CN116606325A - 2-tert-butylimino-phenanthroline imine metal (II) complex and synthetic method and application thereof - Google Patents

2-tert-butylimino-phenanthroline imine metal (II) complex and synthetic method and application thereof Download PDF

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CN116606325A
CN116606325A CN202310583082.6A CN202310583082A CN116606325A CN 116606325 A CN116606325 A CN 116606325A CN 202310583082 A CN202310583082 A CN 202310583082A CN 116606325 A CN116606325 A CN 116606325A
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phenanthroline
tert
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imine metal
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陈宁
付雨晴
许家喜
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Beijing University of Chemical Technology
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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
    • B01J31/1825—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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Abstract

The invention discloses a 2-tert-butylimino phenanthroline imine metal (II) complex, a synthesis method and application thereof, and the invention uses 2-R 1 The 8-aminoquinoline and 3, 3-dimethylbutyryl chloride are used as raw materials for de novo synthesis, the synthesized ligand side chain is tert-butyl, and the large steric hindrance characteristic ensures that the ligand has the characteristics of high oligomerization activity, good selectivity, no polymer and wide industrial prospect in olefin oligomerization reaction.

Description

2-tert-butylimino-phenanthroline imine metal (II) complex and synthetic method and application thereof
Technical Field
The invention belongs to the field of organic matter synthesis, and in particular relates to a 2-tert-butylimino phenanthroline imine metal (II) complex, and a synthesis method and application thereof.
Background
Ethylene oligomerization is an important process in industry for the synthesis of alpha-olefins. Alpha-olefin is a basic raw material for fine chemical engineering, can be used for synthesizing detergents, plasticizers, lubricating oil and the like, has very wide application value, and therefore, the design of a catalyst for ethylene oligomerization is very important.
There are a wide variety of ethylene oligomerization catalysts, with the diimine ferric pyridine and cobalt tridentate complex being the earliest and most milestone catalysts. In 1998, brookhart and Gibson et al reported that diimine pyridine complex iron and cobalt catalysts can be used for oligomerization and polymerization of ethylene, and can selectively control oligomerization and polymerization by controlling steric hindrance of substituents on benzene rings. When R is H, ethylene oligomerization is selectively carried out, and when R is other groups, ethylene polymerization occurs, and the molecular weight of the polyethylene is larger when R is more hindered, the structure of the polyethylene is shown in the following formula 1 (J.am.chem.Soc.1998, 120,4049-4050; chem.Commun.,1998,849-85):
in 2006, the Sun Wenhua group reports a series of cobalt (II) complexes containing 2-imine-1, 10-phenanthroline, which exhibit high catalytic activity in the presence of MAO or MMAO as a cocatalyst, and the chain length of the product is also related to R, and the structure is shown in the following formula 2. When A is H, the products obtained by catalysis under 1atm ethylene conditions are almost all ethylene dimerized C4 butene products. And under 10atm ethylene conditions, when R 1 The steric hindrance gradually increases and a small amount of C6 product appears, when R 1 The highest proportion of C6 in isopropyl is 5.2%. When R is methyl, the product obtained by catalysis is almost all C4 butene product of ethylene dimerization, and the product is along with R 1 The steric hindrance increases and the long chain products increase. Under 1atm ethylene conditions, when R 1 16.5% of the C product is isopropyl and 3.5% of the product greater than C8 is present; r under ethylene condition of 10atm 1 Even 23% of C6 product can be obtained in case of isopropyl. When R is phenyl, the product obtained by catalysis is mainly C4 butene product of ethylene dimerization, and the product is along with R 1 The steric hindrance increases and the long chain products increase. Under 1atm ethylene conditions, there was 28.1% C product when R1 was isopropyl, and 16.7% of product greater than C8 was present; under 10atm ethylene conditions, R1 is isopropyl, the C4 product is present in a ratioThe example was reduced to 46.7% with 34.0% and 19.3% C6 and greater than C8, respectively. The above data illustrates that changing R can change the chain length of the alpha olefins produced (C.R.Chimie 2006,9,1500-1509; eur.J.Inorg.chem.,2007, 5584-5598).
