CN100355499C - Transition metal catalyst of polymerized ethene agent, prepartion method and application - Google Patents

Transition metal catalyst of polymerized ethene agent, prepartion method and application Download PDF

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CN100355499C
CN100355499C CNB2004100817112A CN200410081711A CN100355499C CN 100355499 C CN100355499 C CN 100355499C CN B2004100817112 A CNB2004100817112 A CN B2004100817112A CN 200410081711 A CN200410081711 A CN 200410081711A CN 100355499 C CN100355499 C CN 100355499C
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toluene
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栗同林
孙文华
唐秀波
介素云
张凌燕
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China Petroleum and Chemical Corp
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Sinopec Beijing Yanhua Petrochemical Co Ltd
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Abstract

The present invention discloses a 2-(2-(diphenyl phosphine) phenyl) oxazoline nickel halogenide series complex, which has the right structural formula, wherein R1 to R5 are respectively and independently selected from hydrogen, alkyl containing 1 to 6 carbon atoms, aryl, alkaryl, aralkyl and alkoxyl; X is halogen. The present invention also discloses a preparation method of the novel complex, which comprises the catalyst composition of the novel complex and an application thereof in ethene oligomerization. The complex of the present invention has the advantages of preparation starting from simple cheap raw materials, easy realization of all the steps, high yield, large space modified by ligand, medium to high ethylene oligomerization activity expressed by the corresponding catalyst composition, and main obtained oligomers of ethylene dimers and trimers.

Description

Ethylene oligomerization late transition metal catalyst, Preparation Method And The Use
Technical field:
The present invention relates to a kind of ethylene oligomerization late transition metal catalyst, in particular to a kind of novel N-P bidentate ligand nickel complex as catalyst agent, its preparation method.The invention still further relates to carbon monoxide-olefin polymeric that comprises this novel N-P bidentate ligand nickel complex as catalyst agent and the purposes that is used for the catalyzed ethylene oligomerisation thereof.
Background technology:
Ethylene oligomerization is the important means of industrial preparation linear alpha-alkene.Linear alpha-alkene can be used for preparing washing agent, plasticizer, fine chemicals and as the comonomer of LLDPE.Therefore, the production of linear alpha-alkene has become an individual branches in the petro chemical industry.In recent years, the research of late transition metal olefinic polymerization and catalyst for oligomerization has obtained developing rapidly (Angew.Chem.Int.Ed.1999,38,428～447; Chem.Rev.2000,100,1169～1203).In addition, the development of olefinic polymerization impels people that ethene and other olefin-copolymerization are obtained the polyolefine material of different structure, different performance, so presses for preparation C 4, C 6, C 8Oligomer Deng ethene.
Since the seventies, polymerization of transient metal complex homogeneous catalytic olefin and oligomerisation research are subject to people's attention, and people make great efforts to study raw catelyst and improve existing catalyst, improve the selectivity of activity of such catalysts and catalysate.In numerous metals that research is explored, research early, development soon, what relatively concentrate is nickel cation type catalyst system, as the United States Patent (USP) of reporting already: USP3,686,351 and USP3,676,523, the SHOP of shell (Shell) company (ShellHigher Olefin Process) technical process is based on these patented technologies.For this P-O bridging type ligand catalyst, its ethylene oligomerization catalysis activity is approximately 10 5Gram ethene/(mole Ni hour).Multiple patents such as O-O, P-N, P-P type and N-N type coordination Raney nickel had been developed afterwards again, wherein the nitrogen-atoms catalyst of doing the coordination tooth is subjected to people's extensive attention, as recent patent: Jpn.Kokai Tokkyo Koho JP 11060627, A2 (on March 2nd, 1999), Heisei; WO9923096A1 (on May 14th, 1999); WO9951550A1 (on October 14th, 1999).Yet; shortcomings such as the selectivity that most catalyst of having reported have oligomerization product is low, activity is low; and above-mentioned catalyst is subjected to the protection or the covering of foreign patent mostly; seriously limited China's ethylene oligomerization industrial expansion, it is extremely urgent to research and develop the ethylene oligomerisation catalyst with independent intellectual property right.The present invention developed a class preparation technology simple, have high selectivity, highly active ethylene oligomerisation catalyst, be expected to be applied in that ethylene oligomerization is industrial.
