
  • the main uses of ⁇ -olefins are as follows: 1) comonomers.
  • the comonomers used in the production of linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) are mainly 1-butene, 1-hexyl.
  • the production method of the ⁇ -olefin mainly includes a wax cracking method, an alkane dehydrogenation method, an ethylene oligomerization method, and an extraction separation method.
  • ethylene oligomerization is the main method for producing ⁇ -olefins, and the ⁇ -olefin produced by this method accounts for 94.1% of the total ⁇ -olefin production.
  • the catalyst to be used is mainly an alkyl aluminum system, a titanium system, an iron system, a nickel system, a chromium system or the like.
  • the main technologies of ethylene oligomerization are the Ziegler process of CPChem, the improved Ziegler process of INEOS, and the SHOP process of Shell. Idemitsu process of Japan Iwate Petrochemical Company, VERSIPOL process of Dupond Company, etc. Among them, Shell's SHOP process route is complex and the process route is long. In addition to the oligomerization process, there are disproportionation and isomerization, so the production cost is the highest, but the product quality is good, the distribution is flexible, and the ⁇ -olefin conversion can be produced. Internal olefin. The research on the polymerization of ethylene oligomers into ⁇ -olefins has made great progress.
  • the object of the present invention is to provide a series of catalyst compositions capable of increasing the relative content of linear ⁇ -olefins having a carbon number distribution of C 6 -C 18 in a product, a preparation method thereof and a catalyst for catalyzing ethylene oligomerization using the catalyst composition
  • Linear alpha-olefins are available to meet the immediate needs of the chemical industry.
  • the present invention relates to a series of ethylene oligomerized iron-based catalyst compositions and uses thereof, characterized in that the main catalyst is an iron-based (II) imine-based coordination compound, and the cocatalyst is methylaluminoxane or triisobutyl chloride. And a mixture of borane or GaCl 3 .
  • These catalyst compositions are used to catalyze ethylene oligomerization such that the carbon number distribution to the linear alpha olefin is between C 4 - C 28 with a C 6 - C 20 component greater than 80%.
  • the present invention provides a novel linear poly- ⁇ olefin catalyst comprising a main catalyst and a cocatalyst, wherein the main catalyst is an iron-based imine coordination compound having the structure of the general formula (I):
  • R 21 and R 22 and R 22 and R 23 are each ring-bonded to an aromatic ring and form a fused ring structure
  • R 11 is H, C1-C6 alkyl, isopropyl or trifluoromethyl
  • R 13 is phenyl, wherein a carbon atom between R 11 and a is a single bond, and a carbon at the a site and a carbon at the c site are double key;
  • R' 11 is H, C1-C6 alkyl, isopropyl or trifluoromethyl, and R 14 is phenyl, wherein the b-position carbon and the d-position N are double bonds, and the d-position between N and R 14 is single bond;
  • R 21 , R 22 and R 23 are each H or a C1-C6 alkyl group
  • R 11 is H, C1-C6 alkyl, isopropyl or trifluoromethyl
  • R 13 is phenyl, wherein a carbon atom between R 11 and a is a single bond, and a carbon at the a site and a carbon at the c site are double key;
  • R' 11 is H, C1-C6 alkyl, isopropyl or trifluoromethyl
  • R 14 is C(R')R"
  • R' is C1-C6 alkyl, isopropyl or trifluoromethyl
  • R" is a phenyl group, wherein a carbon bond between the b site carbon and the d site N is a single bond, and a d bond between N and R 14 is a double bond;
  • R 21 and R 11 and R 11 and R 13 are each ring-bonded to form an aromatic ring, and form a fused ring structure
  • R 23 and R' 11 are ring-bonded to a naphthene structure, and R 14 is a phenyl group, wherein a carbon bond between the b-position carbon and the d-site N is a double bond, and a single bond between R 14 and the d-position N is a single bond.
  • the main catalyst has the structural formula (IA), (IB) or (IC), that is,
  • R 1 to R 11 are each independently selected from H, C 1 -C 6 alkyl, halogen, C 1 -C 6 alkoxy; R 11 is C 1 -C 6 alkyl, isopropyl or trifluoromethyl;
  • R 1 -R 10 are each independently selected from H, C1-C6 alkyl, halogen, C1-C6 alkoxy;
  • R 11 is a C1-C6 alkyl, isopropyl or trifluoromethyl;
  • R 12 is C1-C6 alkyl, isopropyl or trifluoromethyl; or
  • R 1 to R 5 are each independently selected from the group consisting of H, C1-C6 alkyl, halogen, and C1-C6 alkoxy.
  • the main catalysts can be divided into three categories in preparation:
  • the first type is a pyridine non-alkenyl derivative, and the catalyst is obtained by ring-forming a non-alkenylene and a substituted pyridine;
  • the second type is a pyridine derivative
  • the catalyst is obtained by reacting 2-acetyl-6-methylaminopyridine with a substituted aniline, and 2-formyl-6-methylaminopyridine is obtained from a pyridine as a raw material through several steps;
  • the third type is a derivative of phenanthroline, and the catalyst is obtained by reacting 9,10-dihydrobenzo[b][1,10]phenanthroline-11(8H)-one with a substituted aniline, 9 , 10-Dihydrobenzo[b][1,10]phenanthroline-11(8H)-one is prepared by [1,10]phenanthroline in several steps.
  • the cocatalyst is a mixture of methyl aluminoxane, triisobutylaluminum borane or GaCl 3, and three parts.
  • the amount ratio of the substance of methylaluminoxane to triisobutylaluminum is from 100:1 to 1:1, especially from 90:1 to 10:1.
  • the mass ratio of GaCl 3 to methylaluminoxane and triisobutylaluminum is from 1:100:10 to 1:10000:100.
  • the iron-based catalyst composition is used for catalyzing ethylene oligomerization to prepare a linear ⁇ -olefin, comprising: adding ethylene pressure to 0.1-20 MPa under anhydrous and anaerobic conditions, and sequentially adding the reaction temperature to 0-100 ° C.