In 2013, patent 201310422030.7 of China petrochemical industry Co., ltd synthesizes a series of iron catalysts of 2-isobutyryl-1, 10-phenanthroline polyaniline, and the iron catalysts are used for ethylene oligomerization, so that alpha-olefin can be effectively synthesized, more than 50% of the alpha-olefin synthesized under the catalysis of the catalysts is a product with more than 6 carbon atoms, and therefore, the chain length 7 of the alpha-olefin can be effectively improved by increasing the steric hindrance of the phenanthroline side chain. However, the more sterically hindered tertiary butyl groups remain unexplored. The reason for this is that no suitable tertiary butyl reagent, such as tertiary butyl aluminum reagent, tertiary amyl lithium reagent, etc., can be found by the above method, and construction of such specific large steric hindrance molecules can not be achieved.
Over the last several decades, there have been many studies on catalysts for ethylene oligomerization. The existing catalyst mainly comprises a catalyst with a side chain of a linear substituent, smaller steric hindrance and a side chain of which steric hindrance reaches tertiary butyl, and has no systematic research on the influence on the polymerization degree and distribution in olefin oligomerization.
Disclosure of Invention
The invention provides a tert-butyl imine substituted 1, 10-phenanthroline metal complex, a synthesis method and application thereof, and aims to overcome the defects in the prior art.
The invention is realized by the following technical scheme:
a 2-tert-butyliminophenanthroline imine metal (II) complex of formula (i):
wherein R is 1 Hydrogen, methyl, ethyl, propyl, phenyl, isopropyl or tert-butyl; r is R 2 Hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl; r is R 3 Hydrogen, methyl, ethyl, propyl, isopropyl or tert-butyl; r is R 4 Methyl, ethyl, isopropyl, tert-butyl or phenyl; m is a late transition metal.
In the above technical scheme, M is Fe 2+ Or Co 2+ 。
A preparation method of a 2-tert-butylimino phenanthroline imine metal (II) complex comprises the following steps:
synthesis of 2-alkyl-1, 10-phenanthroline
Will 2-R 1 Mixing 8-aminoquinoline with 3-alkoxy-2-tert-butylcyclobutanone, adding Lewis Acid (LA), reacting in an organic solvent, stirring at room temperature or by heating, and purifying by column chromatography after the reaction is finished to obtain 2-alkyl-1, 10-phenanthroline;
(II) Synthesis of 2-pivaloyl-1, 10-phenanthroline
Mixing 2-alkyl-1, 10-phenanthroline, an oxidant and an organic solvent, heating and refluxing, and purifying by column chromatography after the reaction is finished to obtain 2-pivaloyl-1, 10-phenanthroline;
(III) Synthesis of 2-alkanoyl-1, 10-phenanthroline-anilide ligand
Mixing 2-pivaloyl-1, 10-phenanthroline and substituted aniline, adding 0.2 equivalent of acid, heating and refluxing in an organic solvent for reaction, and purifying to obtain 2-alkanoyl-1, 10-phenanthroline aniline ligand;
synthesis of 2-t-butyliminophenanthroline imine metal (II) complex
2-alkanoyl-1, 10-phenanthroline aniline ligand and anhydrous metal (II) chloride react in an organic solvent to obtain the 2-tert-butylimino phenanthroline imine metal (II) complex.
In the above technical scheme, the lewis acid in the step (i) is any one or more of boron trifluoride, aluminum trichloride, aluminum tribromide, tin dichloride or zinc dichloride.
In the above technical scheme, the oxidant in the step (ii) is any one of selenium dioxide, iodine, liquid bromine, dimethyl sulfoxide, nitrobenzene, tert-butyl peroxy-alcohol, hydroiodic acid or hydrobromic acid.
In the above technical scheme, the metal chloride is anhydrous CoC1 2 Or anhydrous FeCl 2 。
In the above technical scheme, the organic solvent is any one or more of dichloromethane, chloroform, dichloroethane, carbon tetrachloride, ethanol, acetonitrile, benzene, toluene, xylene, chlorobenzene, trifluoromethyl benzene, tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate or tetrabutyl orthosilicate.
