TW201213363A - Catalyst composition for oligomerization of ethylene and processes of oligomerization - Google Patents

Abstract

Disclosed are a catalyst composition for oligomerization of ethylene and processes of oligomerization, wherein the catalyst composition comprises chloride of Fe (II), Co (II) or Ni (II) complexed with 2-imino-1, 10-phenanthroline as the main catalyst and triethylaluminium as the cocatalyst. One of the processes of oligomerization of ethylene is using the above catalyst composition, and a molar ratio of metallic aluminum in the cocatalyst and the central metal in the main catalyst is from 30 to less than 200. The other process of oligomerization of ethylene is using the above catalyst composition, and the reaction temperature of oligomerization of ethylene is -10 to 19DEG C. The price of triethylaluminium as the cocatalyst is low, the use amount of the cocatalyst is small, and the cocatalyst has better catalytic activity, therefore the cost of oligomerization of ethylene reduces significantly, and the oligomerization of ethylene has wide industrial application prospect.

Description

201213363 ' VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an ethylene oligomeric collar-1,10-morpholine iron (1), cobalt (1) agent composition. The present invention also relates to a method. , specifically related to chlorinated 2 -imine) or nickel (E) #triethylaluminum. The use of the above composition of the ethylene polymerizer [prior art] linear alpha-dilute hydrocarbon in ethylene comonomer, interfacial activity It has a wide range of applications in the fields of synthetic intermediates, plasticizer alcohols, synthetic lubricants and oil additives. In recent years, with the continuous development of the polyolefin industry, the demand for α-olefins has increased rapidly worldwide. At present, most of the α-olefins are prepared by oligomerization of ethylene. Catalysts used in the ethylene polymerization process are mainly nickel, chromium, stray and aluminum. In recent years, the Br〇〇khart group (Brookhart, et al., J. Am. Chem. Soc., 1998, 120 7143). -7144; WO99/02472, 1999), Gibson Group (Gibson, vc et al, Chem. Commun., 1998 '849-850; Chem. Eur. J., 2000, 2221-223 1) found some Fe ( II) and c〇(II) tridentate pyrimimine complexes can catalyze ethylene oligomerization, which not only has high catalytic activity, but also has high selectivity to α-olefins. Patent CN185033 9A of the Institute of Chemistry, Chinese Academy of Sciences reports a catalyst for ethylene oligomerization and polymerization, which is a 2-imido-oxime-morpholine-coordinated Fe2, 〇:〇2 + and Ni2+ chloride. Under the action of co-catalyst methyl oxy-oxygenation, the catalyst as a main catalyst has better condensing and polymerization catalytic properties of ethylene 201213363, wherein the iron complex exhibits high oligomerization and polymerization activity for ethylene; When the reaction temperature is 4〇〇c, the oligomerization activity is the highest; while the oligomerization and polymerization activity increase with the increase of pressure; the oligomerization products include c4, c6, c8, Cl. , c, 2, (: 14, Cl6, e 1 〇 ^ 20 C22, etc.; the polymer is a low molecular weight polyolefin and a waxy polyolefin. This patent also discloses triethyl aluminum as a cocatalyst, gasification [2· Ethyl _i_10,10-phenanthroline (2,6-diethylaniline)] iron (11) as the main catalyst, Ai / Fe ratio is 5 (10) reaction temperature 4 (TC, reaction time ih, polymerization pressure At 1 MPa, the polymerization activity is 2.71x1 〇5; this patent also discloses the use of high isocatalyst (A丨/Fe ratio of 5〇〇) with triisobutylaluminum and vaporized diethylaluminum as cocatalyst. The oligomerization activity is also low. It can be seen from the teaching of the patent that when triethylaluminum is used as a cocatalyst, the oligomerization activity is still low and the practicability is poor even in the amount of the cocatalyst of rhodium, so it is mainly in its patent. The use of high-cost fluorenyl aluminoxane is a catalyst for catalyzed catalysis. The cost of methylaluminum oxymethane is too high. If it is used as a cocatalyst for large-scale application in ethylene oligomerization, it will inevitably lead to high production costs. Sun Wenhua of the Institute of Chemistry, etc. in Ir〇n Complexes Bearing 2-Imino-1,1 〇-phenanthrolinyl Ligands as Highly Active Catalysts for Ethylene Oligomerization (〇rganometallics2〇〇6 25 666_677 ) Table 2 shows the use of chlorinated [2-ethylindenyl], 〇 啡 morpholine (2,6-diethylaniline) )] The iron-based oligomerization of ethylene as the main catalyst, the ethylene oligomerization activity does not increase monotonically or monotonously with temperature, but the concentration of the polymerization activity increases with temperature when the reaction temperature is 2〇~4〇<t High and increasing, when the reaction temperature is 40~60 201213363 °c, the oligomerization activity decreases with the increase of temperature. This phenomenon is in Sun Wenhua et al. (Organometalli CS2〇〇7,26,2720-2734) - Table 4 Further experimental results have been confirmed in the experimental results of ethylene oligomerization using vaporized diethylaluminum as a cocatalyst. SUMMARY OF THE INVENTION In view of the deficiencies of the prior art, it is desirable to find a low-cost and practical ethylene oligomerization catalyst composition and oligomerization method. In order to use it for large-scale industrial use. After a lot of experimental research, it was surprisingly found that a small amount of triethylaluminum was used as a cocatalyst, and vaporized imido-deca- phenanthroline iron (Π), cobalt ( π) or recorded (] J) 催化剂士) When the catalyst composition of the main catalyst is subjected to ethylene condensing, there is an acceptable preparation activity, which is significantly different from the prior property. The amount of W is small and the catalytic activity is appropriate. The use of this catalyst group in the ethylene oligomeric art can provide a strong guarantee for large-scale industrialization. 'A group of compositions according to the present invention, including the following formula _ 亍 = = a kind of ethylene polymerization catalyst (&quot ; 1 (1) or bis = imino group - iron which makes the cocatalyst agent 'genus molar ratio of 30 to less than = the central gold of the main catalyst fiscal 201213363

Wherein each variable is defined as follows: M is a central metal selected from the group consisting of Fe2+, c〇2 + and Ni2+; R丨~Rs are each independently selected from the group consisting of hydrogen, Ci~C6 alkyl, halogen, c丨~^ alkoxy and nitrate base. In the present invention, the term "C-C: 6 alkyl" means a saturated straight or branched hydrocarbon group having from i to 6 carbon atoms. As a Cl~C6 alkyl group, a methyl group or an ethyl group may be mentioned. , n-propyl 'isopropyl, n-butyl, isobutyl second butyl, tert-butyl, n-pentyl, second pentyl, n-hexyl and second hexyl; methyl, ethyl and Isopropyl. In the present invention, the term "Ci~C6 alkoxy" refers to a group obtained by linking the above CpQ alkyl group to an oxygen atom. As the oxime alkoxy group, reference is made to a decyloxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy first butoxy group, a second butoxy group. , n-pentyloxy, second pentyloxy, n-hexyloxy and second hexyloxy; particularly preferred are decyloxy and ethoxy. In the present invention, the term "halogen" means fluorine, chlorine, bromine and iodine, and particularly preferably fluorine, gas and bromine. In a preferred embodiment of the above catalyst composition, the molar ratio of the metal aluminum in the cocatalyst to the central metal (ie, Feh, C〇2+ or Ni2+) in the procatalyst is from 5 〇 to less than 2 〇〇. Preferably, ι〇〇~ΐ99 8 , more excellent 6 201213363 is selected as 148~196, most preferably 178~196. In a particularly preferred embodiment of the above catalyst composition, ruthenium and R 丨 R R5 in the main catalyst have the following definitions: 1 : M = Fe 2+ , Ri = Me, r2 = R3 = r4 = R5 = H ; : M = Fe2+, R2 = Me, Ri = R3 = R4 = R5 = H ; 3 : M = Fe2+, R3 = Me, Ri = r2 - R4 = R5 = H ; 4 : Fe2+, Ri = R2 ~ Me, R3 = R4 = R5 = H ; 5 : M = Fe2+, Ri = R3 = Me, R2 = R4 = R5 = H ; 6 : M = Fe2+, Ri = R4 = Me, R2 = R3 = R5 = H ; 7 : M = Fe2+, Ri = R5 = Me, r2 = R3 = R4 = H ; 8 : M = Fe2+, r2 = R3 = Me, Ri = R4 = R5 = H ; 9 : M = Fe2+, R2 = R4 = Me, Ri = R3 = R5 = H ; 10 : M: =Fe2 + , Ri = R3 = R5 = Me , R2 = R4 = H ; 11 : M = T - 2 + = Fe , Ri = Et, R3 = R4 = R5 = H ; 12 :M= Fe2 + ,Ri =Et R5 = Me ' R〗^ R3 = R4 = 13 :M: =Fe2 + ,Ri =R5 = Et, R2 = r3 = R4 = H ; 14 :M: = Fe2 + , R! = iPr , R2 = R3: = R4 = R5 = H ; 15 : M: = Fe2 + , R, = R5 = iPr > R2 = R3 = R4 = H ; 16 : M = Co2 + , R, two Me ' R2 = r3 = r4 = r5 = H 17 :M: =Co2 + , R-2 =Me > R. Two R3 =r4 =R5 Two H ; 18 :M: :Co2 + ,r3 =Me > Ri =R2 =r4 =r5 =H ; 19 :M: =Co2 + « Ri —r2 =Me ' R3 =r4 =R5 =H ; 20 :M =Co2 + -Ri —R3 =Me ,R2 二r4 =R5 =H ; 21 :M = Co2 + ,R , =r4 =Me ' R_2 =r3 =r5 =H ; 7 201213363 22 · Μ ^ Cο * Rι — R-5 ~ Mg 5 R2 = R3 = -^-4 == H * 23 : M=Co2+, R2= R3=Me, R1=R4=R5—Η; 24: Μ = Co2+ ' R2 = R4= Me,Ri = R3= R5 = Η ; 25 . M = Co 5 Rj — R3 — R5 = Me * R-2: =: R4 = H > 26 · ]V1 - Co 5 R] = Et, Ρ.2==Κ·3 =^-5=H>

27 : M=Co2+, Ri=Et, R5=Me,.R2=R3=R4=H 28 : M= Co2+, R1 - R5 = Et , R2 = R3 ~ r4 = H ; 29 : M = =Co2+, Ri = iPr 9 R2 =R3 = r4 = r5: =H ; 30 : M = =Co2+, Ri = R5= iPr , R_2 = R3 = R4 = H ; 31 : M= Ni2+, Ri = Me 9 R-2 =R3 = R4 = R5 = H ; 32 : M = =Ni2+, R2 = Me ' R, ——R 3 — R4 = r5 = =H ; 33 : M = =Ni2+, R3 = Me , R! —"D — —IV 2 — R4 = R5 = H ; 34 : M= Ni2+, Ri = R2 = :Me , R3 = R4 = r5 = =H ; 35 : M = =Ni2+, Ri = R3 = :Me , r2 = R4 = R5 = =H ; 36* M=Ni2+» Ri=R4=Me>R2=R3=R5=H; 37 : M = Ni2+ > R, = R5= Me > R2 = R3 = R4 = H ; 38: M=Ni2+, R2=R3=Me' Ri=R4=R_5二H; 39: M = Ni2+, R2= R4 = Me, = R3 = R5 = H; 40 '· M=Ni2+ > Ri = R3=R5 =:Me > R2=R4=H. 41 : M = Ni2+, Ri= Et, R2= R3= R4= R5 = H ;

