WO2002096919A1 - Catalysts for the oligomerization of ethylene, method for preparing them and their usage - Google Patents

Abstract

The present invention relates to a group of catalysts for oligomerization of ethylene, method for preparing them and their usage. They are complexes of haloarylpyridine-bis-(imine) and lower transition metals, which can be synthesized by reacting haloarylpyridine-bis-(imine) with lower transition metals, and have the following structure represented by (I): Wherein: X1 or/and X2 is halogen, R4 or/and R8 is (are) hydrogen, halogen, C¿1-4?-hydrocarbyl, C1-6 ester, C1-6 amine or C1-6 ether, Z is H, -C1-4 hydrocarbyl, aryl, nitro, cyano or trihalomethyl, Y?1,Y2¿=chloro, bromo, iodo, C¿1-4? hydrocarbyl, acetylacetone or fluoroarylboron, M=Fe(II),Fe(III),Co(II) or Ru(II), and R?1,R2,R3,R5,R6 or R7¿=halogen, -H, nitro, cyano, C¿1-4 ?hydrocarbyl, aryl, C1-6 ester, C1-6 amine or C1-6 ether, R?3 and R4¿ together, and/or R?7 and R8¿ together form benzene ring(s). The catalysts of the invention can be combined with co-catalysts to be used for the catalysis of ethylene oligomerization, in which the selectivity for short-chain olefins and the activity of catalysis are both high. Thus, under a pressure of 10 atm. And at a temperature of 60 °C, the activity of catalysis can reached 3.8X107g/mol Fe h, while the content of C¿4?-C12 oligomer on basis of weight percent (wt%) is greater than 91, and the selectivity for α-olefin is greater than 98%.

Description

 Ethylene oligomerization catalyst, synthesis method and application

 The invention relates to an ethylene oligomerization catalyst, a synthesis method and an application. The catalyst is a halogenated arylpyridylbisimine late transition metal complex, which is synthesized from a halogenated arylpyridylbisimine and a late transition metal compound. Can be used to catalyze the oligomerization of ethylene.

 Background technique

The annual output of α-olefins in the world is about 4 × 10 ⁹ pounds. It is an important industrial raw material, mainly used for copolymerization with ethylene to produce linear low density polyethylene and for preparing lubricants, surfactants, plasticizers, etc.

 These α-olefins are mainly obtained by oligomerization of ethylene. At present, the catalytic systems used to catalyze the oligomerization of ethylene mainly include alkyl aluminum systems, pre-transition metal compounds / alkyl aluminum systems, and neutral divalent compounds containing bidentate monoanionic ligands. (Vogt, D. In Applied Homogeneous Catalysis with Organometallic Compounds: Cornils, Beta, Hermann, WA. Eds ,; VCH Publishers: 1996; Vol. I: pp245-256. SkupinSka, J. Chem. Rev. 1991, 91, 613.) At present, some anionic divalent nickel compounds containing diimide bidentate ligands have also been reported to catalyze the oligomerization of ethylene. (Killian, C. M .; Johnson, L. K .; Brookhart, M. Organometallics 1997, 16, 2005)

 Recently, Brookhart's group and Gibson's group found that tridentate pyrimidinide complexes of Fe (II) and Co (II) can catalyze the oligomerization of ethylene with the following structural formula −

催化剂的催化活性很高， 而且 α-烯烃的选择性很高 （Brookhart, M 等， J. Am. Chem. Soc.1998, 120, 7143; WO 99/02472, 1999。 Gibson, V. C. 等， Chem. Commun. 1998, 849; Chem. Eur. J. 2000, 2221 )。

The catalyst has high catalytic activity and high selectivity to α-olefins (Brookhart, M, et al., J. Am. Chem. Soc. 1998, 120, 7143; WO 99/02472, 1999. Gibson, VC et al., Chem. Commun. 1998, 849; Chem. Eur. J. 2000, 2221).

In the tridentate imine complexes they reported, one ortho substituent of aniline must be hydrogen, and the rest of the substituents were hydrogen, alkyl or aryl (methyl, ipr) and other electron-donating groups. People are still discussing and Find new tridentate imine complexes to improve catalytic activity.

 Recently, Qian Changtao et al. (Application No. CN 01105268.6) and BASF (WO 01/07491 A1) have synthesized two Fe (II) complexes with the following structural formula:

These two complexes catalyze the polymerization of ethylene to obtain high molecular weight polyethylene having a number average molecular weight of several thousands to tens of thousands and a weight average molecular weight of tens of thousands to several hundreds of thousands.

 Whether a complex catalyzes the polymerization of ethylene to obtain a high molecular weight polyethylene or a low molecular weight ethylene oligomer (molecular weight less than 500) depends on its structure. If its structure makes the β-fluorene elimination reaction difficult to proceed, a high-molecular-weight polyethylene is obtained, otherwise a low-molecular-weight ethylene oligomer is obtained. So for a complex, if it is a good ethylene polymerization catalyst, it will not be a good ethylene oligomerization catalyst. For example, the above two complexes catalyze the polymerization of ethylene to obtain only high molecular weight polyethylene, rather than low molecular weight ethylene oligomers. New catalysts for the formation of low molecular weight ethylene oligomers are still desired.

 Object of the invention

 An object of the present invention is to provide an ethylene oligomerization catalyst. It is a halogenated arylpyridylbisimine post-transition metal complex.

 An object of the present invention is also to provide a method for synthesizing the above-mentioned ethylene oligomerization catalyst. It is synthesized by the reaction of a halogenated arylpyridylbisimine and a late transition metal compound; the halogenated arylpyridylbisimine can be obtained through 2, 6-pyridinedione and an aniline derivative or naphthylamine derivative In an organic solvent, an aluminum compound or a composite of an aluminum compound and a silicon compound is used as a catalyst, and the reaction is performed for 1 to 50 hours to form.

 Another object of the present invention is to provide an application of the above-mentioned ethylene oligomerization catalyst, which can be used to catalyze the oligomerization of ethylene.