In the technical scheme, the reaction temperatures of the steps (I) - (IV) are all 0-170 ℃.
In the above technical solution, the aniline is any one of 2-methylaniline, 3-methylaniline, 4-methylaniline, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, 26-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline or 2, 6-diethylaniline.
An application of 2-tert-butyl imino phenanthroline imine metal (II) complex in catalyzing ethylene oligomerization.
In the technical scheme, the 2-tert-butyliminophenanthroline imine metal (II) complex is an active component, and the cocatalyst is one or two of aluminoxane or alkyl aluminum compounds.
In the technical scheme, the polymerization temperature is 20-60 ℃ and the polymerization pressure is 0.1-1.0 Mpa.
The beneficial effects of the invention are as follows:
the invention provides a 2-tert-butyl imino phenanthroline imine metal (II) complex, a synthesis method and application thereof, and a preparation method thereof, wherein 2-R is 1 The 8-aminoquinoline and 3, 3-dimethylbutyryl chloride are used as raw materials for de novo synthesis, the synthesized ligand side chain is tert-butyl, and the large steric hindrance characteristic ensures that the ligand has the characteristics of high oligomerization activity, good selectivity, no polymer and wide industrial prospect in olefin oligomerization reaction.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 2-neopentyl-1, 10-phenanthroline prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of 2-pivaloyl-1, 10-phenanthroline prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of ligand 2-pivaloyl-1, 10-phenanthroline condensed-2, 4, 6-trimethylaniline prepared in example 1 of the present invention;
FIG. 4 is an x-ray single crystal diffraction pattern of the catalyst 2-pivaloyl-1, 10-phenanthroline formal-2, 4, 6-trimethylaniline cobalt complex prepared in example 1 of the present invention.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be further described below by means of specific embodiments in combination with the accompanying drawings of the specification.
Example 1
1. Preparation of phenanthroline imine ligand
Preparation of 2-neopentyl-1, 10-phenanthroline
To a dried 100mL round bottom flask was added 984mg of 8-aminoquinoline (7.0 mmol), after nitrogen substitution, 40mL of redistilled dichloromethane was added, 2.190g of 3-ethoxy-2-tert-butylcyclobutanone (14.0 mmol) and 0.88mL of boron trifluoride diethyl ether (7.0 mmol) were added sequentially by syringe, and the reaction mixture was stirred at room temperature for 60h; the reaction was quenched with 1mL of triethylamine and 30mL of saturated NaHCO 3 The solution was washed, extracted with DCM (20 mL. Times.3) and the organic phase was washed with anhydrous Na 2 SO 4 Drying, concentrating under reduced pressure to remove solvent; finally, the mixture was passed through a silica gel column (using 1% Et 3 The crude product was purified by chromatography on N-activated silica gel (PE/ea=2:1 elution) to give 1.042g of a reddish brown viscous liquid, 54% yield, which was 2-neopentyl-1, 10-phenanthroline.
As shown in fig. 1, nuclear magnetic analysis:
1 H NMR(400MHz,CDCl 3 )δ(ppm):9.21(dd,J＝4.4,2.0Hz,1H),8.20(dd,J＝8.0,2.0Hz,1H),8.11(dd,J＝8.4,2.0Hz,1H),7.75(dd,J＝8.8,2.4Hz,1H),7.71(dd,J＝8.8,2.4Hz,1H),7.58(ddd,J＝8.0,4.4,1.2Hz,1H),7.48(d,J＝8.0Hz,1H),3.15(s,2H),1.06(s,9H). 13 C NMR(101MHz,CDCl 3 )δ(ppm):161.0,150.1,146.3,145.6,135.8,135.1,128.6,126.8,126.3,125.4,124.6,122.6,52.4,32.4,29.7.HRMS(ESI)calcd for[M+H,C 17 H 19 N 2 ] + :251.1543,found251.1545.