42 : M = Ni2+, Ri = Et, R5 = Me, R2 = R3 = R4 = H 43 · M = Ni2+, R] = R5 = Et, R2 = R3 = R4 =: H'» 44 : M = Ni2+, R!= iPr, R2= R3 Two R4= R5 = H ; 45 : M=Ni2+, RpRfiPr, R2=R3=R4=H. 8 201213363 In a particularly preferred embodiment of the above catalyst composition, the main catalysts of R and R5 are ethyl and the ruthenium 2 to 1 are both gases. The preparation of the procatalyst, which is referred to by reference to the present invention, is CN185 339 A, the preparation method in the literature. The method for preparing the procatalyst of the formula (I) as defined in the present invention generally comprises The following steps are carried out: (1) 2-Ethyl-1,10-morpholine and substituted aniline (substituent is selected from the group consisting of c丨~C6 alkyl, dentate, C丨~Cg alkoxy and nitrate Reaction to synthesize 2-imino-1,10-morpholine ligand; and (2) using the 2-iminyl-indenyl quinone ligand obtained in step 1, respectively, with FeClr4H2 〇, CoCl2 Or the reaction of NiCl2.6H20 can obtain the complex. The specific preparation process of the main catalyst used in the method of the present invention is as follows: 1. General method for ligand synthesis 1) 2-Ethyl hydrazine, 10, phenanthroline and Cl~c6 alkyl substituted aniline in ethanol The acid is refluxed for 1 to 2 days. The reaction liquid is concentrated and then passed through an alkaline oxidation column, rinsed with petroleum ether/ethyl acetate (4: hydrazine), and the second fraction is the product 'solvent to obtain a yellow solid. 2_Imino-based, 〗 〇 啡 morphine ligand. 2) 2-Ethyl fluorenyl-no-phenanthroline and fluorine, Ci~C6 alkoxy or nitro-substituted stilbene amine with p-toluenesulfonic acid as catalyst and added to molecular sieve or anhydrous sodium sulfate as dehydrating agent to reflux in toluene After 1 day, the solvent was removed from the solvent, the benzene-benzene-external alumina column was rinsed with petroleum ether/ethyl acetate (4:1), the second fraction was the product, and the solvent was removed to obtain a yellow solid. i, 1 〇 _ morphine ligand. 3) 2-Ethyl phenyl 4,1 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The reaction was heated at 〇 ° C for 1 day, and the ruthenium oxalate was removed under reduced pressure, and then passed through an anatized alumina column, rinsed with petroleum ether/ethyl acetate (4:1), and the second part was a product' Removal of the solvent gave the yellow solid 2-imino-1,1 phenanthroline ligand. The alkyl substituted aniline is preferably 2,6-diethyl stilbene. All of the above synthesized 2-imino-1,10-morphine ligands were confirmed by nuclear magnetic, infrared and elemental analysis. Second, the general method for the synthesis of iron (II), cobalt (11), nickel (11) complexes FeCl2.4H2 〇, CoC12 or NiCi2.6H2 〇 ethanol solution Massage 1.1 1.1, 2 drops added to 2-Asia In the solution of the aminofibrin ligand, the mixture is stirred at room temperature, the precipitate is precipitated, filtered, and dried by washing with acetonitrile to obtain a J imido-1,10 phenanthroline complex. Complexes 1 to 45 were confirmed by elemental analysis and infrared spectroscopy. According to another aspect of the invention

The molar ratio of the metalloid metal in the cocatalyst is, on the other hand, a method for the oligomerization of ethylene, a catalyst combination of ketone-1,10-morpholine iron (Π) and cobalt (π) as a promoter. The metal aluminum in the agent is between 30 and less than 200 in the main catalyst:

(I) 10 201213363 wherein each variable is defined as follows: M is a central metal, also from Fe2+, Co2+ and 2+; ·^~'r5 are each independently selected from the group consisting of gas, Ca~C6 alkane, #素,κ6 Base and nitro group. In a preferred embodiment of the method of escaping the polymerization, the metal aluminum in the promoter and the central metal in the ruthenium catalyst (i.e., 2+, c〇2+ or

The molar ratio of Ni2+) is from 50 to less than 200, preferably from 1 〇〇 to ι 99·8, more preferably from 148 to 196, most preferably from 178 to 196. In a preferred embodiment of the method of polypolymerization, R丨~R5 in the main catalyst each have an entropy + ^ 蜀, which is selected from the group consisting of hydrogen, mercapto, ethyl, isopropyl, fluorine, gas, bromine, methoxy, , & ^ Ethoxy and nitro. In the above embodiment of the oligomerization method, and in the embodiment of R rabbit 7* ,,

5 is an ethyl group and R is hydrogen in the above oligomerization sides 2 to 4. In a particularly preferred embodiment of hydrazine and RR of the agent t, 'the main urging 1 : M = Fe 2 + 2 : M = Fe 2 + 3 : M = Fe 2 + 4 · M = Fe 2 + 5 · M = Fe 2 + 6 · M = 7 * M = Fe2 + R, ~I has the following definition: R1 = Me, I? A R2 = R3 - R4 = R5 = = H ^ R2 = Me . R __ n

Kl== R3= R4= R.= H R~e,R — D 5

^ = ^2=K4=K5=H 'R2==Me ' R3-R4=r5==H R3-Me,R2=,R4==R5==h R,== R5= Me > l? 8 : M = pe2+,r = R3 = R4 - ^ ^ K4〇, r> 10 * Fe2+ ~ R3 = R5 1 ^ R3 = R,

9 : M = Fe2+ , p , Ri = Han 4 = R5 = H

H

Me ' R2 = r4 < H 11 201213363 11 : 12 : 13 : 14 : 15 : 16 : 17 : 18 : 19 : 20 : 21 : 22 : 23 : 24 : 25 : 26 : 27 : 28 : 29 : 30 : 3 1 : 32 : 33 : 34 : M=Fe2+ > Ri=Et 5 R2=R3 — R4=R5==H ; M=Fe2+, R】 = Et, R5=Me ' R2=R3=R4=H ; M=Fe2+ 1 Ri=R5=Et j R2=R3=R4=H ; M=Fe2+, Ri=iPr* R2=R3=R4=R5=H; M=Fe2+ 5 Ri=R5=iPr » R2=R3= R4=H i M=Co2+, Ri = Me' R2=R3 — R4=R5—H; M=Co2+, R2=:Me, Ri = R3=R4=R5=H; M=Co2+, Rs^Me* Ri = R2=R4=R5=H; M=Co2+, Ri=R2=Me, R3=R4=R5=H; M=Co2+, Ri=R3=Me, R2=R4=R5=H; M=Co2+,Ri =R4=Me, R2=R3=R5=H; M=Co2+, Ri=R5=Me, R2=R3=R4=H; M=Co2+ 5 R2=R3=Me > Ri = R4=R5=H ; M=Co2+, R2=R4=Me, Ri=R3=R_5=H; M=Co2+, Ri=R3=R5=Me, R2=R4=H; M=Co2+, Rj=Et» R2=R3=R4= R5=H; M=Co2+, Ri = Et>R5=Me>R2=R3=R4=H; M=Co2+, Rj-Rs^Et5 R2=:R3:=R4=H; M= Co“ > Rj = =iPr , R2 = r3 = R4 = Rs = H ; M = Co2H ♦ Ri = R5 = iPr > r2 = R3 = r4 = H ; M = : Ni2 + , = Me ! 1 R2 = R3 = R4 = R5 = H ; M = = Ni2 + , R2 = = Me 1 Rj = r3 = R4 = R5 = H ; M = Ni2 + , R3 = =Me ! 1 Ri = R2 = R4 = R5 = Ή ; M = =Ni2 + , Ri = R2 = Me, R3 = R4 Two R5 = H; 12 201213363 Person 35 : M = Ni2+ > Ri = R3 = Me, R2 = R4 = r5 = H ; 36 : M = Ni2+, Ri = R4 = Me, R2 = R3 = r5 = H ; 37 : M = Ni2+, Ri = R5 = Me * R2 = R3 = r4 = H ; 38 : M = Ni2+, R_2 = R3 = Me, Ri = R4 = r5 = H ; 39 : M = Ni2+, R2 = R4 = Me, Ri- R3 = r5 = H ; 40 : M = Ni2+, Ri = R3 = R5 = Me, R2 = R4 = H ; 41 : M = Ni2+, Ri = Et, R2 = R3 = R4 = r5- H ; 42 : M = Ni2+, Ri = Et, R5 = Me, r2 Two R3 = R4 = H ; 43 : M = Ni2+, R i = R5 = Et, R2 = R3 = r4 = H 44 : M = Ni2+, Ri = iPr R2 = R3 = :R4 = r5 = H ; 45 : M = Ni2+, Ri = R5 = iPr R2 = R3 = :R4 = H. The oligomerization reaction conditions involved in the above oligomerization methods are well known in the art, and the above oligomerization method is preferably as follows: The organic solvent and the catalyst composition are added to the reaction vessel, and then at a pressure of 0.1: ~3 MPa and the reaction temperature is 20 to 150. (: The next reaction is 3 Torr to 1 Torr, then cooled to _1 Torr to 1 〇 ac, and a small amount of the reaction mixture is taken out and neutralized with 5% dilute hydrochloric acid, and then subjected to gas chromatography (GC) analysis. The reaction temperature is preferably 20 to 8 Torr, the force is preferably 1 to 5, and the reaction time is advantageously 30 to 60 minutes. In the method of oligomerization, the organic squama, tetrachloro sulphate, south, Ethanol, benzene, xylene and one: cyclohexyl benzene. T and a methane, etc., excellent by the fugitive oligomers including c4, c6, c έ to collect acetonitrile 8, C10, c12, c14, c, Γ Cl6 c18, c20, c, etc. 13 201213363 α-olefin selectivity can reach more than 95%. At the end of the ethylene oligomerization reaction mixture with 5% dilute hydrochloric acid And gc analysis after the results. The results show that the oligomerization activity can reach above Wg.morU-1, and the oligomeric product knife cloth is more reasonable. In addition, the remaining reaction mixture is neutralized with 5% diluted hydrochloric acid acidified ethanol solution, no Obtaining a polymer. By the above oligomerization method, low cost (the monovalent amount of triethyl aluminum is only the unit price of methyl aluminoxane) One tenth of the aluminum triethylaluminum (AlEt3) is a catalyst for the catalyst to vaporize 2 -imidomorpholine iron (II), cobalt (II) or nickel (ruthenium) as the main catalyst, in the cocatalyst The molar ratio of the metal in the main catalyst to the medium in the main catalyst is in the range of 30 to less than 200, and the catalytic activity is acceptable, and the amount of the cocatalyst is low, which is highly practical. According to the present invention, another A method for ethylene oligomerization using a gasification of 2-imino-no-morpholine iron (π), cobalt (11) or nickel (11) as a main catalyst of the following formula (I), and diethyl ester as a cocatalyst Catalyst composition, ethylene polymerization reaction temperature is -1 〇~19 °c:

Wherein each variable is defined as follows: Μ is a central metal, preferably selected from the group consisting of Fe2+, Co2+, and Ni2+; R丨~R5 are each independently selected from the group consisting of hydrogen, Cl~c6 alkyl, halogen, Ci~C6 alkoxy, and nitro . 14 201213363

In a preferred embodiment of the above-described method of polymerizing, the RcRs in the main catalyst are each independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, fluorine, gas, bromine, methoxy, ethoxy, and Nitro. In a more preferred embodiment of the above oligomerization method, the sum R5 in the main catalyst is ethyl and the scales 2 to 1 are both hydrogen. In a particularly preferred embodiment of the above oligomerization process, the ruthenium and ruthenium in the procatalyst have the following definitions: 1 : M = Fe 2+ ' R ' = Me, R 2 = R 3 = R 4 2 : M = Fe2+, R2=Me. R1=R3=R

3 : M = Fe2 4 : M = Fe2' 5 : M = Fe2 6 · M = Fe2' 7 : M = Fe2H 8 : M 2 Fe2H 10 11 12 13 14 15 16 17 M = Fe2 M = Fe2H M = Fe2H M = Fe2H M = Fe2H M= Fe24 M= Co2 M= Co2 R3= Me,r丨=R2== RR丨=R2= Me,r3== R Ri = R3 == Me Ri = R4= Me R> = R5 -Me R2= R3= Me R2 = R4 = Me (Ri = R3= R< R,

Rs"Rs" r5 = r5 = Rs- r5- R2= R3= r4^ Ri = r4 = r5 ; R1 = R3 = R5 ^ Me,r2== R4

H H H H H H H H H

Et 5 R2 = R3 = r4== H ;

Ri = Et,r5 = R* = R5= Et . r2=k ~ iPr > R

Me, R3 < R4 H ; H ; :R, R3= R4== r5

= R5= iPr,RH : H ; R3 = r4 : Rl = Me, R2=R3=R4=r5 R2==Me,Ri=R3=R4=r5<H ; H ; 15 201213363 18: M=Co2+,R_3 =Me,Ri=R2=R4=R5=H; 19: M=Co2+, RfR^sMe, R3=R4=R5=H; 20: M= Coz + ' R i = R3 = Me, r2 =r4 =r5 =H ; 21 : M = :Co2 + > Ri = =R4 = Me, r2 =R3 =R5 =H ; 22 : M = =Co2 + ,Ri = R5 = Me, r2 =R3 =r4 =H ; : M = Co2 + , R2 = : R3 = Me > Ri = r4 = r5 = H ; 24 : M = = Co2 + , R2 = = R4 = Me, Ri ~ R3 = r5 = H ; 25 : M = Co2 + ,Ri = R3 = R5 = Me ' R-2 =r4 =H ; 26 : M = = Co2 + ,R,= =Et, R2 ~ R3 = R4 = R5 — H 9 27 : M= Co2 + ,R != Et , R5 = Me 5 R-2 =R3 =R4 = H 28 : M = =Co2 + » R] = R5 = Et, R2 = R3 = R4 = H, 29 : M = =Co2 + * Ri = =iPr, R2 = :R3 =r4 =R5 =H ; 30· M=Co2+, Ri = R5=iPr' R2=R3=R4=H; 31 : M=Ni2+, RfMe, R2=R3 II R4=R5= H ; 32 : M=Ni2+ 5 R2=Me » Ri=R3=R4=R5=H ; 33 · M=Ni2+ » R3=Me » Ri=R2=R4=R5=H ; 34 : M = Ni2+ ' R, = R2= Me, R3= R4= R5 = H ; 35 : M = Ni2+, R, = R3 = Me, R2 = R4 = R5 = H ; 36 : M=Ni2+ » Ri=R4=Me * R2=R3=R5=H ; 37 : M=Ni2+ ' Rj^RfMe, R2=R3=R4=H ; 38 : M = Ni2+, R2 = R3 Two Me, R! = R4 = R5 = H; 39: M=Ni2+ ' R_2=R4=Me,; 40 ^ M=Ni2+ > Ri=R3=R5=Me * R2=R4=H ; 41 : M=Ni2+> R!=Et » R2=R3=R4=R5=H; 16 201213363 42 : M=Ni2+, 1 — Et, R5 = Me, R2 = R3 = r4 = η ; 43 · M= Ni2+ , R __ __ — R5=Et ' R2 =R3=R4=H ; 44 : M= n,-2+ r, ,R丨,' R2=r3=R4=R5=h; 45:,i2+,Wm=H; i φ: oligomerization method' Preferably, the reaction is carried out according to the following technical scheme: the organic solvent and the catalyst composition are added to the reaction, and then the ethylene pressure is 0.1 to 30 MPa, and the 讦nc + temperature is -1 to 19 ° C, and the reaction is carried out for 30 to 100 minutes. Then, gas chromatography (GC) analysis was carried out at -1 〇 〜1 (ΓΓ下'), and the gas chromatographic (GC) analysis was carried out after neutralization with 5% dilute hydrochloric acid. In the above oligomerization method, the main catalyst is usually used in the form of a solution. The ☆ agent is a conventional solvent, for example, the solvent may be selected from the group consisting of A$, Cyclohexylamine, tetranitrogen, ethanol, xylene, and aerobic, etc., preferably toluene. In the above oligomerization method, the temperature is preferably - 10 to 15. (:, more preferably 〇 15 15 ' is most preferably 5 to 1 (rc; the reaction time is advantageously minutes; the reaction pressure is preferably 1 to 5 MPa. In the above oligomerization method, the cocatalyst The molar ratio of the central metal in the main catalyst in the metal (iv) is 49 to 500, preferably 1 to 4 Torr, more preferably 200 to 3 Torr, and most preferably 3 Torr. The organic solvent is selected from the group consisting of toluene, cyclohexane, diethyl ether, tetrahydrofuran 'ethanol' benzene, diphenylbenzene, and dichlorodecane, etc. The polyethylene oligomer is obtained by the above oligomerization method, and the obtained ethylene oligomerization product includes c4. , c6, c8 'c丨., Cl2, C", Ci6, c18, c20, c22, etc.; α-ene The selectivity of hydrocarbons can reach above 96%; the polymerization activity is high. In addition, 17 201213363 The remaining reaction mixture is produced with a small amount of polymer. 5 /〇 diluted with hydrochloric acid acidified ethanol solution, only by the above oligomerization method, Catalyst composition using gasification 2_iminomorphine iron (4), guar (4) or nickel (Π) as the main catalyst and low-cost triethyl sulphate (4) as a cocatalyst, at a lower temperature (heart ~ grasp, Under the condition of catalyzed ethylene oligomerization, low amount of cocatalyst and high oligomerization activity, a new ethylene oligomerization pathway has been developed. Compared with the prior art, the invention adopts low cost (triethyl sulphate is only methyl methoxide) The triethylamine (4) Et3), which is a fraction of the price of the material, is a catalyst composition for the promoter of chlorinated 2-imidomorphine iron (π), gu (1) or jin (hong) as the main catalyst, not only catalyzing The activity is acceptable, the selectivity of the heart olefin is high, and the amount of the cocatalyst is low, and the catalytic effect and the cost are well balanced. The use of the present invention overcomes the technical bias, optimizes the reaction conditions, and makes Ethylene oligomerization The following is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto. The changes and modifications should be within the scope of the present invention. Example 1 1. Preparation of the main catalyst 2-Ethyl-1,1 〇 phenanthroline (〇4445g, 2lnm〇l) and 2 ,6-diethylbenzene 18 201213363 Amine (0.4175g '2.8mmol) Add 40mg p-toluenesulfonic acid as a catalyst and add 2g 4A molecular sieve as dehydrating agent, reflux in 30ml ethanol for 1 day, remove the solvent after the hydrazine Dissolved with dioxane methane, over-alkaline alumina column, leaching petroleum ether / ethyl acetate (4:1), the second fraction is the product, the solvent is removed to obtain a yellow solid, which is 2-ethyl decyl-l , l-porphyrin (2,6-diethylaniline) ligand, yield 0.6 g' yield 84%. Nuclear magnetic analysis ^HNMRpOO MHz, CDC13): 6 9.25 (dd, J = 3.0 Hz, 1H); 8.80 (d, J = 8.3 Hz, 1H), 8.35 (d, J = 8.3 Hz, 1H); 8.27 (dd, J = 7.8 Hz, 1H); 7.86 (s, 2H); 7.66 (m, 1H); 7.15 (d, J = 7.6 Hz, 2H); 6.96 (t, J = 7.5 Hz, 1H); 2.58 (s, 3H, CH3); 2.43 (m, 4H, CH2CH3); 1.16 (t, J = 7.5Hz, 6H, CH2CH3). Elemental analysis: c24H23N3 (353.46), rational value 6. C: 81.55; Η: 6.56; N: 11.89. Measured value ‘c: 80 88 ; Η : 6_59 ; N : 11.78. 5 ml of FeCl2.4H20 (48 mg '0.24 mm〇l) in absolute ethanol was added dropwise to 5 ml of 2-ethylindenyl-l,l-phenanthroline (2,6-diethylaniline) ligand (70.6 mg). , 〇. 2mmol) in absolute ethanol solution, stirred at room temperature for 6 hours, precipitated, filtered, washed with diethyl ether and dried to give a dark green powder solid, which is gasified [2-ethyl fluorenyl-l,l-morphine Porphyrin (2,6-diethylaniline)] iron (ruthenium) complex with a yield of 95. /. . Elemental analysis: C24H23Cl2FeN3 (48() 21), 测试: 4.83; N: 8.75. 2. Ethylene oligomerization reaction: Toluene and ruthenium. 53 ml of diethylaluminum toluene solution (concentration of 〇74 m〇1/1) and 8 ml of main catalyst chlorinated [2_acetylmorpholine (2,6-diethyl) 19 201213363 Entering 300ml of unrecorded steel

Gm〇l_ (Fe).h., the oligomer content is q 12.〇〇/〇, c 〇64.7%, C6~C18 87.0% (including linear aniline)] iron (Π) (2 The toluene solution of Ομηποί) was added to the crucible to make the total volume l〇〇ml, and when the Ai/pe was 40 ° C, the reaction vessel was charged with ethylene, and the reaction was stirred for 30 min. After that, cry with the injection,