  • Organic solvent hexane or cyclohexane
  • cocatalyst and main catalyst solution after reacting for 5 to 60 minutes, cooling to -10 ° C to 0 ° C, adding methanol to terminate the reaction, and finally separating by linear distillation to obtain linear ⁇ -olefin selection
  • the property is >97%, and the carbon number is distributed between C 4 -C 28 , wherein the component of C 6 -C 20 is more than 80%.
  • the ratio of the amount of the cocatalyst to the main catalyst is from 5000:1 to 500:1 in terms of Al/Fe, especially from 1000:1 to 500:1. optimal.
  • R 11 is exemplified by a methyl group:
  • Compound 4 (10 g, 0.028 mol) is dissolved in THF 50 mL, cooled to -78 ° C, and butyl lithium (0.06 mol) is added dropwise, and after completion of the dropwise addition, the temperature is raised to room temperature, and DMAC (21 g) is added. After the completion of the dropwise addition, the mixture was heated to 50 ° C for 2 hours, the reaction was stopped, the ammonium chloride solution was added to quench, and the organic phase was extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated. Crystallization from ethanol gave pure compound 5 (3.5 g, 48%).
  • the compound 5 and the substituted aniline were reacted under anhydrous and oxygen-free conditions, wherein the molar ratio of the compound 5 to the substituted aniline was 1:1.2, the solvent was toluene, and refluxing was carried out using p-toluenesulfonic acid as a catalyst.
  • the reaction time is 3-6 hours, and the reaction is monitored by TLC. After completion of the reaction, the solvent is removed under reduced pressure, and then subjected to column chromatography (with petroleum ether and ethyl acetate as eluent) to give the desired product.
  • the aniline in the process of the invention may be 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethyl Aniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 3,6-dimethylaniline, 2,4,6-trimethylaniline, 4 -bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2,3,4-tri Fluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, most preferably 4-methylaniline.
  • 4-methylaniline is exemplified: compound 5 (1 g, 3.85 mmol) is dissolved in 50 ml of toluene, and 1.2 eq of 4-methylaniline is added dropwise. After the addition is completed, 0.1 eq of p-toluenesulfonic acid is added and refluxed. After 3 hours, TLC showed complete reaction. The reaction was stopped and the solvent was removed under reduced pressure. Purified by column chromatography to give compound R 3 is methyl 6 (1.35g, 80%).
  • the compound 10 and the substituted aniline were reacted under anhydrous and oxygen-free conditions, wherein the molar ratio of the compound 10 to the substituted aniline was 1:1.2, the solvent was toluene, and refluxing was carried out using p-toluenesulfonic acid as a catalyst.
  • the reaction time was 3-6 hours, and the reaction was monitored by TLC. After the reaction was completed, the solvent was removed under reduced pressure, and then column chromatography (with petroleum ether and ethyl acetate as eluent) to give the desired product.
  • the aniline in the process of the invention may be 2-methylaniline, 3- Methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-di Methylaniline, 3,5-dimethylaniline, 3,6-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-ethyl Aniline, 2-ethyl-6-methylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2,3,4-trifluoroaniline, 2,4,5-trifluoroaniline, 2,4 , 6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, most preferably 4-methylaniline.
  • 4-methylaniline is exemplified: Compound 10 (1 g, 7 mmol) is dissolved in 50 ml of toluene, and 1.2 eq of 4-methylaniline is added dropwise. After the addition is completed, 0.1 eq of p-toluenesulfonic acid is added and refluxed. TLC showed complete reaction after 3 hours. The reaction was stopped and the solvent was removed under reduced pressure. Purified by column chromatography to give R 3 is a methyl group 11 (1.3g, 85%).
  • the substituted benzophenone in the method of the present invention may be 2-methylacetophenone, 3-methylacetophenone, 4-methylacetophenone, 2,3-dimethylacetophenone, 2,4- Dimethylacetophenone, 2,5-dimethylacetophenone, 2,6-dimethylacetophenone, 3,4-dimethylacetophenone, 3,5-dimethylacetophenone, 3,6-dimethylacetophenone, 2,4,6-trimethylacetophenone, 4-bromo-2,6-dimethylacetophenone, 2-ethylacetophenone, 2-B Base-6-methylacetophenone, 2-fluoroacetophenone, 2-fluoro-4-methylacetophenone, 2,3,4-trifluoroacetophenone, 2,4,5-trifluorobenzene Ketone, 2,4,6-trifluoroacetophenone, 2,3,4,5,6-pentafluoroacetophenone, 2-methylpropiophenone, 3-methylpropiophenone, 4-methyl
  • Example 3 phenanthroline as a substrate
  • the compound 16 and the substituted aniline were reacted under anhydrous and oxygen-free conditions, wherein the molar ratio of the compound 16 to the substituted aniline was 1:1.2, the solvent was toluene, and refluxing was carried out using p-toluenesulfonic acid as a catalyst. Reaction time is 3- After 6 hours, the reaction was monitored by TLC. After completion of the reaction, the solvent was removed under reduced pressure, and then subjected to column chromatography (with petroleum ether and ethyl acetate as eluent).
  • the aniline in the process of the invention may be 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethyl Aniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 3,6-dimethylaniline, 2,4,6-trimethylaniline, 4 -bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2,3,4-tri Fluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, most preferably 4-methylaniline.
  • 4-methylaniline is exemplified: Compound 16 (1 g, 4 mmol) is dissolved in 50 ml of toluene, and 1.2 eq of 4-methylaniline is added dropwise. After the addition is completed, 0.1 eq of p-toluenesulfonic acid is added and refluxed. TLC showed complete reaction after 3 hours. The reaction was stopped and the solvent was removed under reduced pressure. Purification by column chromatography gave Compound 17 (1.1 g, 80%).
  • the 250 mL three-necked flask equipped with a magnetic stirrer and dried was vacuumed, replaced with nitrogen several times, and then charged with ethylene, and then quantitatively added toluene, cocatalyst MAO and a catalyst were sequentially added, and an oligomerization reaction was carried out at a predetermined temperature.
  • the pressure is kept constant by the solenoid valve automatically, the pressure in the buffer tank is changed with time, the polymerization time is 30 min, and finally the reaction is terminated with methanol or acidified ethanol having a mass fraction of 10%.