Summary of the invention:
The purpose of this invention is to provide a kind of novel ethylene oligomerization after-trasition metal coordination catalyst;
Another purpose of the present invention provides above-mentioned Preparation of catalysts method;
A further object of the present invention provides a kind of carbon monoxide-olefin polymeric that comprises above-mentioned catalyst as active component;
Also purpose of the present invention provides the application of above-mentioned carbon monoxide-olefin polymeric in ethylene oligomerization.
Ethylene oligomerization after-trasition metal coordination catalyst of the present invention is 2-(2-(diphenylphosphine) phenyl) the  azoles quinoline nickel halogenide series complex with following general structure:
Figure C20041008171100061
Wherein:
R 1-R 5Be selected from hydrogen independently of one another, contain alkyl, aryl, alkaryl, aralkyl or the alkoxyl of 1-6 carbon atom; Preferably be selected from hydrogen independently of one another, methyl, ethyl, propyl group, methoxyl group, ethyoxyl, propoxyl group or phenyl;
X is a halogen, preferred chlorine or bromine.
For the present invention, the serial complex of preferred 2-(2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide is the substituent R in the structural formula 1-R 5With X be complex 3a-3j and 4a-4j as described below:
3a：R 1＝R 2＝R 3＝R 4＝H，R 5＝CH 3，X＝Br； 4a：R 1＝R 2＝R 3＝R 4＝H，R 5＝CH 3，X＝Cl；
3b：R 1＝R 2＝R 3＝R 4＝H，R 4＝C 2H 5，X＝Br； 4b：R 1＝R 2＝R 3＝R 5＝H，R 4＝C 2H 5，X＝Cl；
3c：R 1＝R 2＝R 5＝H，R 3＝R 4＝CH 3，X＝Br； 4c：R 1＝R 2＝R 5＝H，R 3＝R 4＝CH 3，X＝Cl；
3d：R 1＝R 3＝R 4＝CH 3，R 2＝R 5＝H，X＝Br； 4d：R 1＝R 3＝R 4＝CH 3，R 2＝R 5＝H，X＝Cl；
3e：R 1＝R 5＝H，R 2＝OCH 3，R 3＝R 4＝CH 3，X＝Br；?4e：R 1＝R 5＝H，R 2＝OCH 3，R 3＝R 4＝CH 3，X＝Cl；
3f：R 1＝R 2＝R 3＝R 5＝H，R 4＝Ph，X＝Br； 4f：R 1＝R 2＝R 3＝R 5＝H，R 4＝Ph，X＝Cl；
3g：R 1＝R 2＝R 3＝R 5＝H，R 4＝CH(CH 3) 2，X＝Br； 4g：R 1＝R 2＝R 3＝R 5＝H，R 4＝CH(CH 3) 2，X＝Cl；
3h：R 1＝R 2＝R 3＝R 4＝H，R 5＝Ph，X＝Br； 4h：R 1＝R 2＝R 3＝R 4＝H，R 5＝Ph，X＝Cl；
3i：R 1＝R 2＝R 3＝H，R 4＝R 5＝CH 3，X＝Br； 4i：R 1＝R 2＝R 3＝H，R 4＝R 5＝CH 3，X＝Cl；
3j:R 1=R 2=R 3=R 4=R 5=H, X=Br; Or 4j:R 1=R 2=R 3=R 4=R 5=H, X=Cl.
The present invention also provides the preparation method of a kind of above-mentioned 2-(2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide series complex, and it comprises:
(1) the  isoxazoline compound of synthetic halogen replacement;
(2)  isoxazoline compound that replaces with the halogen that obtains in the step (1) and diphenylphosphine lithium or diphenylphosphine potassium react, and obtain phosphine- azoles quinoline part;
(3) can obtain the target complex with 2-methoxy ethyl ether nickel halogenide or the reaction of anhydrous nickel halogenide respectively with resulting phosphine in the step (2)- azoles quinoline part.