Α-olefin 98.0%), C CM 1·〇%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Example 2 Using the main catalyst prepared in Example 1, the cocatalyst was triethylaluminum for ethylene polymerization. The difference from Example 1 was that the amount of triethylamine benzene solution was 〇.54 ml (concentration). For 〇74ιη〇1/1), let Ai/Fe = 199.8. At 40 ° (: under '1'\'s ethylene pressure, stir the reaction 3 such as 11. Use a syringe to take a small amount of the reaction mixture and neutralize it with 5% diluted hydrochloric acid for GC analysis: oligomerization activity is a polymer The yttrium is C4 12.1%, C6~Ci〇64.5%, C6~C18 86.8% (containing linear α-olefin 97.5%) 'Cm~CM 1.1%. The remaining reaction mixture is acidified with 5% hydrochloric acid in ethanol. Neutralization, no polymer was obtained. The analysis results are shown in Table 1. Example 3 Using the main catalyst prepared in Example 1, the cocatalyst was triethyl sulphide 20 201213363, and the ethylene oligomerization reaction was different from that of Example 1. The reason is: the amount of triethyl knot toluene solution is ml51ml (concentration is 〇.74mol/l), so that Al/Fe = 189. Under 4〇t, keep the ethylene pressure of iMPa, stir the reaction for 3〇min. A small amount of the reaction mixture was taken out from the syringe and neutralized with 5% dilute hydrochloric acid for GC analysis. The aggregating activity was as follows: C4 11.6%, C6~C10 64.8%, C6~C18 86.9% (including Linear ex-olefin 98.0%), Cm~C2815%. The remaining reaction mixture was neutralized with 5% hydrochloric acid acidified ethanol solution. No polymer was obtained. The results of the analysis are shown in Table 1. Example 4 Using the main catalyst prepared in Example 1, the cocatalyst was ethylene trimerization reaction of triethylaluminum, which differs from Example i in that triethylaluminum The amount of the toluene solution was 0.48 ml (the concentration was A1/Fe = 178. At 4 °TC, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 3 Torr. The reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid. GC analysis: the polymerization activity was 丨, the oligo content was C4 10.5%, C6~C1065.1%, C6~C18 87.7% (including linear "• olefin 98.3〇/〇", C20~C28l 8% The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The analysis results are shown in Table 1. Example 5 Using the main catalyst prepared in Example 1, the cocatalyst was triethyl 21 201213363 for B. The dilute aromatization reaction differs from that of Example 1 in that the amount of the triethylaluminum benzene solution is 〇.4 ml (concentration: 〇74 m〇1/1) such that A1/Fe = 148. At 40 ° C Underneath, maintain the ethylene pressure of iMPa, stir the reaction for 30 min. The reaction mixture was neutralized with 50/N diluted hydrochloric acid for GC analysis: the oligomerization activity was 丨21xl〇6 gm〇rl(Fe)士·!, and the oligomer content was C4 24.7% ' c6~C10 57.4 %, C6~C18 72.7% (including linear ct-olefin 92.9%). The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Example 6 Using the main catalyst prepared in Example 1, the cocatalyst was triethyl sulphide oligomerization reaction, and the difference from the first embodiment is that the use of the solution of the triethyl sulphate solution is 〇.81 ml. (concentration: 〇.25mol/l), let goblet /? 6 = 10 Bu at 40 ° C, maintain the ethylene pressure of IMPa, stir the reaction for 3 〇 min. A small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid for GC analysis: the oligomerization activity was i.〇ix1〇6 gm〇ii(Fe).hi, and the oligomer content was C4 21.6〇/〇, respectively. C6~C10 53.6%, C6~C18 75.3〇/〇 (which contains linear α-olefin 89.9%), (^~(:28 3.1%β remaining reaction mixture neutralized with 5% hydrochloric acid acidified ethanol solution, no The polymer was obtained. The analysis results are shown in Table 1. Example 7 Using the main catalyst prepared in Example 1, the cocatalyst was triethyl sulphide 22 201213363 for ethylene oligomerization, which differs from Example 1 in that: The amount of ethyl sulfamethoxazole solution is 〇Ami (concentration 〇25mol/l), so that Al/Fe = 5〇. Maintain the ethylene pressure of IMPa at 40 C and stir the reaction for 30 min. Remove a small amount of reaction mixture with a syringe. GC analysis was carried out after neutralization with 5% dilute hydrochloric acid: the oligomerization activity was 〇12χ1〇6 gm〇1_1(Fe), and the oligomer content was C4 7.4% ' C6~C10 86.8%, C6~C18 92 • 6% (containing linear ct-olefin 92.5%) 'C2〇~C28〇%. The remaining reaction mixture was acidified with 5% hydrochloric acid. The alcohol solution was neutralized and no polymer was obtained. The analysis results are shown in Table 1. Example 8 Using the main catalyst prepared in Example 1, the cocatalyst was triethylaluminum for ethylene polymerization, which differed from the example 在于 in that : The amount of triethylaluminum toluene solution is 〇.24ml (concentration is 〇25111〇1/1), so that A1/Fe = 30. At 40 °C, 'stay the ethylene pressure of 1MPa, and mix the reaction 3〇_ Use a syringe to remove the small reaction mixture and neutralize it with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity is 0.08xl〇6g.m〇rl, the amount is C6~Cig87 - linear α-olefin 91·5» /.), C2〇~C28〇%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The analysis results are shown in Table 1. Example 9 Preparation method using the main catalyst of Example 1 'The difference is that 23 201213363 5 〇 11 (: ( (: 121.2111 by '0.241111] 1 〇 1) of anhydrous ethanol solution was added dropwise to 5 ml of 2-ethyl fluorenyl-1,10-morpholine (2 , 6-diethyl sulfonamide) ligand (7 〇 6 mg, 〇. 2 mmol) in absolute ethanol solution, stirred at room temperature for 6 hours, precipitated Sinking, filtration, washing with ether and drying to obtain a brown solid, which is gasified [2_Ethyl-1,10-morphine (2,6-diethylaniline)] The yield was 95%. Elemental analysis. C24H23Cl2CoN3 (483.29), calcd. C: 59.69; H. 4.86, N· 8.62 ' Theory C: 59.64; H: 4.80; N: 8.69. The ethylene oligomerization process described in Example 1 was repeated, in which the cocatalyst was still triethyl ing 'toluene and 0.53 ml of triethylaluminum toluene solution (concentration of 0.74 mol/l) and 8 ml of chlorinated [2-B A solution of thiol·ijo-morpholine (2,6-diethylaniline)]cobalt(II) (2.0 μΐη〇1) in toluene was added to 3 〇〇ml of stainless steel high pressure dad to make the total volume 100 ml. , Al/Co = 196. When the temperature is as far as 40 ° C, 'fill the reactor with ethylene' and maintain the ethylene pressure of 1 MPa'. Stir the reaction for 30 min », then take a small amount of the reaction mixture with a syringe and neutralize it with 5 ° / 〇 diluted hydrochloric acid for GC analysis. The oligomerization activity was ι.51χ106 g-mol'CoVh·1, and the oligomer content was c4 100%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Example 10 The preparation method of the main catalyst of Example 1 was used, except that: 5 ml of a solution of NiCl 2 '6H20 (57.0 rng, 0.24 mmol) in absolute ethanol was added dropwise to 5 ml of 2-ethylindenyl-l,l-morphine. The morpholine (2,6-diethylamino) ligand (7. 6 mg, 0.2 mmol) in anhydrous ethanol was stirred at room temperature for 6 hours, 24 201213363 precipitated, filtered, washed with diethyl ether and dried. A yellow-brown solid, chloro[2-ethylindenyl-l,l-phenanthroline (2,6-diethylaniline)] nickel (II) complex, yield 96%. Elemental analysis: C24H23Cl2NiN3 (483 〇5), test value (::59_64; 11:4.82;]^: 8.53; theoretical value (::59.67; 11: 4.80; N: 8_70. The ethylene described in Example 1 was repeated. Oligomerization process in which the cocatalyst is still triethylaluminum 'p-phenylene and ruthenium. 53 ml of triethylaluminum toluene solution (concentration of 0.74 m〇l/l) and 8 ml of gasification [2_ethylhydrazine·Μ〇 _ phenanthroline (2,6-diethylaniline)] nickel (11) (2. (^111〇1) benzene solution was added to the stainless steel autoclave of 3〇〇1111 'to make the total volume l〇 〇ml, Al/Ni = 196. When the temperature reaches 40 °C, 'recharge the ethylene into the reaction dad, keep the ethylene pressure of iMPa, stir the reaction for 30 min. After that, take a small amount of the reaction mixture with a syringe and use 5% dilute hydrochloric acid. And subsequent GC analysis: the oligomerization activity was 丨4〇χΐ〇6 g-mol'NiVh·1' oligomer content was Q } 〇〇%. The remaining reaction mixture was neutralized with 5% hydrochloric acid acidified ethanol solution. The polymer was not obtained. The analysis results are shown in Table 1. Example 11 Using the main catalyst prepared in Example 1, the cocatalyst was triethylaluminum into ethylene oligomerization reaction, triethyl sulphate The amount of the toluene solution was (concentration: 0.74 mol/l)' such that A1/Fe = 196. The difference from the example i is that under the 4th generation, the pressure of the acetonitrile of 2 MPa is maintained, and the reaction mixture is 5 ° ° After neutralization of dilute hydrochloric acid of hydrazine, g-mol'FeVh-i was carried out, and the oligomer was taken out with a syringe to take a small amount of the reaction mixture and analyzed by GC: the oligomerization activity was 3 2 1 x 1 〇6 25 201213363 罝 respectively C4 19.40% 'C6~Ci〇53.02%, C6~C18 75.68% (containing linear α-olefin 96.9%) 'C 2 〇~C 2 8 4.9 2 %. The remaining reaction mixture was acidified in 5% with hydrochloric acid in ethanol And, no polymer was obtained. The results of the analysis are shown in Table 1. Example 1 2 Using the main catalyst prepared in Example 1, the cocatalyst was subjected to ethylene oligomerization reaction of triethylamine, which differs from Example 1 in that: The amount of ethyl oxazepine solution was 0.54 ml (concentration A1/Fe = 199.8; maintain the ethylene pressure of 2 MPa at 40 ° C, stir the reaction for 30 min. Take a small amount of the reaction mixture with a syringe and neutralize with 5% dilute hydrochloric acid. After GC analysis: the oligomerization activity was 3.83χ106 g.mollFe).!!·1, the oligomer content was 〇42 1.05% '〇6~<!:丨.52.37%' (:6~(:18 73.3 6% (which contains linear α-lean smoke 97.5%), C20~C28 5.59〇/〇e remaining reaction mixture Neutralization of 5 〇 / 〇 hydrochloric acid acidified ethanol solution, no polymer was obtained. The results of the analysis are shown in Table 1. Example 1 3 Using the main catalyst prepared in Example 1, the cocatalyst was triethylaluminum for ethylene oligomerization reaction, and the amount of triethylaluminum benzene solution was 0 53 ml (concentration: 74.74 mol/l), so that A1 /Fe= 196. The difference from Example 1 is that it keeps the ethylene pressure of 3 MPa at 40 t, and mixes the reaction core 2 and takes a small amount of the reaction mixture by injection II and neutralizes it with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity is 64〇xl〇6g.m〇1.1(Fe) h丨 oligomer 7 contains 26 201213363 ~ C18 71.5% (the amount of reaction mixture remaining is C4 17.5% 'C6~C丨. 46.2%, C6 linear ex - olefin 98.7%), C2 〇 ~ C28 li.o%. Neutralized with a 5% hydrochloric acid-acidified ethanol solution, no polymer was obtained. The results of the analysis are shown in Table 1. Example 1 4 Using the main catalyst prepared in Example 1, the cocatalyst was subjected to ethylene oligomerization reaction of triethylamine, which was different from the example 在于 in that the amount of triethylamine solution was 0.4 ml (concentration). 0.74 m〇1/1), A1/Fe = 148; at 40 ° C, maintaining an ethylene pressure of 3 MPa 'stirring reaction 3 〇 min. A small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid for GC analysis: the oligomerization activity was 5.21 x 1 〇 6 g. mor ^ F ^.hi, and the oligomer content was C4 19.5% ' C6 ~ Ci 〇 53.4%, C6~Ci8 75_8〇/〇 (which contains linear α-dilute hydrocarbon 98.40/〇), Cm~Cm 4.7%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Comparative Example 1 The main catalyst 'cocatalyst prepared in Example 1 was subjected to ethylene oligomerization reaction of triethyl aluminum, which was different from Example 1 in that the amount of triethyl succinyl solution was 1.35 ml (concentration was 0.74). Mol/l), making Al/Fe = 500. The ethylene pressure of iMPa was maintained at 40 ° C, and the reaction was stirred for 30 min. A small amount of the reaction mixture was taken out with a syringe and neutralized with 5% hydrochloric acid for GC analysis: the oligomerization activity was o.ggxK^g.moilFe)·]^1, and the oligomer contained 27 201213363 was C4 37.0, respectively. /〇, C6~Ci〇 52.0%, C6~C18 63.0% (including linear α-dilute hydrocarbon 91.53⁄4), C2〇~c28 0%. The remaining reaction mixture was neutralized with a 5 % hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Comparative Example 2 Example 34 of the patent CN1850339A is incorporated herein by reference, the main catalyst is gasified [2-ethyl-branched 1, 1 〇 _ _ _ _ _ _ _ _ _ Iron (II), the cocatalyst is triethylaluminum; the polymerization process is as follows: 1000 ml of toluene and 5.0 ml of triethylaluminum (ιο mol/1 in hexane) and 1 〇ml of the main catalyst (ΙΟμηηοΙ) in toluene solution Add to 2 〇〇〇 _ml stainless steel autoclave. Mechanical stirring was started, and 35 rpm was maintained. When the temperature reached 4 〇 c, ethylene was charged into the reaction vessel, and the oligomerization reaction was started. At 4 〇. Under the armpit, maintain the ethylene pressure of IMPA and stir the reaction for 1 h. A small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then subjected to gas chromatography (Gc) analysis: the oligomerization activity was 271.271xl〇6 g.mol-i(Fe).hi, the content of the polymer was respectively It is: C4 39.3%, C6 29.3% 'C8~C22 3 1.4%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Comparative Example 3 Using the main catalyst prepared in Example 1, the cocatalyst was triethylaluminum for ethylene oligomerization, which was different from the example 在于 in that the amount of the triethylaluminum solution was 2.70 ml (concentration was 〇.74mol/l), making Ai/Fe = 28 201213363 1000. The ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 3 Torr. A small amount of the reaction mixture was taken out with a syringe and neutralized with 5% hydrochloric acid for GC analysis: the oligomerization activity was Ο.ΙδχΙΟ^.ιηοΙ^Ρε).!!·1, and the oligomer content was C4 43.9%, respectively. C6 ~ C10 50.9%, C6 ~ C18 55.5% (which contains linear α · olefins 8. 4.3%) 'C2 〇 ~ C 2 8 〇. 6 %. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 1. Comparative Example 4 The main catalyst prepared in Example 1 was subjected to the ethylene agglomeration reaction as described in Example 1, except that the cocatalyst was a mercaptoaluminoxane, and the amount of the mercaptoaluminoxane benzene solution was 〇. 26ml (concentration i Smol / 丨), so that Al / Fe = 195. At 4 CTC, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. A small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2 5 x l 〇 6 g m 〇 r (&) 『! The content of the polymer was C4 14.2%, c6~C10 44.9%, C6~C18 74.1% (including linear α-dilute hydrocarbon 89 〇〇 / small ~ C28 u 7%. The remaining reaction mixture was acidified with 5% hydrochloric acid The ethanol solution was neutralized to obtain a white waxy polymer with a polymerization activity of 6. The analysis results are shown in Table 1 °. It can be seen from Table 1. The gasification of 2-imino-1,10-morpholine was carried out in the ethylene polymerization. Catalyst composition as a procatalyst and triethyl sulphate as a cocatalyst 'has low catalysis, 3⁄4' at higher catalyst loadings (Al/Fe 500, 1000) and at lower catalyst dosages & And the oligomerization activity of 29 201213363 e ratio is 195) the selectivity of sulfhydryl α-olefins reaches 2xl06g.m〇ri.hi 'with similar ratios (the oligomerization activity of ai/f aluminoxane as a cocatalyst is close to And ethylaluminum is a cocatalyst, which has an unexpected effect at a low dosage, and is high. This means that a low catalytic ratio of three has a suitable catalytic activity e molar ratio in the range of 30 to less than 200, with The eight (four) molar ratio increases, the reactivity increases; and the t A1/Fe molar ratio is greater than 2〇〇 to the paradigm In the case of 'in the range of 'molar moles, the reactivity decreased instead. Example 15 Using the main catalyst prepared in Example 1, the cocatalyst was triethyl sulphate for ethylene oligomerization. The ethylene oligomerization process was as follows: And 〗 2imi (0.8954mm〇l) triethylaluminum toluene solution (concentration of 〇74m〇i/i) and 12ml of gasification [2-ethyl fluorenyl-l,l 〇-morpholine (shrink 2,6·two Ethyl aniline)] iron (Π) (3. Ομηιοί) solution of a solution of stupid is added to 3 〇〇ml stainless steel high pressure dad, so that the total volume is 100ml, Al / Fe = 298.5. When the temperature of the reactor is cooled - At 15 ° C, the reactor was charged with ethylene, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at -10 ° C, and the reaction was stirred for 30 min. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid to carry out gc. Analysis: The oligomerization activity was 5,35xl06 g^mor^FeVh·1, and the oligo content was C4 24.92% ' C6~C10 57.03% ' C6~C1874.090/ (including linear α_ 埽 hydrocarbon 98.10/〇) ), C2〇~C280.990/〇. The remaining reaction mixture was neutralized with a 5 〇/0 hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results are shown in Table 2 billion 30201213363 Example 16