  • the ethylene oligomerization product was analyzed by the GC-MS method, and the activity of the catalyst was determined from the pressure drop of the ethylene buffer tank.
  • the alpha olefin content is greater than 99% and the linear alpha olefin selectivity is greater than 96%.
  • Catalysts 7-1 to 7-3 are: the main catalyst structure (Compound 7 obtained in Example 1 of the specification) is as shown in the following figure, wherein R11 is a methyl group, R1, R2, R4 and R6, R7, R9 It is hydrogen.
  • Catalyst 7-1 R3 and R8 are methoxy groups, and R5 and R10 are methyl groups.
  • Catalyst 7-3 R5 and R10 are bromine, and R3 and R8 are hydrogen.
  • Catalysts 13-1 to 13-3 are: the main catalyst structure (Compound 13 obtained in Patent Specification Example 2) is shown below, wherein R11 and R12 are methyl groups, R2, R4, R5 and R7, R9 And R10 is hydrogen.
  • Catalyst 13-1 R1 and R6 are methoxy groups, and R3 and R8 are methyl groups.
  • Catalyst 13-3 R1 and R6 are bromine, and R3 and R8 are hydrogen.
  • Catalysts 18-1 to 18-3 are: The main catalyst structure (Compound 18 obtained in Patent Specification Example 3) is shown below, wherein R2 and R4 are hydrogen.
  • Catalyst 18-1 R3 is a methoxy group, and R1 and R5 are a methyl group.
  • Catalyst 18-2 R3 and R5 are methyl and R1 is hydrogen.
  • Catalyst 18-3 R1 is bromine, R5 is methyl, and R3 is hydrogen.
  • Catalysts 19 to 21 are comparative examples: three catalysts in J. Am. Chem. Soc. 1998, 120, 7143-7144, the main catalyst structural formula is shown below. Wherein catalyst 19 is of formula 7, R is methyl; catalyst 20 is of formula 8, R is ethyl; catalyst 21 is of formula 9, and R is isopropyl.

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Abstract

本发明涉及新型线性α烯烃催化剂及其制备和应用。所述催化剂组合物由主催化剂和助催化剂组成，其中主催化剂为铁系亚胺基配位化合物，助催化剂为甲基铝氧烷、三异丁基铝、硼烷和GaCl3。该催化剂组合物用于催化乙烯齐聚制备线性α烯烃，线性α烯烃选择性大于96％，碳数分布在C4-C28，其中C6-C20大于75％。本发明的催化剂，结构稳定，能够用于乙烯齐聚，催化效率高，本发明的制备方法操作简便、产率高、原料易得，成本低、环境污染小，易于工业化生产。

Description

新型线性α烯烃催化剂及其制备和应用 技术领域
本发明涉及工业催化剂领域，尤其涉及新型线性α烯烃催化剂及其制备方法和应用。
背景技术
线性α-烯烃(LAO)是指C4-C28以上高碳直链端烯烃，是近30年来迅速发展的一种重要的有机化工原料。α-烯烃主要用途有以下五大类：1)共聚单体，在线性低密度聚乙烯(LLDPE)及高密度聚乙烯(HDPE)生产中使用的共聚单体主要有1-丁烯，1-己烯和1-辛烯；2)用于生产洗涤剂和洗涤剂醇，由α-烯烃合成的洗涤剂醇具有很好的生物降解性；3)合成润滑油，聚α-烯烃是优质的合成润滑油，它主要是1-癸烯和1-辛烯的齐聚物；4)增塑剂醇，C8-C10直链α-烯烃经羰基合成制得的增塑剂醇挥发度低，并具有很好的光稳定性和抗氧化性；5)用于生产润滑油添加剂及钻井液，粘合剂，密封剂等。α-烯烃的用量中有50％以上用作聚乙烯的共聚单体。