 Summary of invention

The present invention is a halogenated arylpyridylbisimine late transition metal complex ethylene oligomerization catalyst, which is synthesized by the reaction of a halogenated arylpyridylbisimine and a late transition metal compound; the halogenated aromatic Pyridylbisimine can be obtained by using 2, 6-pyridinedione and aniline derivative or naphthylamine derivative in an organic solvent with aluminum A compound, or a composite of an aluminum compound and a silicon compound, is used as a catalyst, and is formed by reacting for 1 to 50 hours. The catalyst is used in combination with a co-catalyst to catalyze the polymerization of ethylene, and the selectivity and catalytic activity of short-chain olefins are high. When the ethylene pressure is 10 atm and the polymerization temperature is 60 Ό, the catalytic activity of the complex can reach 3.8 X 10 ⁷ g / mol · Fe · h, the mass percentage content (wt%) of C ₄ -C ₁₂ > 91, Alpha-olefin selectivity is> 98%.

 Summary of the Invention

 The ethylene oligomerization catalyst provided by the present invention is a halogenated arylpyridylbisimine having the following structural formula:

。 Post-transition metal complexes:

.

In the above structural formula, X ¹ or / and X ² are halogen, R ⁴ or / and R ⁸ are -H, halogen, CM hydrocarbon group,

C _1-6 ester group, Ci _-6 amine group or C _1-6 ether group, M is Fe (II), Fe (III), Co (Π) and Ru (II),

Z is -H, CM hydrocarbon, aryl or trihalomethyl, Y Υ ² = chlorine, bromine, iodine, CM hydrocarbon, acetylacetone or fluoroarylboron, M = Fe (II), Fe ( III), Co (II), and Ru (II), R ', R 2, R 3,

R ⁵ , R ⁶ or R ⁷ = -H, halogen, nitro, cyano, CM hydrocarbon, aryl, d. ₆ ester group, d. ₆ amine group or C ether group, R ³ and R ⁴ and / or R ⁷ and R ⁸ may form a benzene ring separately or simultaneously.

The above catalysts can be expressed in various forms, such as: X ¹ and X ^{2 in the} molecular formula are halogen, XX ² may be the same or different, and R ⁴ and R ⁸ are -H, halogen, CM hydrocarbon or aryl , R ¹ -R ³ , R ⁵ -R ⁷ are -H, halogen, nitro, cyano, CM hydrocarbon group, aryl group, d. ₆ ester group, .6 amine group or ^ ether group, M , Y Υ ² and Z are as described above;

When R ³ and R ⁴ and / or R ⁷ and R ⁸ can form a benzene ring separately or simultaneously in the above molecular formula, the structural formula can be expressed as follows:

X ¹ , X ² , R ¹ -R ⁸ , M, Y ′, Y ² and Z are as described above, R ⁹ , R ¹⁰ , R ¹¹ or R ¹² is a hydrocarbon group of —H, halogen or —CM;

In the molecular formula, X ¹ and X ² are fluorine, R ¹ — R ⁴ , R ⁵ — R ⁸ are halogen, -H, -C _1-4 hydrocarbon group, aryl group, nitro group, cyano group or d. ₆ ester group , D. ₆ amine group or C ^ ether group, M, V ¹ , Y ² and Z are as described above.

In the molecular formula, X ¹ , R ⁴ , X ² , and R ⁸ are fluorine, R ¹ — R ³ , R ⁵ — R ⁷ are halogen, -H, -C _{1 -4} hydrocarbon group, aryl group, nitro group, cyano group, CM's hydrocarbon group, aryl group, C ^ ester group, C _1-6 amine group or C _1-6 ether group, M, Y ¹ , Y ² and Z are as described above;

 In the above ethylene oligomerization catalyst of the present invention, when one ortho position of aniline is halogen and the other ortho position is hydrogen, for example, the following structural formula:

、 Cl、 Br或 I， R⁴和 R⁸ =H时， 这样的 配合物催化乙烯聚合， 得到齐聚产物。 当苯胺的两个邻位为原子半径很小， 电负

When Cl, Br or I, R ⁴ and R ⁸ = H, such a complex catalyzes the polymerization of ethylene to obtain an oligomerized product. When the two ortho positions of aniline have a small atomic radius, the electronegativity

， 这样的化合物催 化乙烯聚合主要得到 C₄-C₁₂的短链 ct-烯烃。

Such compounds catalyze the polymerization of ethylene to obtain mainly C ₄ -C ₁₂ short-chain ct-olefins.

The catalyst synthesis method of the present invention is obtained by reacting a halogenated arylpyridylbisimine and a late transition metal compound MQ _n · mH ₂ 0 in an organic solvent or water for 0.01 to 20 hours. The molar ratio of the ligand to MQ _n * mH ₂ 0 is 1: 0.2-5, Q is chlorine, bromine, iodine or acetylacetone, n = 2_3, M is Fe (II), Fe (III), (: ₀ ( 11) and (11), m = 0_6. The organic solvent may be tetrahydrofuran (THF), methanol, ethanol, butanol or dichloromethane, etc. The reaction uses more MQ _n «mH ₂ 0 for the reaction No effect. Normal yield is 50 ~ 100%.

 The structural formula of the halogenated arylpyridylbisimine is

Haloaryl pyridyl bisimine method of synthesis may be made of the 2, 6-dione with an aniline derivative of pyridine or naphthylamine derivative, in an organic solvent, such as (: ₅ - ₈ alkanes, In toluene, benzene, xylene, diethyl ether, methanol, or ethanol, etc., an aluminum compound or a composite of an aluminum compound and a silicon compound is used as a catalyst, and the reaction is performed for 1 to 50 hours to form a halogenated arylpyridylbisimine ligand. The molecular sieve can be added as a water absorbing agent in the reaction. The molar ratio of 2, 6-pyridinedione, aniline derivative or naphthylamine derivative, catalyst and molecular sieve is 1: 1-5: 0.005-10: 0-100. The aluminum compound is alumina, aluminum halide, aluminum hydroxide. The composite of the aluminum compound and the silicon compound is an aluminosilicate, or another composite of alumina, aluminum halide, aluminum hydroxide, and silicon oxide, such as Commercially available Silica-alumina catalyst (price is 100 yuan / kg). The yield of the ligand is 20 ~ 90%.