(ii) preparation of 2-pivaloyl-1, 10-phenanthroline
Into a 100mL eggplant-shaped flask, 1.003g of 2-tertiarypentyl-1, 10-phenanthroline (4 mmol) prepared in step (i), 888mg of selenium dioxide (8 mmol), 40mL of 1, 4-dioxane were charged, and the mixture was heated under reflux at 102℃for 4 hours. After the reaction was completed, the mixture was eluted with a silica gel column (activated with 1% et3 n), PE: ea=4:1 eluent to give 536mg of pale yellow solid in 50% yield.
Melting point: 91-93 ℃.
As shown in fig. 2, nuclear magnetic analysis:
1 H NMR(400MHz,CDCl 3 )δ(ppm):9.22(dd,J＝4.4,2.0Hz,1H),8.32(d,J＝8.4Hz,1H),8.25(dd,J＝8.0,2.0Hz,1H),8.16(d,J＝8.4Hz,1H),7.86(d,J＝8.8Hz,1H),7.80(d,J＝8.8Hz,1H),7.65(dd,J＝8.0,4.4Hz,1H),1.67(s,9H). 13 C NMR(101MHz,CDCl 3 )δ(ppm):207.8,154.3,150.8,146.7,144.6,136.6,135.9,129.5,129.0,128.3,126.2,123.1,122.1,44.6,27.8.HRMS(ESI)calcd for[M+H,C 17 H 17 N 2 ] + :265.1336,found 265.1336.
(iii) preparation of ligand (2-pivaloyl-1, 10-phenanthroline-2, 4, 6-trimethylaniline):
264mg of step (ii) was charged into a 50mL eggplant-shaped flask to prepare 2-pivaloyl-1, 10-phenanthroline (1.0 mmol), 0.2 equivalent of p-toluenesulfonic acid,molecular sieve, N 2 20mL of tetraethyl orthosilicate (0.21 mL of 2,4, 6-trimethylaniline (1.5 mmol) was added for displacement, and the mixture was heated under reflux for 36h. The product was purified by column packing with basic alumina, eluting with PE: ea=30:1, then PE: ea=20:1 to give 101mg of yellow solid, 26% yield, melting point: 158-161 ℃.
As shown in fig. 3, nuclear magnetic analysis:
1 H NMR(400MHz,CDCl 3 )δ(ppm):9.22(dd,J＝4.4,1.6Hz,1H),8.17(dt,J＝8.0,1.6Hz,1H),7.90(d,J＝8.4Hz,1H),7.69(dd,J＝8.8,2.4Hz,1H),7.63-7.57(m,2H),7.05(d,J＝8.4Hz,1H),6.52(s,2H),2.15(s,6H),2.03(s,3H),1.52(s,9H). 13 C NMR(101MHz,CDCl 3 )δ(ppm):177.6,156.8,150.4,146.4,145.6,145.1,135.8,134.9,131.5,128.9,128.8,128.1,127.4,126.7,126.2,125.8,122.8,121.0,40.8,29.1,20.6,18.6,17.6.HRMS(ESI)calcd for[M+H,C 34 H 44 N 3 ] + :508.3687,found 508.3690.
(iv) preparation of [ 2-pivaloyl-1, 10-phenanthroline-2, 4, 6-trimethylaniline ] cobalt complex:
88mg of 2- (2, 2-dimethyl) propionyl-1, 10-phenanthroline-2, 4, 6-trimethylaniline (0.23 mmol) was dissolved in 8mL of absolute ethanol at room temperature, 31.6mg of absolute cobalt chloride (0.23 mmol) was dissolved in 8mL of absolute ethanol, and the two solutions were mixed and stirred at room temperature for 8h. Concentrating under reduced pressure to remove part of solvent, vacuum filtering, washing filtrate with anhydrous diethyl ether for three times, and oven drying under infrared lamp to obtain yellow brown solid 73mg with yield of 62%, wherein the yellow brown solid is 2-pivaloyl-1, 10-phenanthroline condensed-2, 4, 6-trimethylaniline cobalt complex, complex Co-1 for short, and its x-ray single crystal diffraction diagram is shown in figure 4.
Elemental analysis: c (C) 26 H 27 N 3 CoCl 2 Theoretical values: c,61.07; n,8.22; h,5.32; experimental values: c,60.53; n,7.97; h,5.28.