α-烯烃的生产方法主要有蜡裂解法，烷烃脱氢法，乙烯齐聚法，萃取分离方法。目前乙烯齐聚是生产α-烯烃的主要方法，利用该方法生产的α-烯烃占整个α-烯烃生产总量的94.1％。所用催化剂主要有烷基铝系，钛系，铁系，镍系，铬系等。根据所用催化剂和生产工艺的不同，乙烯齐聚法主要技术有CPChem公司的Ziegler工艺，INEOS公司的改进的Ziegler工艺，Shell公司的SHOP工艺。日本出光石化公司的Idemitsu工艺，Dupond公司的VERSIPOL工艺等。其中Shell公司的SHOP工艺路线复杂，工艺路线长，除齐聚过程外，还有歧化，异构化等，因此生产成本最高，但其产品质量好，分布灵活，并可使α-烯烃转化生产内烯烃。乙烯齐聚合成α-烯烃的催化剂的研究取得很大进展，近年来出现采用非均相法烯烃齐聚制备α-烯烃的研究报道和专利。随着聚乙烯(PE)工业的迅速发展，对α-烯烃，特别是1-己烯和1-辛烯的需求越来越大。1-己烯共聚PE是目前增长最快的品种。世界上共有11个生产商的13套α-烯烃生 产装置生产运行，主要集中在北美，欧洲，南非，日本等。2009年世界α-烯烃生产能力为4334kt/a，2010年超过4914kt/a。
随着聚烯烃工业和表面活性剂工业的飞速发展，作为聚烯烃共聚单体的C6-C8和作为洗涤剂主要原料的C10-C18部分的线性α-烯烃的需求量日益增大，因此努力提高该部分线性α-烯烃在总产品中的含量具有非常重要的经济价值和现实意义。
发明内容
本发明的目的就是在于提供一系列可以提高碳数分布为C6-C18的线性α-烯烃在产品中的相对含量的催化剂组合物及其制备方法和使用该催化剂组合物催化乙烯齐聚制备线性α-烯烃的方法，以满足目前化工行业的迫切需求。
本发明涉及一系列乙烯齐聚的铁系催化剂组合物及其应用，其特征是主催化剂为铁系(II)亚胺基配位化合物，助催化剂为甲基铝氧烷，三异丁基氯和硼烷或GaCl3的混合物。这些催化剂组合物用于催化乙烯齐聚，使得到线性α-烯烃的碳数分布在C4-C28之间，其中C6-C20组分大于80％。
本发明提供了一种新型线性聚-α烯烃催化剂，包括主催化剂和助催化剂，其中所述主催化剂为铁系亚胺基配位化合物，其具有通式(I)的结构：
Figure PCTCN2016000184-appb-000001
其中，进一步包括基团结构(A)、(B)或(C)：
(A)：
R21和R22以及R22和R23分别成环连接为芳环，并成稠环结构；
R11为H、C1-C6烷基、异丙基或三氟甲基，R13为苯基，其中R11和a位碳之间为单键，a位碳和c位N之间为双键；
R’11为H、C1-C6烷基、异丙基或三氟甲基，R14为苯基，其中b位碳和d位N之间为双键，d位N和R14之间为单键；
(B)：
R21、R22和R23分别为H或C1-C6烷基；
R11为H、C1-C6烷基、异丙基或三氟甲基，R13为苯基，其中R11和a位碳之间为单键，a位碳和c位N之间为双键；
R’11为H、C1-C6烷基、异丙基或三氟甲基，R14为C(R’)R”，R’为C1-C6烷基、异丙基或三氟甲基，R”为苯基，其中b位碳和d位N之间为单键，d位N和R14之间为双键；
(C)：
R21和R11以及R11和R13分别成环连接形成芳环，并成稠环结构；
R23和R’11成环连接为环烷结构，R14为苯基，其中b位碳和d位N之间为双键，R14和d位N之间为单键。
根据本发明的具体实施方式，所述主催化剂的结构式为(IA)、(IB)或(IC)，亦即：
Figure PCTCN2016000184-appb-000002
其中，R1-R11各自独立地选自H，C1-C6烷基，卤素，C1-C6烷氧基；R11为C1-C6烷基，异丙基或三氟甲基；或
Figure PCTCN2016000184-appb-000003
其中，R1-R10各自独立地选自H，C1-C6烷基，卤素，C1-C6烷氧基；R11为C1-C6烷基，异丙基或三氟甲基；R12为C1-C6烷基，异丙基或三氟甲基；或
Figure PCTCN2016000184-appb-000004
其中，R1-R5各自独立地选自H，C1-C6烷基，卤素，C1-C6烷氧基。
所述主催化剂在制备上可分为三类：
第一类为吡啶并非那烯衍生物，所述的催化剂为非那烯和取代吡啶成环所得；
第二类为吡啶衍生物，所述的催化剂为2-乙酰基-6-甲氨基吡啶和取代苯胺反应获得，2-甲酰基-6-甲氨基吡啶从吡啶为原料经过几步反应获得；
第三类是为菲咯啉的衍生物，所述的催化剂为9，10-二氢苯并[b][1，10]菲咯啉-11(8H)-酮和取代苯胺反应获得，9，10-二氢苯并[b][1，10]菲咯啉-11(8H)-酮由[1，10]菲咯啉经过几步反应制得。
所述助催化剂为一种混合物，由甲基铝氧烷，三异丁基铝和硼烷或GaCl3三部分组成。其中甲基铝氧烷与三异丁基铝的物质的量比为100∶1至1∶1混合，尤其是90∶1至10∶1。GaCl3与甲基铝氧烷和三异丁基铝的物质量的比为1∶100∶10至1∶10000∶100。
所述的铁系催化剂组合物用于催化乙烯齐聚制备线性α-烯烃的方法，包括：在无水无氧条件下，乙烯压力为0.1～20MPa，反应温度为0-100℃时，顺序加入有机溶剂(己烷或环己烷)、助催化剂和主催化剂溶液，反应5～60分钟后，冷却至-10℃～0℃，加入甲醇终止反应，最后经精馏分离得到线性α-烯烃选择性＞97％，碳数分布在C4-C28之间，其中C6-C20的组分大于80％。
所述的铁系催化剂组合物的应用，其中所述的有机溶剂为石油醚，甲苯，二甲苯，所述的主催化剂溶液的溶剂为1，2-二氯乙烷，二氯甲烷，三氯甲烷，邻二氯苯，己烷或环己烷，所述的助催化剂与主催化剂的物质的量比以Al/Fe计为5000∶1～500∶1，尤其以1000∶1～500∶1最佳。
具体实施方式
实施例1、2，6-二甲酰基-吡啶并非那烯为底物
Figure PCTCN2016000184-appb-000005