 The use of the halogenated arylpyridylbisimine post-transition metal complex of the present invention is for catalyzing the oligomerization of ethylene.

的烷基， m=l-3, n=0_2), 路易斯酸 （Lewis acid), LiR/Lewis acid(R=C_1-4的垸基）， AIRXL /Lewis acid(R=C_1-3的垸基， m=l-3, n=0-2)作助催化剂。 反应一定时间后， 用含 5%盐酸终止反应。 The oligomerization reaction was performed in a round bottom flask or an autoclave, with an ethylene pressure of 0.1 to 1000 × ^{10 5} P _a and a polymerization temperature of 10 to 300 ° C., using C _{4 -8} alkane or aromatic hydrocarbon as a solvent, and MA0 (formaldehyde yl aluminoxane embankment), MMA0 (modified methyl alumoxane), EA0 (ethyl aluminum oxide embankment), BA0 (butyl aluminoxane _{embankment), LiR (R = C l} -4 alkyl with a),

Alkyl, m = l-3, n = 0_2), Lewis acid, LiR / Lewis acid (R = C _1-4 amidino), AIRXL / Lewis acid (R = C _1-3 Fluorenyl, m = l-3, n = 0-2) as co-catalyst. After a certain period of reaction, the reaction was terminated with 5% hydrochloric acid.

The catalyst of the present invention is compared to the tridentate pyridinium complex of Fe (II) of the Brookhart group and the Gibson group (Brookhart, M, et al., J. Am. Chem. Soc. 1998, 120, 7143; W099 / 02472, 1999. Gibson, VC, etc., Chera. Commun. 1998, 849; Chem. Eur. J. 2000, 2221), is used to catalyze the polymerization and polymerization of ethylene. The short-chain olefins have higher selectivity and high catalytic activity. When the ethylene pressure is 10 atm and the polymerization temperature is 60 ° C, the catalytic activity of the complex can reach 3.8 X 10 ⁷ g / mol · Fe · h, mass percentage content of C ₄ -C ₁₂ (wt%)> 91 The α-olefin selectivity is> 98%.

 detailed description

 The following examples will help to further understand the present invention, but not limit the content of the present invention.

 Example 1

 Preparation of 2, 6-diacetylpyridine di (2, 6-difluoroaniline)

A 50 ml flask was charged with 2.8 g of 2,6-difluoroaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 24 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridinebis (2,6-difluoroaniline) as a pale yellow solid with a yield of 70%. 'Η NMR (300M Hz, CDC1 ₃ ): 8.47 (d, 2H, Py-H); 7.93 (t, 1H, Py-H); 7.07 (d, 4H, Ar-H); 6.99 (t, 2H, Ar-H); 2.46 (s, 6H, N = CMe). Elemental analysis: C ₂₁ H ₁₅ N ₃ F _4: Calculated value C, 65.45; H, 3.92; N, 10.90. Found C, 65.49; H, 4.06, N, 10.65.

 Example 2

 Preparation of 2, 6-diacetylpyridine di (2, 6-difluoroaniline)

 In a two-necked flask, 0.81 g (5 mmol) of diacetylpyridine, 1.61 g (12.5 mmol) of 2.6-difluoroaniline, 17 mg of p-toluenesulfonic acid, and 50 ml of toluene were added. Stir and begin heating under reflux, and separate the water with a water separator. After 4 days of reaction, the solvent was spin-dried. The product was separated through a column. 2,6-diacetylpyridine bis (2,6-difluoroaniline) was obtained as a pale yellow solid with a yield of 13%. Product analysis was the same as in Example 1.

 Example 3

 Preparation of 2, 6-diacetylpyridine di (2-fluoroaniline)

A 50 ml flask was charged with 2.5 g of 2-fluoroaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 20 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridinebis (2-difluoroaniline) as a pale yellow solid in a yield of 65%. 'HNMR (300MHz, CDC1 ₃ ): 8.39 (d, 2H, Py-H); 7.90 (t, 1H, Py-H); 7.19- 7.09 (m, 6H, Ar-H); 6.93 (t, 2H, Ar-H); 2.42 (5,611,? ^^ 6). Elemental analysis: C ₂₁ H ₁₇ N ₃ F _2: Calculated C, 72.19; H, 4.90; N, 12.03. Found C, 71. 88; H, 4. 96, N, 11. 99.

 Example 4

 Preparation of 2,6-diacetylpyridine di (2-chloroaniline)

A 50 ml flask was charged with 3 g of 2-chloroaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 24 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridinebis (2-chloroaniline) as a pale yellow solid with a yield of 70%. Ή NMR (300M Hz, CDC1 ₃ ): 8.44 (d, 2H, Py― H _m ); 7.94 (t, 1Η,-H _p ); 7.43 (dd, 2H, Ar― H); 7.28 (pseudo t, 2Η , Ar-H); 7.07 (pseudo t, 2Η, Ar-H); 6.86 (dd, 2Η, Ar-H); 2.38 (s, 6Η, N = CMe) .. Elemental analysis: C ₂₁ H ₁₇ N ₃ C1 _2: Calculated value C, 65.97; H, 4.48; N, 10.99. Found C, 65.48; H, 4.70, N, 10.87.