The reaction equation of 2-of the present invention (2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide series complex preparation can exemplarily clearly be represented with following reaction equation 1.
Reaction equation 1 complex 3a-j, the synthetic route of 4a-j a
Figure C20041008171100081
3a：?R 1＝R 2＝R 3＝R 4＝H，R 5＝CH 3，X＝Br； 4a：R 1＝R 2＝R 3＝R 4＝H，R 5＝CH 3，X＝Cl；
3b：?R 1＝R 2＝R 3＝R 5＝H，R 4＝C 2H 5，X＝Br； 4b：R 1＝R 2＝R 3＝R 5＝H，R 4＝C 2H 5，X＝Cl；
3c：?R 1＝R 2＝R 5＝H，R 3＝R 4＝CH 3，X＝Br； 4c：R 1＝R 2＝R 5＝H，R 3＝R 4＝CH 3，X＝Cl；
3d：?R 1＝R 3＝R 4＝CH 3，R 2＝R 5＝H，X＝Br； 4d：R 1＝R 3＝R 4＝CH 3，R 2＝R 5＝H，X＝Cl；
3e：?R 1＝R 5＝H，R 2＝OCH 3，R 3＝R 4＝CH 3，X＝Br； 4e：R 1＝R 5＝H，R 2＝OCH 3，R 3＝R 4＝CH 3，X＝Cl；
3f：?R 1＝R 2＝R 3＝R 5＝H，R 4＝Ph，X＝Br； 4f：R 1＝R 2＝R 3＝R 5＝H，R 4＝Ph，X＝Cl；
3g：?R 1＝R 2＝R 3＝R 5＝H，R 4＝CH(CH 3) 2，X＝Br； 4g：R 1＝R 2＝R 3＝R 5＝H，R 4＝CH(CH 3) 2，X＝Cl；
3h：?R 1＝R 2＝R 3＝R 4＝H，R 5＝Ph，X＝Br； 4h：R 1＝R 2＝R 3＝R 4＝H，R 5＝Ph，X＝Cl；
3i：?R 1＝R 2＝R 3＝H，R 4＝R 5＝CH 3，X＝Br； 4i：R 1＝R 2＝R 3＝H，R 4＝R 5＝CH 3，X＝Cl；
3j：?R 1＝R 2＝R 3＝R 4＝R 5＝H，X＝Br； 4j：R 1＝R 2＝R 3＝R 4＝R 5＝H，X＝Cl。
aNote: when part 2f synthesizes, X=F, M=K; Other part when synthetic, X=Br, M=Li.
Particularly, in the preparation method of 2-of the present invention (2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide series complex, the  isoxazoline compound that the halogen in the step (1) replaces is synthetic according to literature method well known in the art, and for example Tetrahedron 1996,52,7547-7583.Wherein when the chlorobenzoyl chloride of synthetic replacement, the benzoic proportioning of thionyl chloride and replacement can be 2-5, preferred 3; Reaction temperature can be 25-50 ℃, preferred 40 ℃.Reaction time was generally 24 hours.When containing N-(1-hydroxyl) benzamide of different substituents, the hydramine that contains different substituents can be 1.5-3 with the proportioning that contains the chlorobenzoyl chloride of different substituents synthetic, preferred 2; Generally select the solvent of carrene for use as reaction; Reaction at room temperature; Reaction time was generally 4 hours.When containing N-(1-chlorine) benzamide of different substituents, thionyl chloride is generally 3-5, preferred 4 with the proportioning that contains N-(1-hydroxyl) benzamide of different substituents synthetic; Generally select the solvent of toluene as reaction for use, reaction temperature is generally 80 ℃; Reaction time was generally 5 hours.At the  isoxazoline compound that synthetic halogen replaces, NaOH is generally 1.5 with the proportioning that contains N-(1-chlorine) benzamide of different substituents; The solvent of reaction is generally methyl alcohol; Reaction is carried out under the methanol eddy temperature usually.Reaction time was generally 5 hours.When the phenyl ring diverse location has methyl, ethyl, isopropyl, methoxyl group during substituting groups such as ethyoxyl, all is applicable to this course of reaction.Similarly, methyl is arranged on alcohol amine compound, ethyl also all is applicable to this course of reaction on the different substituting group such as isopropyl and phenyl.