化合物1的合成参照文献Chemische Berichte.，Vol20，P662.化合物1(10g，0.052mol)溶于醋酸100mL，加入AlCl3(35g，0.26mol)，反应溶液加热回流2小时，TLC显示原料已经消失，停止反应，加入冰水淬灭，二氯甲烷萃取，有机相用无水无水硫酸钠干燥后蒸干溶剂，粗产品经柱层析分离(淋洗液为石油醚和乙酸乙酯)后得到纯的化合物2(9g，73％)。1H NMR(CHCl3d3)δppm：8.06(d，1H，芳环H)，7.72(d，1H，芳环H)，7.52(d，1H，芳环H)，7.35(d，1H，芳环H)，7.24(d，1H，芳环H)，6.31(d，1H，芳环H)，6.23(d，1H，芳环H)，4.29(d，1H)。
化合物2(9g，0.038mol)溶于50mL甲醇，冷至0℃，加入氨水(1.6g，0.045mol)，反应2小时，然后停止反应，抽干溶剂得到化合物3(8.93g，100％)。1H NMR(CHCl3d3)δppm：10.0(s，1H，NH-)，7.88(d，1H，芳环H)，7.69(d，1H，芳环H)，7.52(d，1H，芳环H)，7.35(d，1H，芳环H)，7.24(d，1H，芳环H)，6.31(d，1H，芳环H)，6.23(d，1H，芳环H)，4.40(d，1H)。
Figure PCTCN2016000184-appb-000006
化合物3(8g，0.034mol)溶于50mL甲苯，加入三溴化磷(46g，0.17mol)，回流反应2小时，冷却，蒸干溶剂后柱层析纯化得到化合物4(11g，90％)。1H NMR (CHCl3d3)δppm：8.08(d，2H，芳环H)，7.62(d，2H，芳环H)，7.39(d，2H，芳环H)，7.32(d，2H，芳环H)。
这里R11以甲基为例：将化合物4(10g，0.028mol)溶于THF 50mL，冷却至-78℃，滴加丁基锂(0.06mol)，滴加完毕后升温至室温加入DMAC(21g，0.29mol)，滴加完毕后升温至50℃反应2小时，停止反应，加入氯化铵溶液淬灭，有机相用二氯甲烷萃取。有机相用无水硫酸钠干燥后，过滤，蒸干。乙醇冲结晶可得到纯的化合物5(3.5g，48％)。1H NMR(CHCl3d3)δppm8.45(d，2H，芳环H)，7.73(d，2H，芳环H)，7.49(d，2H，芳环H)，7.32(d，2H，芳环H)，2.55(s，6H，CH3 CO-)
Figure PCTCN2016000184-appb-000007
化合物5和取代苯胺在无水无氧的条件下进行反应，其中化合物5和取代苯胺的摩尔比为1∶1.2，溶剂为甲苯，用对甲苯磺酸为催化剂回流下进行。反应时间为3-6个小时，TLC监测反应，反应完毕后，减压除掉溶剂，然后柱层析(用石油醚和乙酸乙酯为淋洗液)，即可得到目标产物6。本发明方法中的苯胺可以是2-甲基苯胺，3-甲基苯胺，4-甲基苯胺，2，3-二甲基苯胺，2，4-二甲基苯胺，2，5二甲基苯胺，2，6-二甲基苯胺，3，4-二甲基苯胺，3，5-二甲基苯胺，3，6-二甲基苯胺，2，4，6-三甲基苯胺，4-溴-2，6-二甲基苯胺，2-乙基苯胺，2-乙基-6甲基苯胺，2-氟苯胺，2-氟-4-甲基苯胺，2，3，4-三氟苯胺，2，4，5-三氟苯胺，2，4，6-三氟苯胺，2，3，4，5，6-五氟苯胺，最优选4-甲基苯胺。
这里以4-甲基苯胺为例：化合物5(1g，3.85mmol)溶于50毫升甲苯，滴加1.2eq当量的4-甲基苯胺，滴加完毕后加入0.1eq的对甲苯磺酸，回流，3个小时后TLC显示反应完全。停止反应，减压除掉溶剂。柱层析纯化后得到R3为甲基的化合物6(1.35g，80％)。特征：1H NMR(CHCl3d3)δppm：7.87(d，2H，芳环H)，7.50(d，2H，芳环H)，7.49(d，2H，芳环H)，7.32(d，1H，芳环H)，7.1(m，8H，芳环H)，2.35(s，6H，CH3 )，0.9(s，6H，CH3 N-)。
Figure PCTCN2016000184-appb-000008
这里以4-甲基苯胺，4-甲基苯甲醛为例，在惰性气体的保护下，将化合物6(1g，2.3mmol)溶于50毫升甲苯中，用惰性气体赶走溶剂中的氧气，然后加入氯化亚铁(5.2g，4.08mmol)，在惰性气体保护下搅拌过夜，TLC检测已经反应完全，过滤，蒸干溶剂，粗品用乙醚洗涤后可得化合物7(0.89g，68％)。1H NMR(CHCl3d3)δppm：7.90(d，2H，芳环H)，7.50(d，2H，芳环H)，7.49(d，2H，芳环H)，7.32(d，1H，芳环H)，7.1(m，8H，芳环H)，2.35(s，6H，CH3 )，0.9(s，6H，CH3 N-)。
实施例2、2-乙酰基-6甲胺基为底物
Figure PCTCN2016000184-appb-000009
化合物8的方法遵循文献Synthetic Communications，2005，35，2317-2324的报道从2，6-二甲基吡啶为原料经氧化在还原得到。化合物8(10g，0.07mol)溶于二氯甲烷，冷却至0℃然后加入氨水(1.2g，0.079mol)，搅拌反应半小时后停止反应，蒸干溶剂。柱层析可得到单取代的化合物9(5.8g，60％)。特征：1H NMR(CHCl3d3)δppm：8.12(m，1H，芳环H)，7.66(m，1H，芳环H)，7.60(m，1H，芳环H)，5.12(m，2H，CH2 -)，4.24(m，2H，CH2 -)。