 Example 5

 Preparation of 2,6-diacetylpyridine (2-bromoaniline)

A 50 ml flask was charged with 3.8 g of 2-bromoaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 24 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridinebis (2-bromoaniline) as a pale yellow solid with a yield of 80%. Ή NMR (300M Hz, CDC1 ₃ ):. Elemental analysis: C ₂ , H ₁₇ N ₃ Br ₂ : 8.47 (d, 2H, Py-H _m ); 7.94 (t, 1Η, P_y-H _p ); 7.62 ( dd, 2Η, Ar-H); 7.34 (pseudo t, 2Η, Ar-H); 7.01 (pseudo t, 2Η, Ar-H); 6.85 (dd, 2Η, Ar-H); 2.38 (s, 6Η, N = CMe). Calculated C, 53.53; Η, 3.64, N, 8.92. Found C, 53.66; 66, 3.65; N, 8.88.

 Example 6

 Preparation of 2,6-diacetylpyridine di (2-iodoaniline)

A 50 ml flask was charged with 5 g of 2-iodoaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 24 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridine bis (2-iodoaniline) as a pale yellow solid with a yield of 80%. Ή NMR (300M Hz, CDC1 ₃ ): 8.52 (d, 2Η, Py- H _m ); 7.96 (t, 1Η, Vy-Hp); 7.90 (dd, 2Η, Ar-H); 7.37 (pseudo t, 2Η, Ar-H); 6.85 (pseudo t, 2H, Ar-H); 6.80 (dd, 2H, Ar-H); 2.37 (s, 6H, N = CMe). Elemental analysis: C ₂₁ H ₁₇ N ₃ Br _2: Calculated C, 44.63; H, 3.03, N, 7.43. Found C, 44.95; H, 3.06; N, 7.30. Preparation of 2,6-diacetylpyridine bis (2,4-difluoroaniline)

A 50 ml flask was charged with 2.8 g of 2,4-difluoroaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 24 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridine bis (2,4-difluoroaniline) as a pale yellow solid with a yield of 72%. 'H NMR (300M Hz, CDC1 ₃ ): Ή NMR (CDC1 ₃ ): 8.38 (d, 2H, Py-H _m ); 7.9 (t, lH, Py-H _p ); 6.93 (m, 6H, Ar- H); 2.41 (s, 6H, N = CMe). Elemental analysis: C ₂₁ H _l5 N ₃ F _4: Calculated value C, 65.45; H, 3.92; N, 10.90. Found C, 65.83; H, 4.14, N, 10.51.

 Example 8

 Preparation of 2,6-diacetylpyridine di (2,5-difluoroaniline)

A 50 ml flask was charged with 2.8 g of 2,5-difluoroaniline, L63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 24 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridine bis (2,5-difluoroaniline) as a pale yellow solid with a yield of 70%. 'H Li R (300M Hz, CDC1 ₃ ): 8.38 (d, 2H, Py-H _m ); 7.91 (t, lH, P_y-H _p ); 7.07 (m, 2Η, Ar-H); 6.80 (m , 2Η, Ar-H); 6.69 (m, 2Η, Ar-H); 2.43 (s, 6Η, N = CMe). Elemental analysis: C ₂₁ H ₁₅ N ₃ F _4: Calculated C, 65.45; H, 3.92; N, 10.90. Found C, 65.51; H, 4.12, N, 10.44.

 Example 9

 Preparation of 2,6-diacetylpyridine di (2-chloro-6-methylaniline)

A 50 ml flask was charged with 3.5 g of 2-chloro-6-methylaniline, 1.63 g of 2,6-diacylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 10 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridinebis (2-chloro-6-methylaniline) as a pale yellow solid in a yield of 78%. 'H wake R (300M Hz, CDC1 ₃ ): 8. 50 (d, 2H, Py-H); 7. 93 (t, 1H, Py-H); 7. 33 (d, 2H, Ar-H) 7. 07 (d, 2H, Ar-H); 6. 83 (t, 2H, Ar-H); 2. 20 (s, 6H, N = CMe). Elemental analysis: C ₂₃ H ₂₁ N ₃ C1 _2: Calculated values C, 67.32; H, 5.16; N, 10.24. Found C, 67.87; H, 5.34, N, 10.56 c

 Example 10

 Preparation of 2,6-diacetylpyridine di (2,4-dibromoaniline)

In a 50 ml flask, add 5.3 g of 2,4-dibromoaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g Molecular sieve and 0.6g Silica-alumina catalyst. After 10 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridinebis (2,4-dibromoaniline) as a pale yellow solid with a yield of 81%. Ή NMR (300M Hz, CDCl ₃ ): 8. 53 (d, 2H, Py-H); 7. 96 (t, 1H, Py-H); 7. 68 (s, 2H, Ar-H); 7 . 37 (d, 2H, Ar- H); 6. 62 (d, 2H, Ar— H); 2. 36 (s, 6H, N = CMe). Elemental analysis: C ₂₁ H ₁₅ N ₃ Br _4: Calculation Values C, 40.06; H, 2.38; N, 6,68. Found C, 40.32; H, 2.57; N, 6.75.

 Example 11

 Preparation of 2,6-diacetylpyridine di (2,4,6-trifluoroaniline)

A 50nil flask was charged with 3.5 g of 2,4,6-trifluoroaniline, 1.63 g of 2,6-diacetylpyridine, 15 ml of toluene, 3 g of molecular sieve and 0.6 g of Silica-alumina catalyst. After 20 hours of reaction, it was filtered and washed with 20 ml of toluene. The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridine bis (2,4,6-trifluoroaniline) as a pale yellow solid with a yield of 65%. Ή NMR (300 Hz, CDC1 ₃ ): 8. 55 (d, 2H, Py-H); 7. 97 (t, 1H, Py-H); 7. 67 (s, 4H, Ar-H); 2 46 (s, 6H, N = CMe). Elemental analysis: C ₂₁ H ₁₃ N ₃ F _6: Calculated C, 59.86; H, 3.11; N, 9.97. Found C, 60.35; H, 3.36, N, 9.51.