In step (2), the proportioning of diphenylphosphine lithium or diphenylphosphine potassium and  isoxazoline compound is generally 1.2-2.0, and preferred 1.5; Reaction generally selects for use oxolane as solvent; Reaction is carried out under the reflux temperature of oxolane usually; The time of reaction was generally 7 hours.
In step (3), the proportioning of part and 2-methoxy ethyl ether nickelous bromide or anhydrous chlorides of rase nickel is generally 1.1-1.2, when using 2-methoxy ethyl ether nickelous bromide as reactant, generally uses carrene as solvent, at room temperature reacts 6 hours; When selecting anhydrous chlorides of rase nickel as reactant for use, generally with the solvent of ethanol as reaction, the time of reaction was generally 5 hours.
Be representative with preferred catalyst 3a-f below, introduce the Preparation of catalysts process in detail:
One, part is synthetic
The synthetic route of part is listed at reaction equation 1, and experiment divides following 5 steps to carry out:
Step 1: the chlorobenzoyl chloride that different substituents is arranged on the synthetic phenyl ring
Be starting material with o-fluorobenzoic acid, o-bromobenzoic acid, 4-methyl o-bromobenzoic acid, 5-methoxyl group o-bromobenzoic acid respectively, refluxed 5 hours at excessive thionyl chloride (mol ratio of substituted benzoic acid and thionyl chloride is about 1: 3), excessive thionyl chloride is removed in decompression down, then the substituted benzoyl chloride that obtains is distilled under high vacuum condition, obtain pure product.
Step 2: synthetic N-(1-hydroxyl) benzamide that contains different substituents
The hydramine that will contain different substituents places single neck bottle, add carrene and make its dissolving, be cooled to 0 ℃ then, to the dichloromethane solution of the substituted benzoyl chloride that in step 1, obtains that wherein dropwise adds 0.5 equivalent, after dripping, progressively rise to room temperature, there are a large amount of precipitations to occur in the whipping process, reaction was filtered after 2 hours under the room temperature, the benzamide that the white solid compound that obtains is replaced.
Step 3: synthetic N-(1-chlorine) benzamide that contains different substituents
The N-that contains different substituents (1-hydroxyl) benzamide that obtains in the step 2 is placed single neck bottle, adding toluene is partly dissolved it, be cooled to 0 ℃ then, to the toluene solution that wherein dropwise adds the excess chlorination sulfoxide, after dripping, progressively rise to room temperature to 80 ℃, solution progressively becomes clarification, under this temperature, continue reaction 5 hours, excess chlorination sulfoxide and toluene are removed in decompression, obtain lurid solid, thin-layer chromatographic analysis shows that the solid matter purity that obtains is better, directly carries out next step reaction without separating.