Single crystal data:
(v) ethylene oligomerization
1.02g of the complex Co-1 prepared in the step (iv) is weighed and dispersed in 100mL of toluene by means of ultrasonic and the like to prepare a solution with the concentration of 2.0mmol/L for later use. After replacing 300mL of autoclave for several times by means of vacuumizing-filling nitrogen, filling ethylene, adding 50mL of toluene, starting stirring, heating the reaction kettle to 80 ℃, and then sequentially adding 2mL of complex Co-1 solution, 4mL of methylaluminoxane solution (1.5 mol/L) and 44mL of toluene, wherein the total volume of the reaction solvent is 100mL. Then stirring is started, ethylene is introduced to 1MPa, stirring reaction is carried out for 30 minutes, pressure is slowly released after the reaction is finished, a small amount of mixture is taken out by a sample bottle, and after the mixture is neutralized by 5% dilute hydrochloric acid, gas Chromatography (GC) analysis is carried out.
Oligomerization activity was 19.4X10 6 g·mol -1 (Co)·h -1 The oligomer content was found to be C4:8.72%, C6-C10:24.35%, C6-C18:83.97%, C20+:15.8%, K1=0.67, K2=0.71, respectively. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, no polymer was formed, and no polymerization activity was observed.
Example 2
In this example, the same steps (i) to (iii) as in example 1 are carried out, and the metal chloride in step (iv) is anhydrous ferrous chloride, which comprises the following specific steps:
(iv) preparation of [ 2-pivaloyl-1, 10-phenanthroline-2, 4, 6-trimethylaniline ] iron complex
88mg of 2- (2, 2-dimethyl) propionyl-1, 10-phenanthroline-2, 4, 6-trimethylaniline (0.23 mmol) was dissolved in 8mL of anhydrous tetrahydrofuran, 29.2mg of anhydrous ferrous chloride (0.23 mmol) was dissolved in 8mL of anhydrous tetrahydrofuran, and the two solutions were mixed and stirred under reflux at 66℃for 12h. Concentrating under reduced pressure to remove part of solvent, filtering, washing filtrate with anhydrous diethyl ether for three times, and oven drying under infrared lamp to obtain yellow brown solid 88mg with 73% yield, wherein the yellow brown solid is 2-pivaloyl-1, 10-phenanthroline condensed-2, 4, 6-trimethylaniline iron complex, for short complex Fe-1.
Elemental analysis: c (C) 26 H 27 N 3 FeCl 2 Theoretical values: c,61.44; h,5.35; n,8.27; experimental values: c,60.99; n,7.87; h,5.58.
(v) ethylene oligomerization
1.01g of complex Fe-1 is weighed and dispersed in 100mL of toluene by means of ultrasonic and the like to prepare a solution with the concentration of 2.0mmol/L for standby. After replacing 300mL of autoclave for several times by means of vacuumizing-filling nitrogen, filling ethylene, adding 50mL of toluene, starting stirring, heating the reaction kettle to 80 ℃, and then sequentially adding 2mL of complex Fe-1 solution, 4mL of methylaluminoxane solution (1.5 mol/L) and 44mL of toluene, wherein the total volume of the reaction solvent is 100mL. Then stirring is started, ethylene is introduced to 1MPa, stirring reaction is carried out for 30 minutes, pressure is slowly released after the reaction is finished, a small amount of mixture is taken out by a sample bottle, and after the mixture is neutralized by 5% dilute hydrochloric acid, gas Chromatography (GC) analysis is carried out.
Oligomerization activity was 1.61×10 7 g·mol -1 (Fe)·h -1 The oligomer content was found to be C4:8.72%, C6-C10:44.32%, C6-C18:84.67%, C20+:14.81%, K1=0.67 and K2=0.71, respectively. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, no polymer was formed, and no polymerization activity was observed.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (10)

1. A2-tertiary butyl imino phenanthroline imine metal (II) complex is characterized in that: the general formula of the complex is shown in the following formula (I):
wherein R is 1 Hydrogen, methyl, ethyl, propyl, phenyl, isopropyl or tert-butyl; r is R 2 Hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl; r is R 3 Hydrogen, methyl, ethyl, propyl, isopropyl or tert-butyl; r is R 4 Methyl, ethyl, isopropyl, tert-butyl or phenyl; m is a late transition metal.