化合物9(5g，0.036mol)溶于二氯甲烷，加入PCC氧化剂(8.6g，0.04mol)，室温反应2小时，TLC显示反应结束，停止反应，蒸干溶剂。柱层析了得到2-位醛基的化合物。2-位醛基的化合物溶于二氯甲烷，降温至-78℃，滴加二甲基锂溶液(1.1eq)，加入后反应2小时，加入氯化铵溶液淬灭，有机相用二氯甲烷萃取，干燥，蒸干后柱层析后可得化合物10(4.5g，92％)。特征：1H NMR(CHCl3d3)δppm：8.24(m，1H，芳环H)，8.22(m，1H，芳环H)，8.08(m，1H，芳环H)，4.24(m，2H，CH2 -)，2.36(s，3H，CH3CO-)。
Figure PCTCN2016000184-appb-000010
化合物10和取代苯胺在无水无氧的条件下进行反应，其中化合物10和取代苯胺的摩尔比为1∶1.2，溶剂为甲苯，用对甲苯磺酸为催化剂回流下进行。反应时间为3-6个小时，TLC监测反应，反应完毕后，减压除掉溶剂，然后柱层析(用石油醚和乙酸乙酯为淋洗液)，即可得到目标产物11。本发明方法中的苯胺可以是2-甲基苯胺，3- 甲基苯胺，4-甲基苯胺，2，3-二甲基苯胺，2，4-二甲基苯胺，2，5二甲基苯胺，2，6-二甲基苯胺，3，4-二甲基苯胺，3，5-二甲基苯胺，3，6-二甲基苯胺，2，4，6-三甲基苯胺，4-溴-2，6-二甲基苯胺，2-乙基苯胺，2-乙基-6甲基苯胺，2-氟苯胺，2-氟-4-甲基苯胺，2，3，4-三氟苯胺，2，4，5-三氟苯胺，2，4，6-三氟苯胺，2，3，4，5，6-五氟苯胺，最优选4-甲基苯胺。
这里以4-甲基苯胺为例：化合物10(1g，7mmol)溶于50毫升甲苯，滴加1.2eq当量的4-甲基苯胺，滴加完毕后加入0.1eq的对甲苯磺酸，回流，3个小时后TLC显示反应完全。停止反应，减压除掉溶剂。柱层析纯化后得到R3为甲基的化合物11(1.3g，85％)。特征：1H NMR(CHCl3d3)δppm：8.06(m，1H，芳环H)，7.93(m，1H，芳环H)，7.82(m，1H，芳环H)，4.24(m，2H，CH2 -)，2.35(s，3H，CH3 -)，0.9(s，3H，CH3 N-)。
Figure PCTCN2016000184-appb-000011
化合物11和取代苯酮在无水无氧的条件下进行反应，其中化合物11和取代苯胺的摩尔比为1∶1.2，溶剂为甲苯，用对甲苯磺酸为催化剂回流下进行。反应时间为3-6个小时，TLC监测反应，反应完毕后，减压除掉溶剂，然后柱层析(用石油醚和乙酸乙酯为淋洗液)，即可得到目标产物12。本发明方法中的取代苯酮，可以是2-甲基苯乙酮，3-甲基苯乙酮，4-甲基苯乙酮，2，3-二甲基苯乙酮，2，4-二甲基苯乙酮，2，5二甲基苯乙酮，2，6-二甲基苯乙酮，3，4-二甲基苯乙酮，3，5-二甲基苯乙酮，3，6-二甲基苯乙酮，2，4，6-三甲基苯乙酮，4-溴-2，6-二甲基苯乙酮，2-乙基苯乙酮，2-乙基-6甲基苯乙酮，2-氟苯乙酮，2-氟-4-甲基苯乙酮，2，3，4-三氟苯乙酮，2，4，5-三氟苯乙酮，2，4，6-三氟苯乙酮，2，3，4，5，6-五氟苯乙酮，2-甲基苯丙酮，3-甲基苯丙酮，4-甲基苯丙酮，2，3-二甲基苯丙酮，2，4-二甲基苯丙酮，2，5二甲基苯丙酮，2，6-二甲基苯丙酮，3，4-二甲基苯丙酮，3，5-二甲基苯丙酮，3，6-二甲基苯丙 酮，2，4，6-三甲基苯丙酮，4-溴-2，6-二甲基苯丙酮，2-乙基苯丙酮，2-乙基-6甲基苯丙酮，2-氟苯丙酮，2-氟-4-甲基苯丙酮，2，3，4-三氟苯丙酮，2，4，5-三氟苯丙酮，2，4，6-三氟苯丙酮，2，3，4，5，6-五氟苯丙酮，2-甲基三氟苯乙酮，3-甲基三氟苯乙酮，4-甲基三氟苯乙酮，2，3-二甲基三氟苯乙酮，2，4-二甲基三氟苯乙酮，2，5二甲基三氟苯乙酮，2，6-二甲基三氟苯乙酮，3，4-二甲基三氟苯乙酮，3，5-二甲基三氟苯乙酮，3，6-二甲基三氟苯乙酮，2，4，6-三甲基三氟苯乙酮，4-溴-2，6-二甲基三氟苯乙酮，2-乙基三氟苯乙酮，2-乙基-6甲基三氟苯乙酮，2-氟三氟苯乙酮，2-氟-4-甲基三氟苯乙酮，2，3，4-三氟三氟苯乙酮，2，4，5-三氟三氟苯乙酮，2，4，6-三氟三氟苯乙酮，2，3，4，5，6-五氟三氟苯乙酮，最优选4-甲基苯乙酮。
这里以4-甲基苯乙酮为例：化合物11(1g，4mmol)溶于50毫升甲苯，滴加1.2eq当量的4-甲基苯乙酮，滴加完毕后加入0.1eq的对甲苯磺酸，回流，3个小时后TLC显示反应完全。停止反应，减压除掉溶剂。柱层析纯化后得到R8为甲基的化合物12(1.2g，90％)。特征：1H NMR(CHCl3d3)δppm：8.11(s，1H，CHN-)，7.98(m，1H，芳环H)，7.86(m，1H，芳环H)，7.51(m，3H，芳环H)，7.09(m，2H，芳环H)，5.14(m，2H，CH2 -)，2.35(s，6H，CH3 -)，0.9(s，3H，CH3 N-)。
Figure PCTCN2016000184-appb-000012
这里以4-甲基苯胺，4-甲基苯乙酮为例，在惰性气体的保护下，将化合物12(1g，3mmol)溶于50毫升甲苯中，用惰性气体赶走溶剂中的氧气，然后加入氯化亚铁(4.5g，3.55mmol)，在惰性气体保护下搅拌过夜，TLC检测已经反应完全，过滤，蒸干溶剂，粗品用乙醚洗涤后可得化合物13(1.2g，88％)。1H NMR(CHCl3d3)δppm： 7.98(m，1H，芳环H)，7.86(m，1H，芳环H)，7.51(m，3H，芳环H)，7.50(s，1H，CHN-)，7.10(m，2H，芳环H)，5.10(m，2H，CH2 -)，2.35(s，6H，CH3 -)，0.9(s，3H，CH3 N-)。
实施例3、菲咯啉为底物
Figure PCTCN2016000184-appb-000013
化合物15的方法遵循文献Organometallics，25(3)，2006的报道从1，10-菲咯啉为原料经两步得到。