Using the main catalyst prepared in Example 1, triethyl sulphate was used as a cocatalyst to carry out ethylene oligomerization. The oligomerization reaction conditions were as in Example 15. The difference was that when the reaction temperature was lowered to -1 0 c, the reaction was filled with ethylene, and the ethylene pressure of 1 MPa was maintained. The temperature was maintained at _5 °c, and the mixture was stirred. Reaction for 30 min. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid, followed by GC analysis: the oligomerization activity was 7.74 X 106 g.mol 'Fe)·!!-1, and the oligomer content was c4 26.66%, respectively. C6~C1Q 48.32%, C6~C1868.16% (including linear a-olefin 98.4%), C2〇~C285 ·1 8%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to give a white waxy polymer with a polymerization activity of 9.2X 1 〇 3 g. mollFeVh-1. The results of the analysis are shown in Table 2. Example 1 7 The main catalyst prepared in Example 1 was used, and triethylaluminum was used as a cocatalyst to carry out ethylene oligomerization. The oligomerization process was as in Example 15. The difference was: ‘When the reaction temperature was lowered to 5 °C, the reaction dad was charged with ethylene, and the ethylene pressure of IMPa was kept at the temperature. 〇, stir the reaction for 3 〇 min. After that, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% hydrochloric acid for GC analysis: the oligomerization activity was 7.92 χ1〇6 gm〇i-丨(Fe), hi, and the content of the polymer was C4 20.60%. , C6~C1() 48.4%, C6~C1875.03. /. (containing 98.3% of linear α-olefins), Cm~CM 4.37%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to give a white smected polymer 'polymerization activity <RTI ID=0.0>> The results of the analysis are shown in Table 2. 〇 31 201213363 Example 1 8 The main catalyst prepared in Example 1 was used, and triethylaluminum was used as a cocatalyst to carry out ethylene oligomerization. The oligomerization process is as in Example 15. The difference is: When the temperature of the reaction is lowered to 2 °C, the reaction dad is filled with ethylene, the ethylene pressure of IMPa is maintained, the temperature is maintained at 5t:, and the reaction is stirred for 3〇min. . Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was i〇.24xl〇6 gm〇ri(Fe).hi, and the oligomer content was C4 20.43%, respectively. C6~C1() 45.12%, C6~C18 69.81% (including linear α·olefin 98.1%), C20~C28 9.76%. The remaining reaction mixture was neutralized with a 5% aqueous solution of hydrochloric acid in ethanol to give a white crystalline polymer "polymerization activity QJxloig.mol^Fe).!!.1. The results of the analysis are shown in Table 2 ^ Example 1 9 The main catalyst prepared in Example 1 was used, and triethylaluminum was used as a cocatalyst to carry out ethylene oligomerization. The aggregation process is as in Example ,5, except that: When the reaction temperature is lowered to 5, the temperature is lowered. (:, the reactor was filled with ethylene, the ethylene pressure of IMPa was maintained, the temperature was maintained at 1 Torr, and the reaction was stirred for 3 Torr. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid to carry out GC. Analysis: The oligomerization activity was 9.35 χ 1〇6 g.mol'Feyh.i, the oligo content was C4 19.50%, C6~C1Q44.13%, C6~C18 69.52% (including linear α-smoke 98) 3%), c20 to C28 i0_98%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white waxy polymer 32 201213363. The polymerization activity was 6.8 χ1 〇 4 g. moil F ^. The results of the analysis are shown in Table 20. The main catalyst prepared in Example 1 was used, and triethylaluminum was used as a cocatalyst to carry out ethylene aggregating reaction. The oligomerization process was as in Example 15, except that: when the temperature of the reactor was lowered to 1, Ethylene was charged into the reaction vessel, the ethylene pressure of IMPA was maintained, the temperature was maintained at irc, and the reaction was stirred for 3 Torr. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis. The activity is 6.88χ 1〇6 g.mol'Fe).!!-1, the content of the polymer To C4 20.23% '() 49.23%, C6~C1872.75% (cx- which linear olefins containing 97.7%), Cu~GAM% C6~Cl. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to give a white waxy polymer, which had a polymerization activity of 2.1.times.sup.4g.moilF^.h-i. The results of the analysis are shown in Table 2. Example 21 Using the main catalyst prepared in Example 1, triethylaluminum as a cocatalyst was subjected to ethylene agglutination. The polymerization process was as in Example 15, except that the temperature of the reactor was lowered to 15 °C. (:, the reactor was filled with ethylene, the ethylene pressure of IMPa was maintained, the temperature was maintained at 19 ° C, and the reaction was stirred for 3 ° min. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid to carry out GC. Analysis: oligomeric activity was 5.53x1〇6 g.morkFe).!^1, the content of the polymer was C4 20.60%, C6~C1Q 48.49%, (:6~(:1872.21%(; which contains linear α- The olefin was 98.2%), C2〇~GW 19%. The remaining reaction mixture was neutralized with 5 〇/〇 hydrochloric acid acidified ethanol to give white waxy polymerization 33 201213363, polymerization activity 1·4χ104 g.mor'FeVh· 1. The analysis results are shown in Table 2. Example 22 The main catalyst prepared in Example 1 was used, and triethylaluminum was used as a cocatalyst to carry out ethylene oligomerization. The oligomerization process was as in Example 15, except that: The amount of benzene solution is 1.62ml (1.198 8mmol), Al/Fe = 3 99.6. When the temperature of the reactor is lowered to 〇 °C, the reactor is filled with ethylene, maintaining the ethylene pressure of IMPa, and the temperature is maintained at 5 °C, stir the reaction for 3 〇 min. After that, take a small amount of the reaction mixture with a syringe and use 5% of the diluted GC analysis after acid neutralization: oligomerization activity was 7.18x106 g.mol 'Fe).}!-1, oligomer content was C4 20.24%, C6~C1() 46.56%, C6~ C1871.52% (containing linear a-olefin 98. 1%), C2〇~c288.23〇/❶. The remaining reaction mixture was neutralized with a 5 % hydrochloric acid-acidified ethanol solution to obtain a white waxy polymer 'polymerization activity 2.7×10 4 g.mor'Fe).!!·1. The results of the analysis are shown in Table 2. Example 23 Using the main catalyst prepared in Example 1, triethylaluminum was used as a cocatalyst to carry out ethylene oligomerization. The oligomerization process was as in Example 15, except that the amount of the diethyl ether solution was 〇 81 πι to 0,5994 mmol) and Al/Fe = 199.8. When the temperature of the reactor was lowered, the reactor was charged with ethylene, and the ethylene pressure of 1 MPa was maintained, and the temperature was maintained at 5. 〇 ' Stir the reaction for 3 〇 min. After that, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: oligomerization activity was 8 96×1〇6 gm〇1-i(Fe).hi, oligomer 34 201213363 content was C4 20.02 %, C6~C1Q 45.88%, c6~C1870.09% (including linear cx-olefin 98.30/0), C2〇~C289 88%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white smected polymer 'polymerization activity S.SxlOAg.mor^PO.h·1. The results of the analysis are shown in Table 2. Example 24 Using the main catalyst prepared in Example 1, triethylaluminum was used as a cocatalyst to carry out ethylene copolymerization. The agglomeration process is as in Example 15, except that the amount of diethyl sulphonate solution is 0.40 ml (〇.296 mmol;), AJ/Fe = 98.7 ^ when the reaction temperature is 〇 ° C, the reaction The kettle was filled with ethylene, maintaining an ethylene pressure of 1 MPa, the temperature was maintained at 5 t, and the reaction was stirred for 3 Torr. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% hydrochloric acid for GC analysis. The agglomeration activity was 8.26 > 106, and the content of the polymer was C4 23.56%, C6 to C1Q 47.31%, C6~ CU 69.32% (which contains linear α-dilute hydrocarbon 98.5%), Cm~C287.1 2%. The remaining reaction mixture was neutralized with a 5 % hydrochloric acid-acidified ethanol solution to give a white-yellow polymer 'polymerization activity 7.8xl 〇4 g. mor^Fe)·]!-1. The results of the analysis are shown in Table 2. Example 25 Ethylene agglutination reaction was carried out using the main catalyst 'Triethylamine' prepared as a cocatalyst prepared in Example 1. The polymerization process is as in Example 15, except that the amount of triethylaluminum toluene solution is 〇.2〇ml (O.MSmmol), Al/Fe = 35 201213363 49.3 ° when the temperature of the reactor is lowered to 〇 < In the case of »c, ethylene was charged into the reaction vessel, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes. After that, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5 〇/〇 of dilute hydrochloric acid for GC analysis: the polymerization activity was 5 81×1 〇6 gm〇ri(Fe).hi, and the oligo content was C4 2 1.95%, respectively. , C6~C1q 43.78%, (:6~