 Example 12

 Preparation of 2,6-diacetylpyridine di (2,6-dichloroaniline)

A 50 ml flask was charged with 1.63 g of 2,6-diacetylpyridine, 3.5 g of 2,6-dichloroaniline, 15 ml of toluene, 3 g of molecular sieve, and 0.6 g of Silica-alumina catalyst. After 15 hours of reaction, it was filtered and washed with 20 ml of toluene . The solvent was removed under reduced pressure. The crude product was recrystallized from methanol to obtain 2,6-diacetylpyridine bis (2,6-dichloroaniline) as a pale yellow solid with a yield of 40%. Ή NMR (300M Hz, CDC1 ₃ ): 8. 52 ( d, 2H, Py-H); 7. 95 (t, 1H, Py-H); 7. 35 (d, 4H, Ar-H); 7. 01 (t, 2H, Ar-H); 2. 36 (s, 6H, N = CMe). Elemental analysis: C ₂₁ H ₁₅ N ₃ C1 _4: Calculated C, 55.88; H, 3.33; N, 9.31. Found C, 55.70; H, 3.57, N, 9.25.

 Example 13

 Preparation of (2,6-diacetylpyridine di (2,6-difluoroaniline)) ferrous chloride (A)

The preparation reaction was performed under an argon atmosphere. Take 27 mg of FeCl ₂ 4H ₂ 0, add 14 ml of THF, and stir. 72 mg of 2,6-diacetylpyridinebis (2,6-fluoroaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed with 15 ml of ether three times. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridine bis (2,6-fluoroaniline)) was obtained as ferrous chloride (A). Yield 89%. Element Analysis: C ₂₁ H, ₅ N ₃ FeF ₄ Cl ₂ : Calculated C, 49.25; H, 2.95; N, 8.20. Found C, 48.42; H, 3.36: N, 7.66.

 Example 14

 Preparation of (2,6-diacetylpyridine di (2,6-difluoroaniline)) cobalt chloride (B)

The preparation reaction was performed under an argon atmosphere. Take 21 mg of CoCl ₂ , add 13 ml of THF, and stir. 53 mg of 2,6-diacetylpyridinebis (2,6-fluoroaniline) was added, and a brownish yellow precipitate was formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed with 15 ml of ether three times. Dry under vacuum for 10 hours. A brownish yellow solid (2,6-diacetylpyridinebis (2,6-fluoroaniline)) was obtained as cobalt chloride (B). Yield was 81%. Elemental analysis: C ₂ , H, 5N ₃ CoF ₄ Cl ₂ : Calculated C, 48.95; H, 2.93; N, 8.15. Found C, 48.18; H, 3.17; N, 7.78.

 Example 15

 Preparation of (2,6-diacetylpyridine di (2-fluoroaniline)) ferrous chloride (C)

The preparation reaction was performed under an argon atmosphere. Take 80 mg of FeCl ₂ 40, add 16 ml of THF, and stir. 157 mg of 2,6-diacetylpyridine bis (2-fluoroaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridinebis (2-fluoroaniline)) was obtained as ferrous chloride (C). Yield: 93%. Elemental analysis: C ₂₁ Hi ₇ N ₃ FeF ₂ Cl ₂ : Calculated C, 52.97; H, 3.60; N, 8.82. Found C, 52.63; H, 3.46, N, 8.13.

 Example 16

 Preparation of (2,6-diacetylpyridine di (2-chloroaniline)) ferrous chloride (D)

The preparation reaction is performed under a fluorine gas atmosphere. Take 80 mg of FeCl ₂ 4¾0, add THF or 16 ml of dichloromethane, and stir. 172 mg of 2,6-diacetylpyridinebis (2-chloroaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge or concentrate to remove the solvent. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridine bis (2-chloroaniline)) was obtained as ferrous (D) chloride. The yield was 82%. Elemental analysis: C ₂₁ H ₁₇ N ₃ FeCl _4: Calculated C, 49.55; H, 3.37; N, 8.25. Found C, 49.76; H, 3.96, N, 7.59.

 Example 17

 Preparation of (2,6-diacetylpyridine di (2-bromoaniline)) ferrous chloride (E)

Each reaction was carried out under an argon atmosphere. Take 160mg of FeC 4H ₂ 0, add 36ml of THF, stir Stir. 424 mg of 2,6-diacetylpyridinebis (2-bromoaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridinebis (2-bromoaniline)) was obtained as ferrous (E) chloride. The yield was 87%. Elemental analysis: C ₂₁ H ₁₇ N ₃ Br ₂ FeCl2 THF: Calculated C, 44.81; H, 3.45; N, 6.27. Found C, 43.72; H, 3.54, N, 6.27.

 Example 18

 Preparation of (2,6-diacetylpyridine di (2-fluoro-6-methylaniline)) ferrous chloride (F)

The preparation reaction was performed under an argon atmosphere. Take 160 mg of FeCl ₂ 40, add 36 ml of THF, and stir. 400 mg of 2,6-diacetylpyridinebis (2-fluoro-6-methylaniline) was added, and a blue precipitate immediately formed. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridine bis (2-fluoro-6-methylaniline)) was obtained as ferrous (F) chloride. Yield was 81%. Elemental analysis: C ₂₃ H ₂ iN ₃ FeF ₂ Cl ₂ : Calculated C, 54.26; H, 4.19; N, 8.33. Found C, 54.32; H, 3.98, N, 8, 13.

 Example 19

(2,6-diacetylpyridine bis (2-fluoro-6-methoxyaniline)) Preparation of ferrous chloride (G) The preparation reaction was performed under an argon atmosphere. Take 160mg of FeCl ₂ 4¾0, add 36ml of THF or butanol, and stir. 412 mg of 2,6-diacetylpyridinebis (2-fluoro-6-methoxyaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge or concentrate to remove the solvent. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridine diC2-fluoro-6-methoxyaniline) was obtained) and ferrous chloride (G). The yield was 82%. Elemental analysis: C ₂₃ H ₂₁ N ₃ FeF ₂ Cl ₂ 0: Calculated C, 51.49; H, 3.95; N, 7.84. Found C, 51.87; H, 3.97, N, 7.53.