化合物15(2.2g，1mmol)溶于二氯甲烷，然后滴加1.1eq二氯亚砜，滴加完毕后，搅拌2小时，不经分离直接加入AlCl3(2g，1.5mmol)和3-氯溴丙烷(1.57g，1.1mmol)，室温反应1小时后加热回反应过夜，冷却，将反应后倒入冰水中，用二氯甲烷萃取，有机相用无水硫酸钠干燥，过滤，蒸干后得到催产品3。粗品用石油醚和乙酸乙酯重结晶可得化合物16白色固体(1.4g，56％)。特征：1H NMR(CHCl3d3)δppm：8.81(m，1H，芳环H)，8.00(m，1H，芳环H)，7.87(s，1H，芳环H)，7.68(m，1H，芳环H)，7.43(m，1H，芳环H)，7.26(m，1H，芳环H)，2.55(m，2H，CH2 -)，2.40(m，2H，CH2 -)，1.95(m，2H，CH2 -)。
Figure PCTCN2016000184-appb-000014
化合物16和取代苯胺在无水无氧的条件下进行反应，其中化合物16和取代苯胺的摩尔比为1∶1.2，溶剂为甲苯，用对甲苯磺酸为催化剂回流下进行。反应时间为3- 6个小时，TLC监测反应，反应完毕后，减压除掉溶剂，然后柱层析(用石油醚和乙酸乙酯为淋洗液)，即可得到目标产物17。本发明方法中的苯胺可以是2-甲基苯胺，3-甲基苯胺，4-甲基苯胺，2，3-二甲基苯胺，2，4-二甲基苯胺，2，5二甲基苯胺，2，6-二甲基苯胺，3，4-二甲基苯胺，3，5-二甲基苯胺，3，6-二甲基苯胺，2，4，6-三甲基苯胺，4-溴-2，6-二甲基苯胺，2-乙基苯胺，2-乙基-6甲基苯胺，2-氟苯胺，2-氟-4-甲基苯胺，2，3，4-三氟苯胺，2，4，5-三氟苯胺，2，4，6-三氟苯胺，2，3，4，5，6-五氟苯胺，最优选4-甲基苯胺。
这里以4-甲基苯胺为例：化合物16(1g，4mmol)溶于50毫升甲苯，滴加1.2eq当量的4-甲基苯胺，滴加完毕后加入0.1eq的对甲苯磺酸，回流，3个小时后TLC显示反应完全。停止反应，减压除掉溶剂。柱层析纯化后得到R3为甲基的化合物17(1.1g，80％)。特征：1H NMR(CHCl3d3)δppm：8.81(m，1H，芳环H)，8.03(m，1H，芳环H)，8.00(m，1H，芳环H)，7.68(m，1H，芳环H)，7.43(m，1H，芳环H)，7.26(m，1H，芳环H)，7.1(m，4H，芳环H)，2.55(m，2H，CH2 -)，2.35(s，3H，CH3 -)，1.70(m，2H，CH2 -)，1.30(m，2H，CH2 -)。
Figure PCTCN2016000184-appb-000015
这里以4-甲基苯胺为例，在惰性气体的保护下，将化合物17(1g，3mmol)溶于50毫升甲苯中，用惰性气体赶走溶剂中的氧气，然后加入氯化亚铁(4.5g，3.55mmol)，在惰性气体保护下搅拌过夜，TLC检测已经反应完全，过滤，蒸干溶剂，粗品用乙醚洗涤后可得化合物18(1.1g，80％)。特征：1H NMR(CHCl3d3)δppm：8.81(m，1H，芳环H)，8.00(m，2H，芳环H)，7.70(m，1H，芳环H)，7.40(m，1H，芳环H)，7.30(m，1H，芳环H)，7.1(m，4H，芳环H)，2.55(m，2H，CH2 -)，2.35(s，3H，CH3 -)，1.70(m，2H，CH2 -)，1.30(m，2H，CH2 -)。
乙烯齐聚反应实验过程及方法：
将装有磁力搅拌子且干燥的250mL三口烧瓶趁热抽真空、氮气置换数次后充入乙烯，依次加入定量的甲苯、助催化剂MAO和催化剂，在预定的温度下进行齐聚反应，反应体系的压力由电磁阀自动调节保持恒定，记录缓冲罐中压力随时间的变化，聚合时间为30min，最后用甲醇或质量分数为10％的酸化乙醇终止反应。乙烯齐聚产物用GC-MS法进行分析，催化剂的活性则由乙烯缓冲罐的压力降求出。
乙烯齐聚实验结果示例
下表列举了一些实施例的实验结果。
Figure PCTCN2016000184-appb-000016
注：1.乙烯齐聚催化反应条件：催化剂浓度1.5μmol，50mL甲苯作溶剂，MAO为助催化剂；
2.α烯烃含量大于99％，线性α烯烃选择性大于96％。
3.各催化剂的结构及说明如下：
A.催化剂7-1至7-3为：主催化剂结构(专利说明书实施例1中所获得的化合物7)如下图所示，其中R11为甲基，R1、R2、R4和R6、R7、R9为氢。催化剂7-1：R3和R8为甲氧基，R5和R10为甲基。催化剂7-2：R3和R8为甲基，R5和R10为氢。催化剂7-3：R5和R10为溴，R3和R8为氢。
Figure PCTCN2016000184-appb-000017
B.催化剂13-1至13-3为：主催化剂结构(专利说明书实施例2中所获得的化合物13)如下图所示，其中R11和R12为甲基，R2、R4、R5和R7、R9、R10为氢。催化剂13-1：R1和R6为甲氧基，R3和R8为甲基。催化剂13-2：R3和R8为甲基，R1和R6为氢。催化剂13-3：R1和R6为溴，R3和R8为氢。
Figure PCTCN2016000184-appb-000018
C.催化剂18-1至18-3为：主催化剂结构(专利说明书实施例3中所获得的化合物18)如下图所示，其中R2和R4为氢。催化剂18-1：R3为甲氧基，R1和R5为甲基。催化剂18-2：R3和R5为甲基，R1为氢。催化剂18-3：R1为溴，R5为甲基，R3为氢。
Figure PCTCN2016000184-appb-000019
D.催化剂19至21为对比实施例：文献J.Am.Chem.Soc.1998，120，7143-7144中的三种催化剂，主催化剂结构式如下图所示。其中催化剂19为结构式7，R为甲基；催化剂20为结构式8，R为乙基；催化剂21为结构式9，R为异丙基。
Figure PCTCN2016000184-appb-000020