Cl868.15〇/o (which contains linear α-olefin 98.8%), C20~C289.890/〇. The remaining reaction mixture was neutralized with a 5% aqueous solution of hydrochloric acid to give a white waxy polymer having a polymerization activity of 5 7 x 〇4 g.m〇ri(Fe).h.i. The results of the analysis are shown in Table 2. Example 26 Using the main catalyst prepared in Example 1, triethylaluminum was used as a cocatalyst to carry out ethylene aggregating reaction. The oligomerization process was as in Example 15, except that when the temperature of the reactor was lowered to 2t:, the reactor was charged with ethylene, and the ethylene pressure of 2 MPa was maintained at a temperature of 3 Torr. After that, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid, and then subjected to GC knife analysis. The oligomerization activity was 11 3 1 X1 〇6 gm〇i_i(Fe).hi, and the oligomer content was C4 2 1.53, respectively. °/. , C6~C1() 44.57%, C6~C18 69.26〇/〇 (which contains linear 0[_olefin 98 3〇/〇), (:2〇~〇;28921%. The remaining reaction mixture is 5% hydrochloric acid The acidified ethanol solution was neutralized to obtain a white waxy polymer having a polymerization activity of 9_8 x 104 g.mol-i(Fe).h-. The analysis results are shown in Table 2. Example 27 36 201213363 The main catalyst prepared in Example 1 was used. Triethylaluminum is used as a cocatalyst for ethylene oligomerization. The oligomerization process differs from Example I5' in that when the reactor temperature is 2 ° C, the reactor is filled with ethylene to maintain an ethylene pressure of 3 MPa. The temperature was kept at 5 ° C, and the reaction was stirred for 30 min. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid to carry out Gc analysis and aggregating activity of 13.54 x 106 g 'nior ^ Fe) '!! The oligo content is C4 22.120 / 〇 ' C6 ~ Ci 〇 44.43%, C6 ~ C18 69 12% (which contains linear α-olefin 98.2%), Cm ~ Cu 8.76%. The remaining anti-corrosive mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white bad aggregate having a polymerization activity of 1.0 OxlO5 g.mol'Fe). The results of the analysis are shown in Table 2. Comparative Example 5 The ethylene oligomerization method of Example 23 was repeated except that when the temperature of the reaction vessel reached 40 ° C, the reaction vessel was filled with ethylene, maintaining the ethylene pressure of ΐΜρ & and maintaining the temperature at 40 ° C. The reaction was stirred for 30 min. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid for GC analysis: the oligomerization activity was 2 12 χ 1 〇 6 ^, and the condensed polymer contained 1 C4 13.1%, C6 to C1 () 64, 0, respectively. %, C6~C18 82.8% (including linear α-lean smoke 98.2%) 'c2〇~C28 4 1 〇/〇. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution, and no polymer was obtained. The results of the analysis are shown in Table 2. Comparative Example 6 The ethylene oligomerization method of Example 15 was repeated except that the temperature of the father was 40 when the anti-37 201213363. (: When the reactor was filled with ethylene, the ethylene pressure of iMPa was maintained, the temperature was maintained at 4 (TC, stirring reaction for 30 min ^, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid for GC analysis. The oligomerization activity is ι·93><106 g.mol'Fe).!!·1, the content of the polymer is C4 20.61%, C6~C1() 55.17%, C6~C18 7 5.37% (wherein Containing linear 01_dilute hydrocarbon 97 〇〇/.), €20~(^28 4.02%. The remaining reaction mixture was neutralized with 5% hydrochloric acid acidified ethyl acetate solution, and no polymer was obtained. The analysis results are shown in Table 2. Comparative Example 7 The main catalyst prepared in Example 1 was subjected to the ethylene oligomerization reaction as described in Example 1. The difference was that the cocatalyst was methylaluminoxane, and the methyloxoxane solution was used in the amount of 〇54rnl. (concentration: 1.5 mol/l), let Al/Fe = 400. At 4 (TC, keep 1 MPa of ethylene pressure, stir the reaction for 30 min. Take a small amount of the reaction mixture with a syringe and neutralize with 5% diluted hydrochloric acid for GC. Analysis: The oligomeric activity was 1 08x 1 〇7 g'mol'FeVh-1 'oligomer content was c4 16.4%, C6~C10 45·20/〇 C6~C丨8 73 ·0% (containing linear α-olefin 95.0%) 'C20~Cm 1 0.6%. The remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white waxy polymer. The polymerization activity was as follows. The analysis results are shown in Table 2. Comparative Example 8 The main catalyst prepared in Example 1 was subjected to the ethylene oligomerization reaction as described in Example 1, and the difference was in the amount of ▼-base oxybenzene solution. 4l.36ml (= methyl pure burned 'toluene solution), so that A1/Fe=1000. Under the ar " ' K5mol / I ar C, keep the IMPa's ethylene house force 'mixing reaction 3 〇 min. Use injection to cry % Shantian, take a small amount of the reaction mixture from the main emitter and neutralize it with 5/〇 dilute hydrochloric acid for knife analysis. The oligomerization activity is i 4ΐχΐ〇7 gm〇r (Fehh·1, oligomer content