 Example 20

 Preparation of (2,6-diacetylpyridine di (2-iodoaniline)) ferrous chloride (H)

The preparation reaction was performed under an argon atmosphere. Take 160 mg of FeCl ₂ 4H ₂ 0, add 36 ml of THF, and stir. Add 509 mg of 2,6-diacetylpyridine bis (2-iodoaniline) and a blue precipitate immediately formed. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridinebis (2-iodoaniline)) was obtained as ferrous (H) chloride. The yield was 87%. Elemental analysis: C ₂ iH, ₇ N ₃ I ₂ FeCl ₂ THF: Calculated C, 39.30; H, 3.30; N, 5.50. Found C, 39.07; H, 3.18, N, 5.30. . Example 21

(2,6-diacetylpyridine bis (2,6-difluoro-4-methylaniline)) Preparation of ferrous (I) chloride The preparation reaction was performed under an argon atmosphere. Take 160 mg of FeCl ₂ 4¾0, add 36 ml of THF, and stir. 430 mg of 2,6-diacetylpyridinebis (2,6-difluoro-4-methylaniline) was added, and a blue precipitate immediately formed. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridine bis (2,6-difluoro-4-methylaniline)) was obtained as ferrous chloride (1). Yield: 82%. Elemental analysis: C ₂₂ H, ₇ N ₃ FeF ₄ Cl ₂ : Calculated C, 5U0; H, 3.52; N, 7.72. Found C, 51.44; H, 3.66, N, 7.56.

 Example 22

 Preparation of (2,6-diacetylpyridine di (2,4,6-trifluoroaniline)) ferrous chloride (J)

The preparation reaction was performed under an argon atmosphere. Take 160 mg of FeCl ₂ 4H ₂ 0, add 36 ml of THF, and stir. 430 mg of 2,6-diacetylpyridine bis (2,4,6-trifluoroaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridine bis (2,4,6-trifluoroaniline)) was obtained as ferrous chloride (J). Yield 88%. Elemental analysis: C ₂ iH ₁₃ N ₃ FeF ₆ Cl _2: Calculated C, 45.98; H, 2.37; N, 7.66. Found C, 46.12; H, 2.46, N, 7.46.

 Example 23

 Preparation of (2,6-diacetylpyridinebis (2,4-difluoroaniline)) ferrous chloride (K)

The preparation reaction was performed under an argon atmosphere. Take 27tng FeCl ₂ 4H ₂ 0, add 14 ml of THF, and stir. 72 mg of 2,6-diacetylpyridinebis (2,4-fluoroaniline) was added, and a blue precipitate immediately formed. Stir overnight at room temperature. Centrifuge to remove THF. Then washed with 15 ml of ether three times. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridinebis (2,4-fluoroaniline)) was obtained as ferrous chloride (K). The yield was 69%. Elemental analysis: C ₂ iH ₁₅ N ₃ F ₄ FeCl ₂ -THF: Calculated C, 51.40; H, 3.97; N, 7.19. Found C, 51.36; H, 4.27, N, 7.16. .

 Example 24

 Preparation of (2,6-diacetylpyridine di (2,5-difluoroaniline)) ferrous chloride (L)

The preparation reaction was performed under an argon atmosphere. Take 27 mg of FeCl ₂ 4H ₂ 0, add 14 ml of THF, and stir. 72 mg of 2,6-diacetylpyridinebis (2,5-fluoroaniline) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed with 15 ml of ether three times. Dry under vacuum for 10 hours. Get Ferrous (L) chloride to blue solid (2,6-diacetylpyridine di (2,5-fluoroaniline)). The yield was 76%. Elemental analysis: C ₂₁ H ₁₅ N ₃ F ₄ FeCl ₂ : Calculated C, 49.25; H, 2.95; N, 8.20. Found C, 49.15; H, 3.18, N, 8.16.

 Example 25

 Preparation of (2,6-diacetylpyridine di (2-chloronaphthylamine)) ferrous chloride (M)

The preparation reaction was performed under an argon atmosphere. Take 80 mg of FeCl ₂ 4H ₂ 0, add 16 ml of THF, and stir. 195 mg of 2,6-diacetylpyridinebis (2-chloronaphthylamine) was added, and a blue precipitate formed immediately. Stir overnight at room temperature. Centrifuge to remove THF. Then washed 3 times with 20 ml of ether. Dry under vacuum for 10 hours. A blue solid (2,6-diacetylpyridinebis (2-chloronaphthylamine)) was obtained as ferrous chloride (M). The yield was 86%. Elemental analysis: C ₂₉ H ₂₁ N ₃ FeCl ₄ : Calculated C, 57.07; H, 3.47; N, 6.89. Found C, 57.71; H, 3.76; N, 6.59.

 Example 26

 In a 0.5L autoclave, add 100 ml of toluene, add 1 mmol of MMAO, and keep the temperature constant to 25 ° C. Another 10 ml of a solution containing 1 μηι 1 (2,6-diacetylpyridine di (2,6-diacetylpyridine di (2,6-difluoroaniline)), ferric chloride and MMAO 1 mmol in toluene and 40 ml of toluene were added. Under vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 1 hour of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomer was determined by GC-MS and the content of each component was determined by GC. As shown in Table 1.

 Example 27

 In a 0.5L autoclave, add 100 ml of toluene, add 1 mmol of MMAO, and keep the temperature constant to 40 ° C. Another 10 ml of a toluene solution containing 1 μηι 1 (2,6-diacetylpyridine di (2,6-diacetylpyridine di (2,6-difluoroaniline)) and MMAO lirimol and 40 ml of toluene were added. Under vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 1 hour of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomer was determined by GC-MS and the content of each component was determined by GC. As shown in Table 1.