Step 4: the  isoxazoline compound that synthetic halogen replaces
The N-that contains different substituents (1-chlorine) benzamide that obtains in the step 3 is placed single neck bottle, add the NaOH and the 30ml methyl alcohol of 1.5 times of equivalents successively, counterflow condition reacted down after 5 hours, solvent is distilled under reduced pressure remove.Add the 50ml ether with dissolving organic matter wherein, give a baby a bath on the third day after its birth inferior (3 * 15ml) with saturated aqueous common salt then.Separatory is collected organic facies later on and is used anhydrous sodium sulfate drying, except that after desolvating, with benzinum and ethyl acetate is leacheate, carrying out column chromatography with silicagel column separates, the different  isoxazoline compounds that replace carry out post when separating selected polarity slightly different, it is comparatively suitable that the  isoxazoline compound of brominated replacement is with the ratio of benzinum and ethyl acetate that 4: 1 leacheate separates, and that the  isoxazoline compound of fluorine-containing replacement is with the ratio of benzinum and ethyl acetate that 8: 1 leacheate separates is comparatively suitable.The productive rate that compound 1a-f begins from the benzoic acid that replaces and the data of sign are as follows: 1a is a colourless oil liquid, productive rate: 67.2%. 1H NMR (300MHz, CDCl 3): δ 7.62-7.70 (m, 2H, Ar-H); 7.24-7.37 (m, 2H, Ar-H); 4.82-4.92 (m, 1H ,-CH); 4.19 (q ,-CH 2In 1H, J=5.9Hz); 3.67 (q ,-CH 2In 1H, J=5.4Hz); 1.45 (d, 3H ,-CH 3, J=6.3Hz).Elementary analysis: C 10H 10BrNO: calculated value: C, 50.02; H, 4.20; N, 5.83.Test value: C, 49.89; H, 4.11; N, 5.65.1b is a colourless oil liquid, productive rate: 59.6%. 1H NMR (300MHz, CDCl 3); δ 7.62-7.69 (m, 2H, Ar-H); 7.27-7.32 (m, 2H, Ar-H); 4.50 (q ,-CH 2In 1H, J=7.8Hz); 4.27-4.33 (m, 1H ,-CH); 4.10 (t ,-CH 2In 1H, J=7.8Hz); 1.6-1.8 (m, 2H, in the ethyl-CH 2); 1.03 (t, 3H ,-CH 3, J=3.8Hz).Elementary analysis: C 11H 12BrNO: calculated value: C, 51.99; H, 4.76; N, 5.51.Test value: C, 52.09; H, 4.78; N, 5.24.1c is a white solid, fusing point: 37-39 ℃. 1H?NMR(300MHz，CDCl 3)：δ7.60-7.65(m，2H，Ar-H)；7.27-7.33(m，2H，Ar-H)；4.14(s，2H，-CH 2)；1.42(s，6H，-CH 3)。Elementary analysis: C 10H 10BrNO: calculated value: C, 51.99; H, 4.76; N, 5.51; Test value: C, 51.61; H, 4.83; N, 5.39.1d is a colourless oil liquid, productive rate: 52.7%. 1H?NMR(300MHz，CDCl 3)：δ?7.53(d，1H，Ar-H，J＝7.8Hz)；7.44(s，1H，Ar-H)；7.12(d，1H，Ar-H，J＝7.9Hz)；4.11(s，2H，-CH 2)；2.34(s，3H，-CH 3)；1.40(s，6H，-CH 3)。Elementary analysis: C 11H 14BrNO: calculated value: C, 53.75; H, 5.26; N, 5.22.Test value: C, 53.72; H, 5.43; N, 5.05.1e is a white solid, productive rate: 68.4%.Fusing point: 43-45 ℃. 1H?NMR(300MHz，CDCl 3)：δ7.48(d，1H，Ar-H，J＝8.9Hz)；7.17(d，1H，Ar-H，J＝3.9Hz)；6.84(dd，1H，Ar-H，J 1＝3.1Hz，J 2＝8.9Hz)；4.13(s，2H，-CH 2)；3.81(s，3H，-OCH 3)；1.41(s，6H，-CH 3)。Elementary analysis: C 11H 14BrNO 2: calculated value: C, 50.72; H, 4.97; N, 4.93.Test value: C, 51.13; H, 5.14; N, 4.78.1f is colourless thickness oily liquids, productive rate: 76.4%. 1H NMR (400MHz, CDCl 3): δ 7.15-7.98 (m, 9H, Ar-H); (5.43 dd, 1H ,-CH, J=9.0,9.0); 4.80 (t ,-CH 2In 1H, J=9.0); 4.28 (t ,-CH 2In 1H, J=9.0).Elementary analysis: C 15H 12FNO: calculated value: C, 74.67; H, 5.01; N, 5.81.Test value: C, 74.50; H, 5.02; N, 5.76.