Knife Nai / Ma C4 35.〇%, C6~C 40,4%'<:6~(:18 64.7% (including the performance, ground, T containing green α_olefin 99.3. /.), C2 The remaining reaction mixture was neutralized with 5% hydrochloric acid in ethanol: liquid neutralized to give a white enamel polymer with a polymerization activity of 4'23xl05g_mol-1(Fe)·^. The analysis results are shown in Table 2. From Table 2 It can be seen that in the ethylene dimerization, a catalyst mixture of 2-iminoethyl uo- morphine iron (ruthenium) as a main catalyst and triethyl sulphate as a cocatalyst is used at a lower reaction temperature (,,) Under the catalysis, it has a high catalytic activity, and it has a high concentration of 0 Γ, 告7 λ7 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , It is more than ten times, even dozens of times. Even when ethylene oligomerization is carried out with methyl oxy-oxygen as a cocatalyst, the oligomerization activity is similar when the oligomerization activity is the highest/dose (40 C). It is confirmed that the method of this month's use of low-cost triethylaluminum has a higher catalytic activity at low temperatures, and has an unexpected effect. And at the reaction temperature _ι〇~19 In the range of C, as the temperature increases, the oligomerization activity first increases and then decreases, and the highest value appears at 5 ° C. 39 201213363 C2〇rC28 got—H 00 T"H CN cn oo 1 1 4.92 5.59 11.0 Ο C8~C2231.4% o 11.7 C^Ci8 Line Ha-Lin S (%) 98.0 97.5 98.0 98.3 92.9 89.9 92.5 91.5 Coffee 1 96.9 97.5 98.7 98.4 91.5 84.3 89.0 87.0 86.8 86.9 87.7 72.7 75.3 92.6 93.1 1 1 75.68 73.36 71.5 75.8 63.0 C6 29.3 55.5 74.1 C^Qo g 64.7 64.5 64.8 65.1 57.4 53.6 86.8 87.1 1 1 53.02 52.37 46.2 53.4 52.0 50.9 44.9 ag 12.0 12.1 11.6 10.5 24.7 21.6 inch OS Ο Ο 19.40 21.05 17.5 19.5 37.0 39.3 43.9 14.2 m± (10&amp ;gtn〇rV) 2.02 2.02 1.98 1.98 (N 1.01 0.12 0.08 1.40 3.21 3.83 6.40 5.21 0.88 0.271 0.18 2.50 Al/center 196 199.8 189 00 o <rH oo cn 196 196 〇\ 199.8 196 00 inch 1-4 500 500 1000 In ON 0 <υ (D 13⁄4 <υ lu. <u <υ <υ a> tin Ο U α><υ ρμ (U Hh <ΰ (U (U Ui <L> pU ( Η ε ooo 〇o O oo Ο Ο ο ο Ο ο Ο oo 〇CLh (MPa) CN <Ν CO cn Hybrid AlEt3 AlEt3 | AlEt3 j AlEt3 AlEt3 AlEt3 1 AlEt3 AlEt3 AlEt3 1 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 MAO ifyJ Odd Example 1 Example 2 | Example 3 j Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 1 Example 12 1 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 201213363 (N< Polymeric Eagle (l(fginolV) 1 1 1 0.92 Inch CN OS 00 CN Inch · Bu (Ν 00 ΓΛ OO Bu OO Os 10.0 0.68 0.57 1 1 1 III 1 1 1 6.21 46.5 42.3 C2CT-C28 (%) 0.99 j 5.18 4.37 "9:76 | 10.98 7.02 7.19 丨8.23 9.88 7.12 9.89 9.21 8.76 rH 4.02 ο C8 ~ C22 31.4% 〇 10.6 rn ο Ce^Cis 98.1 98.4 98.3 98.1 98.3 97.7 98.2 98.1 98.3 98.5 98.8 98.3 98.2 982 97.0 ON 84.3 89.0 95.0 99.3 74.09 68.16 75.03 69.81 69.52 72.75 72.21 1 71.52 70.09 69.32 68.15 69.26 69.12 00 7537 63.0 C6 29.3 55.5 74.1 73.0 64.7 C^Ci〇(%) 57.03^ \4S.32\ 48.40 | 45.12 I 44.13 49.23 48.49 1 46.56 45.88 47.31 43.78 44.57 44.43 64.0 55.17 52.0 50.9 44.9 45.2 40.4 a g | 24.92 | 26.66 20.60 20.43 19.50 20.23 20.60 1 20.24 ] "20.02 1 23.56 1 21.95 21.53 22.12 rn 20.61 37.0 39.3 43.9 1 14·2 1 "脳1 35.0 Oligomerization activity (106g.m〇rV) 5.35 7.74 7.92 10.24 9.35 6.88 5.53 7.18 8.96 8.26 5.81 11.31 13.54 2.12 0.88 0.271 0.18 2.50 10.8 inch · Al / central metal 298.5 298.5 298.5 298.5 298.5 298.5 | 298.5 399.6 1 199.8 98.7 49.3 I 298.5 298.5 199.8 298.5 Ο 500 1 1000 iT) OS t-H 400 1000 o 1 〇in 〇r~H Os ΙΟ »Τϊ oo o ooo Ο ο P (MPa) τ· i rH CN cn τ—Η化剂 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 AlEt3 I AlEt3 AlEt3 AlEt3 i AEt3 AIEt3 AlEt3 AlEt3 AlEt3 MAO MAO MAO jiyJ Example 15 tim 16 WH17 Example 18 i9 Example 20 SEQ ID NO: 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Comparative Example 5 Comparative Example 6 Comparative Example 1 Control Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 7 Comparative Example 8 One inch

Claims (1)