 Example 28

In a 0.5L autoclave, add 100 ml of toluene, add 1 mmol of MMAO, and keep the temperature to 60 ° C. 10 ml of a solution containing 1 μηο1 (2,6-diacetylpyridine di (2,6-diacetylpyridine di (2,6-difluoroaniline)), ferric chloride and 1 mmol of MMAO and 40 ml of toluene were added. Under vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 1 hour of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomer was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1. Example 29

 In a 0.5L autoclave, add 100 ml of toluene, add 1 mmol of MMAO, and keep the temperature constant to 60 ° C. 10 ml of a solution containing 1 μηι1 (2,6-diacetylpyridine di '(2,6-diacetylpyridine di (2-chloroaniline))) ferrous chloride and 1 mmol of MMAO and 40 ml of toluene were added. With vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 1 hour of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1. The results are shown in Table 1.

 Example 30

 In a 0.5L autoclave, add 100 ml of toluene, add 1 mmol of MMAO, and keep the temperature constant to 60 ° C. Then add 10 ml of a toluene solution containing 2 μη> 1 (2,6-diacetylpyridine di (2,6-diacetylpyridine di (2-bromoaniline))), 2 mmol of MMAO and 40 ml of toluene. With vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 1 hour of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1.

 Example 31

 In a 0.5L autoclave, add 100 ml of toluene, add 1 mmol of MMAO, and keep the temperature constant to 60 ° C. Another 10 ml of a solution containing 2 μιηο1 (2,6-diacetylpyridine di (2,6-diacetylpyridine di (2-iodoaniline))) ferrous chloride and MMAO 2 mmol in toluene and 40 ml of toluene were added. With vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 1 hour of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1.

 Example 32

 In a 0.5L autoclave, add 150 ml of toluene, add MMAO 0.48 mmol, and keep the temperature constant to 60 ° C. Another 10 ml of 0.6 μιηο1 (2,6-diacetylpyridine bis (2,6-diacetylpyridine bis (2,4-difluoroaniline))) was added;) Ferrous chloride and MMAO 0.6mmol toluene solution and 40 ml toluene. Under vigorous stirring, ethylene gas was passed in, and the ethylene pressure was constant at 10 atm. After 0.15 hours of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1.

 Example 33

In a 0.5L autoclave, 150 ml of toluene was added, MMAO 0.48 mmol was added, and the temperature was maintained at 60 ° C. Add another 10ml containing 0.6μηι1 (2,6-diacetylpyridine di (2,6-diacetylpyridine di (2,5-di Fluoroaniline)))) Ferrous chloride and MMAO 0.6mmol toluene solution and 40ml toluene. With vigorous stirring, ethylene gas was introduced, and the ethylene pressure was constant at 10 atmospheres. After 0.15 hours of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1.

 Example 34

 In a 100-ml round-bottomed flask, add 40 ml of toluene, add 1 mmol of MMAO, and then cool to 0 ° C. When ethylene gas is introduced, the ethylene pressure is constant to one atmosphere. With vigorous stirring, 10 ml of a toluene solution containing 0.8 μηιο1 (2,6-diacetylpyridinebis (2-chloroaniline)) ferrous chloride was added. After 0.5 hours of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1.

 Example 35

 In a 100-ml round-bottomed flask, add 40 ml of toluene, add 1 mmol of MMAO, and then cool to 0 ° C. When ethylene gas is introduced, the ethylene pressure is constant to one atmosphere. With vigorous stirring, 10 ml of a toluene solution containing 0.8 μιηο1 (2,6-diacetylpyridine di (2-bromoaniline)) ferrous chloride was added. After 0.5 hours of reaction, the reaction was terminated with 5% hydrochloric acid. The composition of the oligomerized product was determined by GC-MS, and the content of each component was determined by GC. The results are shown in Table 1.

 Table 1 Catalytic oligomerization of ethylene

 Compound toluene MMAO temperature pressure time yield activity a linear a-ene

(umol) (ml) (equiv) ('C) (atm) (min) (g) (10 ⁶ g / mol cat h) Hydrocarbon content (%)

1 A (l) 150 2000 25 10 60 34.9 34.9 0.59 97

2 A (l) 150 2000 40 10 60 45.1 45.1 0.49 98

3 A (l) 150 2000 60 10 60 38.4 38.4 0.42 98

4 D (0.8) 50 1250 0 1 30 2.4 6.0 0.69 90

5 D (l) 150 2000 60 10 60 51.9 51.9 0.59 95

6 E (0.8) 50 1250 0 1 30 1.7 4.3 0.83 91

7 E (2) 150 1500 60 10 60 58.1 29.5 0.63 95

8 H (2) 150 1500 60 10 60 18.5 9.3 0.67 93

9 K (0.6) 200 1800 65 10 15 15.9 106 0.33 88

10 L (0.6) 200 1800 65 10 15 19.3 129 0.34 86 In order to facilitate the comparison with the ethylene polymerization catalyst of the following structure, the implementation of 34-37 is further given.

 Example 36

In a 1 L autoclave, 500 ml of toluene was added, and 0.15 ml of Al (iBu) _{3 was added} , and the reaction was stirred at room temperature for 1 hour. Add MMAO 1.2 mmol and cool to 15 ° C. Add 10 ml of a toluene solution containing 0.8 μηιο1 (2,6-diacetylpyridine (2,6-dibromoaniline) ferrous chloride), and pass ethylene gas under vigorous stirring. The ethylene pressure is constant at 6 atmospheres. After 0.5 hours of reaction, the ethylene gas was vented and the reaction was terminated with 5% hydrochloric acid in ethanol. After the polymer was filtered, it was dried under vacuum at 60 ° C to constant weight. 29.2 g of product was obtained. The catalytic activity was 7.3 X 10 ⁷ g PE / mol -Fe · 1 ι. The molecular weight of the polyethylene obtained was M _w = 255,000 (GPC, o-dichlorobenzene as eluent), molecular weight distribution was 20.6, peak meeting point was 133 ° C, and crystallinity was 70%.