Step 5: the synthetic different phosphine- azoles quinoline part 2a-f that replace
The tetrahydrofuran solution that has at first prepared the diphenylphosphine lithium according to the method for document.Concrete implementation method is as follows: for synthetic ligands 2a-e: the lithium metal with triphenylphosphine and 2 times of equivalents joins in the Schlenk bottle under nitrogen atmosphere earlier, vacuumize and with after the nitrogen replacement three times, add the oxolane that 10ml crosses through new processing purifying, at room temperature be stirred to the lithium metal complete reaction, obtain wine-colored solution.After resulting solution is cooled to room temperature, dropwise add the tertiary butyl chloride of 1 times of equivalent.After adding, rise to room temperature and continue reaction 2 hours, obtain cherry solution for standby.The  isoxazoline compound of the brominated replacement of 0.7 times of equivalent is joined in the three-neck flask, vacuumize and with after the nitrogen replacement three times, the tetrahydrofuran solution of the diphenylphosphine lithium that obtains above under nitrogen atmosphere, dropwise adding under the room temperature, after adding, progressively be warming up to about 50 ℃, react after 7 hours, after solvents tetrahydrofurane under reduced pressure removed, add treated absolute ether dissolving organic matter wherein, add distilled water then and make excessive diphenylphosphine lithium hydrolysis, and the inorganic matter that is produced after the dissolving hydrolysis.Collect organic facies behind the separatory and use anhydrous sodium sulfate drying, except that after desolvating, separate with silicagel column, it is comparatively suitable to be with the ratio of benzinum and ethyl acetate that 6: 1 leacheate separates.For synthetic synthetic of part 2f: the tetrahydrofuran solution that at first synthesizes diphenylphosphine potassium with similar method.The tetrahydrofuran solution of the  isoxazoline compound that fluorine is replaced is heated to backflow then, to the tetrahydrofuran solution that wherein drips diphenylphosphine potassium, continues reaction 7 hours after adding under reflux state, carries out post processing according to the method for synthetic 2a-e then.When carrying out the column chromatography separation, the ratio of selecting benzinum and ethyl acetate for use is that 10: 1 leacheate is comparatively suitable.The sign situation of productive rate and compound: 2a is a white solid, productive rate: 52.0%.Fusing point: 92-94 ℃. 1H NMR (300MHz, CDCl 3): δ 7.84 (dd, 1H, Ar-H, J 1=3.0Hz, J 2=6.0Hz); 7.31-7.33 (m, 12H, Ar-H); 6.87 (t, 1H, Ar-H, J=5.7); 4.52-4.55 (m, 1H ,-CH); 3.87 (q ,-CH 2In 1H, J=7.9); 3.34 (q ,-CH 2In 1H, J=7.2); 1.12 (d, 3H ,-CH 3, J=6.0).Elementary analysis: C 22H 20NOP: calculated value: C, 76.51; H, 6.07; N, 4.01.Test value: C, 76.51; H, 6.07; N, 4.06. 31P?NMR(CDCl 3)：δ-4.58(s)。IR(KBr)：2969；1661(v C＝N)；1472；1433；1366；1329cm -1。2b is a white powder, productive rate: 41.0%.Fusing point: 68-70 ℃. 