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，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。

Claims (11)

  1. 一种新型线性聚-α烯烃催化剂，包括主催化剂和助催化剂，其中所述主催化剂为铁系亚胺基配位化合物，其具有通式(I)的结构：
    Figure PCTCN2016000184-appb-100001
    其中，进一步包括基团结构(A)、(B)或(C)：
    (A)：
    R21和R22以及R22和R23分别成环连接为芳环，并成稠环结构；
    R11为H、C1-C6烷基、异丙基或三氟甲基，R13为苯基，其中R11和a位碳之间为单键，a位碳和c位N之间为双键；
    R’11为H、C1-C6烷基、异丙基或三氟甲基，R14为苯基，其中b位碳和d位N之间为双键，d位N和R14之间为单键；
    (B)：
    R21、R22和R23分别为H或C1-C6烷基；
    R11为H、C1-C6烷基、异丙基或三氟甲基，R13为苯基，其中R11和a位碳之间为单键，a位碳和c位N之间为双键；
    R’11为H、C1-C6烷基、异丙基或三氟甲基，R14为C(R’)R”，R’为C1-C6烷基、异丙基或三氟甲基，R”为苯基，其中b位碳和d位N之间为单键，d位N和R14之间为双键；
    (C)：
    R21和R11以及R11和R13分别成环连接形成芳环，并成稠环结构；
    R23和R’11成环连接为环烷结构，R14为苯基，其中b位碳和d位N之间为双键，R14和d位N之间为单键。
  2. 根据权利要求1所述的催化剂，其中所述主催化剂的结构式为(IA)、(IB)或(IC)，亦即：
    Figure PCTCN2016000184-appb-100002
    其中，R1-R11各自独立地选自H，C1-C6烷基，卤素，C1-C6烷氧基；R11为C1-C6烷基，异丙基或三氟甲基；或
    Figure PCTCN2016000184-appb-100003
    其中，R1-R10各自独立地选自H，C1-C6烷基，卤素，C1-C6烷氧基；R11为C1-C6烷基，异丙基或三氟甲基；R12为C1-C6烷基，异丙基或三氟甲基；或
    Figure PCTCN2016000184-appb-100004
    其中，R1-R5各自独立地选自H，C1-C6烷基，卤素，C1-C6烷氧基。
  3. 根据权利要求2所述的催化剂，其中所述主催化剂的结构式为(IA)，所述亚胺基配位化合物由2，6-二乙酰基-吡啶并非那烯和取代苯胺反应获得。
  4. 根据权利要求2所述的催化剂，其中所述主催化剂的结构式为(IB)，所述亚胺基配位化合物由2-乙酰基-6-甲氨基和取代苯胺反应获得。
  5. 根据权利要求2所述的催化剂，其中所述主催化剂的结构式为(IC)，所述亚胺基配位化合物由9，10-二氢苯并[b][1，10]菲咯啉-11(8H)-酮和取代苯胺反应获得，其中所述9，10-二氢苯并[b][1，10]菲咯啉-11(8H)-酮由[1，10]菲咯啉经过几步反应制得。
  6. 根据权利要求1所述的催化剂，其中，被C1-C4烷基一、二或三取代的苯基为：2-甲基苯基，4-甲基苯基，2，4-二甲基苯基，2，6-二甲基苯基，2，4，6-三甲基苯基，2-乙基苯基，4-乙基苯基，2，4-二乙基苯基，2，4，6-三乙基苯基，2-丙基苯基，4-丙基苯基，2，4-二丙基苯基，2，6-二丙基苯基，2，4，6-三丙基苯基，2-异丙基苯基，4-异丙基苯基，2，4-二异丙基苯基，2，6-二异丙基苯基，2，4，6-三异丙基苯基，2-丁基苯基，4-丁基苯基，2，4-二丁基苯基，2，6-二丁基苯基，2，4，6-三丁基苯基，2-叔丁基苯基，4-叔丁基苯基，2，4-二叔丁基苯基，2，6-二叔丁基苯基，2，4，6-三叔丁基苯基，2-叔丁基苯基，4-叔丁基苯基，2，4-二叔丁基苯基，2，6-二叔丁基苯基，或2，4，6-三叔丁基苯基。
  7. 根据权利要求1所述的催化剂，其中，被卤素一、二或三取代的苯基为：2-氯苯基，4-氯苯基，2，4-二氯苯基，2，4，6-三氯苯基，2-溴苯基，4-溴苯基，2，4-二溴苯基，2，4，6-三溴苯基，2-氟苯基，4-氟苯基，2，4-二氟苯基，或2，4，6-三氟苯基。
  8. 根据权利要求1所述的催化剂，其中，被卤素和C1-C4烷基一、二或三取代的苯基为：2-溴-4-甲基苯基，2-溴-6-甲基苯基，2，6-二溴-4-甲基苯基，4-溴-2，6-二甲基苯基，2-氯-4-甲基苯基，2-氯-6-甲基苯基，2，6-二氯-4-甲基苯基，或4-氯-2，6-二甲基苯基。
  9. 根据权利要求1所述的催化剂，其中所述助催化剂为包括甲基铝氧烷、三异丁基铝、以及硼烷或GaCl3三部分的混合物。
  10. 权利要求1所述的催化剂用于催化乙烯齐聚制备线性α烯烃的方法，其包括：在无水无氧条件下，乙烯压力为0.1-20MPa、反应温度为0-100℃时，顺序加入有机溶剂、助催化剂和主催化剂溶液，反应5-60分钟后，冷却至-10℃至0℃，加入甲醇终止反应，最后经精馏得到线性α烯烃，其中，所得到的线性α烯烃的选择性＞97％，碳数分布在C4-C28之间，其中C6-C20组分大于80％。
  11. 权利要求9所述的方法，其中，所述有机溶剂为石油醚、甲苯或二甲苯，所述主催化剂溶液的溶剂为1，2-二氯乙烷、二氯甲烷、三氯甲烷或邻二氯苯，所述助催化剂与所述主催化剂的比率以Al/Fe计为5000∶1至500∶1。
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