201213363 VII. Patent application scope: 1. A kind of ethylene oligomerization catalyst composition, which encapsulates 2-alienyl.uo-morphine iron (m( )) as chlorine J (ΤΤ^± Α& Triethylis-pro-catalyzed sword) catalyst, the central metal in the procatalyst in the promoter, and the molar ratio of the metal to the cerium and the metal is 30 to less than 2 (10): Each of the variables is defined as follows: ruthenium is a central metal selected from the group consisting of Fe2+, Co2+, and Nl2+; and R1 to R5 are each independently selected from the group consisting of argon, C丨~C6 alkyl, halogen, C丨~C6 alkoxy, and nitro. 2. The composition of claim 1, wherein the molar ratio of the metal aluminum in the promoter to the core metal in the procatalyst is from 50 to less than 200. 3. The composition of claim 1, wherein the molar ratio of the metal in the promoter to the central metal in the procatalyst is from 100 to 199.8. 4. The composition of claim 1, wherein the molar ratio of metal aluminum in the 201213363 agent to the central metal of the main catalyst t is 148 to 196. 5. The composition of claim i, wherein the molar ratio of metal aluminum in the promoter to the central metal in the procatalyst is 178 to 196. 6. The composition of claim 1, wherein R and R5 in the main catalyst are each independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, gas, chlorine, bromine, methoxy, Ethoxy and nitro groups. 7. The composition of claim i, wherein R, and Rs in the main catalyst are ethyl 'I~r4 are both hydrogen. 8. The ruthenium and RcRs in the composition of the scope of claim 2 have the following definitions: wherein the main catalyst 2 M = Fe 2+ . R, = Me M = Fe 2+ > R2 = Me M = Fe 2+ > R3 = Me M= Fe2+ » Rj = r2: M= Fe2+, R1== r3: M= Fe2+, R1== r4: M= Fe2+, R1== R5:; M= Fe2+ > R2= R3: > R2= R3 = R4= R$== H * Ri = R3= R4= R5= h * Ri=R2=R4=R5==h Me » R3 = r4 — __ H Me » R2 = R4 = r5 — H Me,R2 = R3 r5 = H Me, R2 = R3 = = H Me > R, = r4=R5==h 4 201213363 9 : M=Fe2+, R2=R4=Me, Ri=R_3=R5=H ; 10 · M= Fe2+ 5 Ri=R3=R5=Me >R2=R4:=H; 11 : M=Fe2+, RpEt, R2=R3=R4=R5=H; 12 : M two Fe2+, RfEt, R5=Me, R2= R3=R4=H; 13 · M=Fe2+, Ri=R5=Et5 R2=R3=R4=H; 14: M=Fe2+, RfiPr, R2=R3=R4=R5=H; 15: M=Fe2+, Ri =R5=iPr, R2=R3 — R4=H; 16: M=Co2+, Ri=Me, R2=R3=R4=R5=H; 17: M=Co2+, R2=Me» Ri = R3=R4=R5 =H; 18 : M = Co2+, R3 = Me ' Ri = R2 = R4 = R5 = H ; 1 9 " M — C o ^ , R i — R-2 ~ Mg ' R3 — Κ.4=Κ. 5=Η > 20: M=Co2+, Ri=R3=Me, R2=R4=R5=H; 2 1 . M = C〇2 * R1 = R4 = Mg 5 R.2 = R-3 = R5~H > 22 . M = C〇2 5 R. 1 = R5 = Mg 5 R.2~R-3=R4=:H > 23 · M — Co^ 5 R-2 = R3 ~ Me 5 R] — R4 = R5 = H > 2 4 . M = C〇2 * R2 = R-4 ~ Με 5 R.] = R.3 — R.5=H » 2 5 · M = C〇2 5 R]=R.3 — R.5== M 6' R-2=R4=H* 26 · M — Co^ ' Rj—Et? R .2=R3:=:R4~R5=H> 27 · M — Co^ ' Ri=Et' R_5 = Me ' R2=R3=R4=H 28 · M — Co^ * Rj — R.5=:Et , R2=R3==R4=H> 29 : M = C〇2 * Ri=iPr* R.2==R3~R4~R-5=H» 30: M=Co2+, R^Rs^iPr» R2 =R3 = R4=H·. 31 : M = Ni2+, R, = Me, R2 Two R3 = R4 = R5 = H ; 32 : Μ = Ni2 · R2 ~ Me ? Ri = R3 — R4 — R.5 — H > 3 201213363 M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, M = Ni2+, 33:34:35:36:37:38:39:40:41:42:43:44:45: R3=Me j Ri=R2=R4=R5 = H ; Ri=R2= Me » R3=R4=R5 = H ; Ri = R3=Me, R2=R4=R5 = H ; R] = R4=Me 5 R2=R3=R5=H Ri=R5=Me » R2=R3=R4=H ; R2=R3=Me » Ri=R4=R5=H ; R2=R4=Me } Ri=R3=R5=H ; Ri = R3 = R5 = Me , R2 = R4 = H ; Ri = Et, R2 = R3 = R4 = R5 = H ; Ri = Et, R5 = Me, R2 = R3 = R4 = H; R1 = R 5 = E t, R 2 = R 3 = R 4 = H, Ri = iPr 5 R2 = R3 = R4 = R5 = H ; Ri = R5 = iPr, R2 = R3 = R4 = Ho 9. A method of ethylene oligomerization, characterized in that the following formula (I a catalyst composition of 2-imino-1,10-phenanthroline iron (ruthenium), cobalt (ruthenium) or nickel (ruthenium) as a main catalyst and triethylaluminum as a cocatalyst, the cocatalyst The molar ratio of the metal aluminum to the central metal in the main catalyst is from 30 to less than 200: R4 4 (i) 201213363 wherein each variable is defined as follows: M is a central metal selected from the group consisting of Fe2+, Co2+, and Ni2+; R丨~R5 are each independently selected from the group consisting of hydrogen, C丨~C6 alkyl, halogen, C丨~C6 Alkoxy groups and exact groups. The method of claim 9, wherein the molar ratio of the metal aluminum in the promoter to the central metal in the main catalyst is from 50 to less than 200. 11. The method of claim 9, wherein the molar ratio of the metal aluminum in the cocatalyst to the central metal in the main catalyst is from 100 to 199.8. 12. The method of claim 9, wherein the molar ratio of the metal aluminum in the promoter to the central metal in the procatalyst is 148 to 196. 13. The method of claim 9, wherein the molar ratio of the metal aluminum in the promoter to the central metal in the procatalyst is 178 to 196. 14. The method of claim 9, wherein the RcRs in the procatalyst are each independently selected from the group consisting of hydrogen, decyl, ethyl, isopropyl, fluoro, ethane, bromo, decyloxy, ethoxy, and Nitro. The method of claim 9, wherein the Ri and the ethyl' to R4 in the main catalyst are all rats. [6] The method of claim 9, wherein the ruthenium and Ri~R5 in the main catalyst have the following definitions: 1 : Fe2+, Ri = Me, R2 = R3 = R4 = r5 = H; 2: M = Fe2+, R2 = Me, Ri = R3 = R4 = R5 = H ; 3 : M = Fe2+, R3 - Me, Ri = R2 = R4 = R5 = H ; 4 : M = Fe2+, Ri = R2 = Me, R3 = R4 = R5 = H ; 5 : M = Fe2+, Ri = R3 ~ Me, R2 = R4 = R5 = H ; 6 : M = Fe2+, Ri = R4 = Me, r2 = r3 = R5 = H ; 7 : M = Fe2+, Ri = R5 = Me, R-2 = R3 = R4 = H ; 8 : M = Fe2+, R2 = R3 = Me, Ri = r4 = R5 = H ; 9 : M = Fe2+, R-2 = R4 = Me, Ri = R3 = R5 = H ; 10 :M: =Fe2 + > Ri =R3 = R5 = Me , R2 = R4 = H ; 11 :M = τ-ί 2 + =Fe ,Ri =Et, R2 = :R3 = r4 = R5 = H ; 12 :M: =Fe2 + , R1 =Et, R5 = Me , R2 = R3 = R4 = H 13 :M: =Fe2 + ,Ri =R5 = Et, R2= r3 = R4 = H ; 14 :M: =Fe2 + ,Ri =iPr ,r2 =r3 =R4 = R5: =H ; 15 :M: =Fe2 + ,R! =R5 = iPr 5 R2 = R3 = R4 : = H ; 16 :M: =Co2 + ,Ri =Me 'R-2 =r3 =r4 =r5 =H ; 17 :M: = Co 2 + , R2 = Me 'Ri = r3 = r4 = r5 = H ; 18 : M = Co2 + , R3 = Me 5 Ri = R2 = r4 = R5 = H ; 201213363 19 : M = Co2+, Ri = R2 2 : M = Co2+, Rl ~ R3 = 21 : M = Co2+, Ri = R4 = 22 : M = Co2+, Ri = R5 = 23 : M = Co2+, R2 = R3 — 24 : M = Co2+, R2 = R4 = 25 : M 2 Co2+ - R, = R3 = 26 : M = Co2+, Ri = Et » 27 : M- Co2+, Ri = Et, 28 : M = Co2+, Ri = R5 — 29 : M = Co2+, R] = iPr , 30 : M di Co2+, Ri = R5 = 31 : M = Ni2+, R1 - Me » 32 : M = Ni2+, R2 = Me » 33 : M = Ni2+, R3 = Me, 34 M = Ni2+, Ri = R2 = 35 M = Ni2+, R1 ~ R-3 ~ 36 M = Ni2+, Ri = R4 = 37 M = Ni2+, Ri = R5 = 38 M = Ni2+, R2 = R3 = 39 M = Ni2+, R2 = R4 = 40 M = Ni2+, R1 = R3 ~ 41 M = Ni2+, Ri = Et, 42 M = Ni2+, Ri = Et j Me, R3 = R4 = R5 Η ; Me » R2 = R4 = R5 = H ; Me 5 R2 — R3 = R5 = H ; Me, R2 = R3 = R4 = H ; Me 5 Ri = R4 = R5 = H i Me, Ri = R3 = R5 = H; R_5 = Me, R_2 = R4 = H; R2 = R3 = R4 - R5 — H ; R5 = Me * R2 R3 — R4 — H Et 5 R2 = R3 = R4 = H ; R2 = R3 = R4 = R5 = Η l iPr» R2=R3=R4=H; R2 — R3 — R4 = R5 = H ; Ri = R3=R4 =R5=H i Rl=R2=R4=:R5=H ; Me 5 R3=R4=R5=:H i Me,R2 = R4 = R5 = H ; Me,R2=R3 二R5二H ; Me,R2 = R3 = R4 二H ; Me > Ri = R4=R5=H ; Me » Ri = R3=R5=H ; R_5=Me, R2=R4=H ; R2 — R3 — R4 = R5 = H ; R5 = Me, R2 = R3 = R4 = H 7 201213363 , R1 = R5 = Et, R2 = R3 = R4 = H ; * Ri = iPr» R, = R, = R, = H 43: M = Nj2 44 : M = Ni2 45 : M = Ni2 17. The method of claim 9, wherein the ethylene oligomerization reaction temperature is 20 to 80. 18. The method of claim 9, wherein the ethylene oligomerization reaction pressure is from 1 to 5 MPa. 19. A method for ethylene oligomerization, wherein a gasified 2-arylimin-1,10-morpholine iron (Π), cobalt (n) or nickel (n) of the following formula (1) is used as a main catalyst and triethyl A catalyst composition of aluminum as a cocatalyst, the ethylene oligomerization reaction temperature is -10 to 19 ° C: Wherein each variable is defined as follows: M is a central metal selected from the group consisting of Fe2+, c〇2 + and Ni2+; Ri~R5 are each independently selected from the group consisting of hydrogen, c丨~c6 alkyl, halogen, c-C6 alkoxy and nitro . The method of claim 19, wherein the oligomerization reaction temperature is -10 to 15 °C. 2 1. The method of claim 19, wherein the oligomerization temperature is from 0 to 15 °C. 22. The method of claim 19, wherein the oligomerization reaction temperature is 5 to 10 °C. 23. The method of claim 19, wherein the Ri-Rs in the procatalyst are each independently selected from the group consisting of argon, decyl, ethyl, isopropyl, fluoro, ethane, bromo, methoxy, Ethoxy and nitro groups. 24. The method of claim 19, wherein R1 and R5 in the primary catalyst are ethyl, and 〜2 to 4 are both wind i. 25. The method of claim 19, wherein the ruthenium and Ri-Rs in the procatalyst have the following definitions: 1 : M = Fe2 + , R ===Me ' R2 = R3 = R4 = R5 = H ; 2 : M = Fe2 + , R2 2 = Me ? Ri = R3 = R4 = R5 = H ; 3 : M = Fe2 + , R3 = =Me , R! 2 R2 = R4 = R5 = H ; 4 : Μ Two Fe2 + > Rj = R2 — :Me, R3 = R4 = R5 = H ; 5 : Μ = Fe2 + , Ri = R3 = :Me, R2 = R4 = R5 = H ; 201213363 6 : M = Fe2+, Ri = R4 = Me > r2 = R3 = R5 = H ; 7 : M = Fe2+, Ri = R5 = Me, R2 = R3 = R4 = H ; 8 : M = Fe2+, R2 = R3 = Me > Ri = R4 = R5 = H ; 9 : M = Fe2+, r2 = R4 = Me, Ri = R3 = R5 = H ; 10 : M ==Fe2 + , Ri = R3 = R5 = Me , R2 = R4: =H ; 11 : M = =Fe2 + , Ri =Et, R2 = R3 = r4 = R5 = H ; 12 :M = =Fe2 + ,Ri =Et R5 = Me R2 == R3 = R4 — H ; 13 :M = =Fe2 + , Ri = R5 : =Et 5 R2 = R3 = R4 = H ; 14 :M = =Fe2 + ,Ri =iPr , R2 = R3 = R4 = R5: =H ; 15 :M = =Fe2 + » Ri =R5 = =iPr , R2; =R3 = R4 : =H ; 16 • M — Co2 + » Ri = Me , R2 = r3 = r4 = R5 = H ; 17 : M = = Co2 + , R_2 = Me 5 Ri = R3 = r4 = r5 = H ; 18 : M = = Co2 + , R3 = Me , Ri = r2 = r4 = r5 = H ; 19 : M = Co2 + j Ri = R2 = Me , R3 = r4 = r5 = H ; 20 : M = = Co2 + , R! = R3 = Me 5 R-2 = r4 = r5 = H ; 21 : M = = C〇2 + > Ri = R4 — Me , r2 = r3 = r5 = H ; 22 : M = = Co2 + 5 Ri = r5 = Me J R2 =R3 =r4 =H ; 23 :M = =Co2 + 9 R-2 ~ R3 =Me > Ri =r4 =r5 =H ; 24 :M= Co2 + * R-2 =r4 =Me ,R! = R3 = r5 = H ; 25 : M: = Co2 + , R! = R3 = R5 = Me , R_2 = r4 = H ; 26 : M = = Co2 + , R, = Et 1 R2 = R3 = R4 = R5 — H ; 27 :M = =Co2 + > Ri =Et ,R5 = Me ,r2 =r3 =R4 = H 28 :M= Co2 + , =R5: =Et, R2 = R3 = R4 = H ; 29 :M = Co2 + , R, = iPr , R2 = R3 = r4 = r5 = H ; 10 201213363 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 M= C〇2+ , M = Ni2+ , M= Ni2+, M =- Ni2+ , M = Ni2+ , M = Ni2+ , M =: Ni2+ , M = Ni2+ , M= Ni2+ , M= Ni2+ , M = Ni2+ , M = Ni2+ , M = Ni2+ , M = Ki2+ , M = Ni2+ , M= Ni2+ , = iPr, R2 = R _3 = Κ·4 = H Ri = Me » R2 — R3 = R4 = R5 = H ^2= Μβ » Rj ^ r3 = R4 = R5 = H = Me » Ri r2 = R4 = R5 = HR,R, Ri R , R2 r3 r4 R, Me Me Me Me = Rt = Me R3 = R4 = R5 = H r2 = R4 = Rs = H r2 = R3 = Rs = H R2 = R3 = — H r. = R4 = R5 — H = R4 = Me > r, = R3 = R5 = H Ri = R3 = Rs = Me * R2 = R4 = H Ri = Et > R2 - R3 = R4 = R5 = H ; Ri = Et, R5 < Me, R2 = r3 = R4 Ri = R5 = Et, r = r3 = R4 = H ; H Ri = iPr » R2 = r3 = ^1 = R5 = iPr » r = r4 = R5 = H R3 = R4 = H 26. The method according to claim 19, wherein the metal aluminum ruthenium in the catalyst is 49 to 500 of the central metal in the main catalyst. 27. The method of claim 19, wherein the metal aluminum and the procatalyst are in the catalyst, wherein the assist is 100 to 400. The molar ratio of the central metal is 201213363. The method of claim i9, wherein the promoter has a molar ratio of 200 to 300 in the metal to the central metal in the main catalyst. ^ 29. The method according to claim 19, wherein the molar ratio of the metal in the cocatalyst to the central metal in the main catalyst is 300 ° 30. As disclosed in claims 19 to 29 The method according to any one of the preceding claims, wherein the ethylene oligomerization reaction pressure is from 1 to 5 MPa. The method according to any one of claims 19 to 29, wherein the organic solvent for ethylene oligomerization is selected from the group consisting of a smectin, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, The method of the present invention, wherein the organic solvent for ethylene oligomerization is a stupid. 12 201213363 IV. Designated representative map: (1) The representative representative figure of this case is: ( ). (2) A brief description of the symbol of the representative figure: [None] 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [None] 2