1H NMR (300MHz, CDCl 3): δ 7.88 (dd, 1H, Ar-H, J 1=3.4Hz, J 1=5.8Hz); 7.30-7.3 (m, 12H, Ar-H); 6.86 (t, 1H, AR-H, J=3.8); 4.18 (q ,-CH 2In 1H); 3.99 (m, 1H ,-CH); 3.70 (t ,-CH 2In 1H, J=7.9); 1.23-1.38 (m, 2H, in the ethyl-CH 2); 0.79 (t, 3H ,-CH 3, J=7.6Hz).Elementary analysis: C 23H 22NOP: calculated value: C, 76.86; H, 6.17; N, 3.90.Test value: C, 76.66; H, 6.48; N, 4.51. 31P?NMR(CDCl 3)：δ-4.93(s)。IR(KBr)：2960；1645(v C＝N)；1584；1476；1433；1360；1327cm -1。2c is a white solid, productive rate: 52.1%.Fusing point: 78-80 ℃. 1H?NMR(300MHz，CDCl 3)：δ7.85(dd，1H，Ar-H，J 1＝4.2Hz，J 2＝8.9Hz)；7.37-7.42(m，1H，Ar-H)；7.33(s，11H，-Ar-H)；6.79(t，1H，Ar-H，J＝6.0)；3.73(s，2H，-CH 2)；1.05(s，6H，-CH 3)。Elementary analysis: C 22H 22NOP: calculated value: C, 76.86; H, 6.17; N, 3.90.Test value: C, 77.27; H, 6.14; N, 3.87. 31P?NMR(CDCl 3)：δ-3.92(s)。IR(KBr)：2968；1646(v C＝N)；1585；1460；1438；1351；1311cm -1。2d is a white solid, productive rate: 43.8%.Fusing point: 76-78 ℃. 1H?NMR(300MHz，CDCl 3)：δ7.75(dd，1H，Ar-H，J 1＝4.1Hz，J 2＝3.8Hz，)；7.32-7.34(m，10H，Ar-H)；7.13(d，1H，-Ar-H，J＝7.5Hz)；6.59(d，1H，Ar-H，J＝4.8)；3.70(s，2H，-CH 2)；2.18(s，3H，-CH 3)；1.04(s，6H，-CH 3)。Elementary analysis: C 24H 24NOP: calculated value: C, 76.86; H, 6.17; N, 3.90.Test value: C, 77.27; H, 6.14; N, 3.87. 31P?NMR(CDCl 3)：δ-3.59(s)。IR(KBr)：2967；1649(v C＝N)；1574；1461；1435；1351；1316cm -1。2e is the liquid of light yellow thickness, productive rate: 58.8%. 1H?NMR(300MHz，CDCl 3)：δ7.53(d，1H，Ar-H，J＝6.0Hz)；7.49(s，1H，Ar-H)；7.28-7.32(m，9H，-Ar-H)；7.01(dd，1H，Ar-H，J 1＝3.0，J 2＝3.0)；6.79(dd，1H，Ar-H，J 1＝3.0，J 2＝6.0)；4.10(s，2H，-CH 2)；1.39(s，6H，-CH 3)；1.09(s，3H，-CH 3)。 31P?NMR(CDCl 3)：δ-5.92(s)。IR(KBr)：2967；1649(v C＝N)；1590；1464；1433；1352；1310cm -1。Elementary analysis: C 24H 24NO 2P: calculated value: C, 74.02; H, 6.21; N, 3.60; Test value: C, 73.96; H, 6.05; N, 3.76.2f is a white solid, productive rate: 44.5%.Fusing point: 55-57 ℃. 1H NMR (400MHz, CDCl 3): δ .6.77-7.96 (m, 19H, Ar-H); 5.70 (t, 1H ,-CH, J=9.4); 4.98 (dd ,-CH 2In 1H, J=8.3,8.3); 4.44 (t ,-CH 2In 1H, J=8.5).Elementary analysis: C 27H 22NOP: calculated value: C, 79.59; H, 5.44; N, 3.44.Test value: C, 79.83; H, 5.39; N, 3.46.IR(KBr)：3054；1650(v C＝N)；1581；1466；1430；1351；1307cm -1。
Two, complex is synthetic
Complex 3a-j, the synthetic method of 4a-j is similar, therefore only states general synthetic method.Under nitrogen atmosphere, join the respective ligand of 2-methoxy ethyl ether nickelous bromide or nickel chloride and 1.1 times of equivalents in the Schlenk bottle, add solvent (can be carrene or ethanol) then, after at room temperature stirring 6 hours, volume is concentrated into 1/2nd, add treated n-hexane then, have a large amount of precipitations to separate out, after the filtration back is washed for several times with n-hexane, dry in a vacuum, obtain bolarious pressed powder.The productive rate of complex is between 67%-90%.All by the sign of elementary analysis and infrared spectrum, the result of sign provides in respective embodiments complex 3a-f.In addition, tested complex 3c with the method for X-ray diffraction, the crystal structure of 3d and 3e, crystal structure figure provide among Fig. 2 and Fig. 3 at Fig. 1.