2. 2-tert-butyliminophenanthroline imine metal (II) complex according to claim 1, characterized in that: the M is Fe 2+ Or Co 2+ 。
3. A process for the preparation of a 2-tert-butylimino-phenanthroline imine metal (II) complex according to claim 1 or 2, characterized in that: the method comprises the following steps:
synthesis of 2-alkyl-1, 10-phenanthroline
Will 2-R 1 Mixing 8-aminoquinoline with 3-alkoxy-2-tert-butylcyclobutanone, adding Lewis Acid (LA), reacting in an organic solvent, stirring at room temperature or by heating, and purifying by column chromatography after the reaction is finished to obtain 2-alkyl-1, 10-phenanthroline;
(II) Synthesis of 2-pivaloyl-1, 10-phenanthroline
Mixing 2-alkyl-1, 10-phenanthroline, an oxidant and an organic solvent, heating and refluxing, and purifying by column chromatography after the reaction is finished to obtain 2-pivaloyl-1, 10-phenanthroline;
(III) Synthesis of 2-alkanoyl-1, 10-phenanthroline-anilide ligand
Mixing 2-pivaloyl-1, 10-phenanthroline with substituted aniline, adding a catalytic amount of acid, heating and refluxing in an organic solvent for reaction, and purifying to obtain 2-alkanoyl-1, 10-phenanthroline aniline ligand;
synthesis of 2-t-butyliminophenanthroline imine metal (II) complex
2-alkanoyl-1, 10-phenanthroline aniline ligand and anhydrous metal (II) chloride react in an organic solvent to obtain the 2-tert-butylimino phenanthroline imine metal (II) complex.
4. The process for producing a 2-t-butyliminophenanthroline imine metal (II) complex according to claim 3, wherein: the Lewis acid in the step (I) is any one or more of boron trifluoride, aluminum trichloride, aluminum tribromide, tin dichloride or zinc dichloride.
5. The process for producing a 2-t-butyliminophenanthroline imine metal (II) complex according to claim 3, wherein: the oxidant in the step (II) is any one of selenium dioxide, iodine, liquid bromine, dimethyl sulfoxide, nitrobenzene, tert-butyl peroxide, hydroiodic acid or hydrobromic acid.
6. The process for producing a 2-t-butyliminophenanthroline imine metal (II) complex according to claim 3, wherein: the metal chloride is anhydrous CoCl 2 Or anhydrous FeCl 2 。
7. The process for producing a 2-t-butyliminophenanthroline imine metal (II) complex according to claim 3, wherein: the organic solvent is any one or more of dichloromethane, chloroform, dichloroethane, carbon tetrachloride, 1, 4-dioxane, ethanol, acetonitrile, benzene, toluene, xylene, chlorobenzene, trifluoromethyl benzene, tetrahydrofuran, tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate or tetrabutyl orthosilicate.
8. The process for producing a 2-t-butyliminophenanthroline imine metal (II) complex according to claim 3, wherein: the reaction temperatures of the steps (I) - (IV) are all 0-170 ℃.
9. The process for producing a 2-t-butyliminophenanthroline imine metal (II) complex according to claim 3, wherein: the aniline is any one of 2-methylaniline, 3-methylaniline, 4-methylaniline, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, 26-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline or 2, 6-diethylaniline.
10. Use of a 2-tert-butylimino-phenanthroline imine metal (II) complex prepared according to the method of claims 2-7 in the catalysis of ethylene oligomerization, characterized in that: the 2-tert-butylimino phenanthroline imine metal (II) complex is an active component, the cocatalyst is one or two of aluminoxane or an alkyl aluminum compound, the polymerization temperature is 20-60 ℃, and the polymerization pressure is 0.1-1.0 Mpa.
CN202310583082.6A 2023-05-23 2023-05-23 2-tert-butylimino-phenanthroline imine metal (II) complex and synthetic method and application thereof Pending CN116606325A (en)

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