 Example 37

In a 1 L autoclave, 500 ml of toluene was added, and 0.15 ml of Al (iBu) _{3 was added} , and the reaction was stirred at room temperature for 1 hour. Add another MMAO 1.2mmol and cool to 15 ° C. 10 ml of a toluene solution containing 0.8 μηιο1 (2,6-diacetylpyridine di (2,6-dichloroaniline)) ferrous chloride was added, and ethylene gas was introduced under vigorous stirring, and the ethylene pressure was constant at 6 atmospheres. . After 0.5 hours of reaction, the ethylene gas was vented and the reaction was terminated with 5% hydrochloric acid in ethanol. After filtering the polymer, it was dried under vacuum at 60 ° C to constant weight. 28.8 g of product were obtained. The catalytic activity was 7.2 X 10 ⁷ g PE / mol · Fe · h. The molecular weight of the obtained polyethylene was M _w = 41,400 (GPC, o-dichlorobenzene as eluent), the molecular weight distribution was 5.3, the peak meeting point was 132 ° C, and the crystallinity was 54%.

 Example 38

In a 100 ml round-bottomed flask, 40 ml of toluene was added, MMAO 2 mmol was added, and then cooled to 0 ° F. When ethylene gas is introduced, the ethylene pressure is constant to one atmosphere. With vigorous stirring, 10 ml of a toluene solution containing 0.8 μηιο1 (2,6-diacetylpyridine di (2,6-bromoaniline)) ferrous chloride was added. After 0.5 hours of reaction, the reaction was terminated with 5% hydrochloric acid in ethanol. After polymer filtration, vacuum at 60 ° C Dry to constant weight. The catalytic activity of polyethylene 4.87go was 1.22 X 10 ⁷ g PE / mol · Fe · h. The molecular weight of the obtained polyethylene was 1 ^^ = 69,000 (GPC, o-dichlorobenzene as eluent), the molecular weight distribution was 45.8, and the peak meeting point was 127. C.

 Example 39

In a 100 ml round bottom flask, add 40 ml of toluene, and then add 1 mmol of MMAO, and then cool to 0 ° C. When ethylene gas is introduced, the ethylene pressure is constant to one atmosphere. With vigorous stirring, 10 ml of a toluene solution containing 0.8 μηι _Ο 1 (2,6-diacetylpyridine bis (2,6-dichloroaniline)) ferrous chloride was added. After 0.5 hours of reaction, a solution containing 5% hydrochloric acid was used. The reaction was stopped by ethanol. After the polymer was filtered, it was dried under vacuum at 60 to constant weight. 5.13 g of polyethylene was obtained. The catalytic activity was 1.28 X 10 ⁷ g PE / mol · Fe · h. The molecular weight of the polyethylene obtained was M _w = 1.26 Wan (GPC, o-dichlorobenzene as eluent), molecular weight distribution is 5.0, peak meeting point is 128 ° C.

Claims

Rights request  1. An ethylene oligomerization catalyst, characterized in that it is a halogenated arylpyridylbisimide with the following structural formula:

In the above structural formula, X ¹ or / and X ² are halogen, R ⁴ or / and ¹⁸ are halogen, CM hydrocarbon group, C _1-6 ester group, C _1-6 amino group or C _1-6 ether group, and M is Fe (II), Fe (III), Co (II) and Ru (II), Z is -H, -C _M hydrocarbon group, aryl, nitro, cyano, trihalomethyl, Y Υ ² = Chlorine, bromine, iodine, CM hydrocarbyl, acetylacetone or fluoroarylboron, M = Fe (II), Fe (111), Co (II) and Ru (II), RR ² , R ³ , R ⁵ , R ⁶ or R ⁷ = halo, -H, a nitro group, a cyano group, the CM hydrocarbon group, aryl group, C _1-6 ester groups, C _1-6 amine or ether group d_ _6, R ³ and R ⁴ and / or R ⁷ and R ⁸ may form a benzene ring separately or simultaneously. 2. An ethylene oligomerization catalyst according to claim 1, characterized in that a structural formula is as follows: Or

Wherein X ¹ , X ² , R ¹ -R ⁸ , M, Y ¹ , Y ² and Z are as described in claim 1, and R ⁹ , R ¹⁰ , R ¹¹ or R ¹² is a hydrocarbon group of -H, halogen or -CM ; 3. The ethylene oligomerization catalyst according to claim 1, wherein a structural formula is as follows:

, Cl, F or I, R ⁴ and R ⁸ = H.  4. The ethylene oligomerization catalyst according to claim 1, wherein a structural formula is as follows:

5. A method for synthesizing an ethylene oligomerization catalyst according to claim 1, characterized in that the halogenated arylpyridylbisimine and the late transition metal compound MQ _n * m 0 are reacted in an organic solvent or water at 0.01. Obtained in -20 hours, the molar ratio of haloarylpyridylbisimine ligand to MQ _n · mH ₂ 0 is 1: 0.2-5, and Q is chlorine, bromine, iodine or levulinium n = 2-3, M is Fe (II), Fe (III), Co (n Ru (II), and the structure formula of haloarylpyridylbisimine is

6. A method for synthesizing an ethylene oligomerization catalyst according to claim 5, wherein the method for synthesizing the halogenated arylpyridylbisimine is via 2, 6-pyridinedione and an aniline derivative. Or a naphthylamine derivative in the presence of a molecular sieve in an organic solvent and using an aluminum compound or a composite of an aluminum compound and a silicon compound as a catalyst, and reacted for 1 to 50 hours to form a halogenated arylpyridylbisimine, of which The molar ratio of 4,6-pyridinedione, aniline derivative or naphthylamine derivative, catalyst and molecular sieve is 1: 1-5: 0.005-10: 0 to 100, the aluminum compound is alumina, aluminum halide , Aluminum hydroxide, aluminum compounds and silicon compounds The composite is an aluminosilicate, or another composite of alumina, aluminum chloride, aluminum hydroxide, and silicon oxide. 7. The use of an ethylene oligomerization catalyst according to claim 1, which is used to catalyze the oligomerization of ethylene.