In another aspect of this invention, also provide a kind of carbon monoxide-olefin polymeric that comprises described 2-(2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide series complex, it comprises major catalyst and is used for the co-catalyst (being activator) of major catalyst activation.Described major catalyst is aforesaid 2-of the present invention (2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide series complex.
Can use aikyiaiurnirsoxan beta as activator, the example of aikyiaiurnirsoxan beta comprises MAO (MAO), modified methylaluminoxane (MMAO), ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.Aikyiaiurnirsoxan beta can produce by the hydrolysis of various trialkyl aluminium compounds.MMAO can produce by the hydrolysis of trimethyl aluminium and more senior trialkylaluminium such as triisobutyl aluminium.
Other activator that is suitable as in the carbon monoxide-olefin polymeric of the present invention is an alkyl aluminum compound, as trialkylaluminium and chlorination alkyl aluminum.The example of these activators comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride etc.
The preferred aikyiaiurnirsoxan beta of using, as MAO as activator.
In carbon monoxide-olefin polymeric of the present invention, aluminium nickel mol ratio can change in 200 to 2000 scope.Than less than 200, active very low situation can appear as aluminium nickel; When aluminium nickel compares greater than 2000, the reduction of catalytic activity also can appear.Evidence, preferred aluminium nickel is 800-1500 than scope, according to different nickel complexes and different.
Optionally, carbon monoxide-olefin polymeric of the present invention can further comprise other assistant ligand, for example triphenylphosphine.The adding of this class assistant ligand of evidence can make the active obviously raising of ethylene oligomerization, and catalyst life prolongs.
Can use any carrying method known in the art, activator and/or polymerization catalyzed immunomodulator compounds are combined with one or more carrier materials.In one embodiment, this activator is to exist with its load form, for example is deposited on the carrier, contacts with carrier, vaporizes with carrier, is incorporated into carrier, is incorporated in the carrier absorption or absorption in carrier or on carrier.In another embodiment, this activator and catalyst compounds can be deposited on the carrier, contact with carrier, vaporize with carrier, are incorporated into carrier, are incorporated in the carrier absorption or absorption in carrier or on carrier.
Employed carrier material can be any of usual carrier materials.Preferably, carrier material is a porous carrier materials, for example inorganic oxide and butter.More preferably, this carrier material is an inorganic oxide, comprises those 2,3,4,5,13 or 14 family metal oxides, and instantiation is the silica supports and the spherical magnesium chloride of pyrolysismethod preparation.Other useful carrier comprises magnesia, titanium dioxide, zirconia, montmorillonite, phyllosilicate, zeolite, talcum and clay etc.
In one embodiment of the invention, provide the method for producing the supported ethylene oligomerisation catalyst system.In the method, with catalyst compounds slurrying in liquid, thereby form catalyst solution or emulsion.This catalyst compounds solution and activator solution are mixed together, heat and join in the porous carrier of heating, maybe the porous carrier with heating joins in this solution.The content of the middle al and ni of supported catalyst is analyzed with emission of ions spectrum-mass spectrometry method.
No matter whether load, and carbon monoxide-olefin polymeric of the present invention is suitable for any prepolymerization and/or the polymerization under the temperature and pressure of wide region.Polymerization comprises solution, slurries, gas phase and high pressure method or their combination.Especially preferred is the solution polymerization process that is used for the carbon monoxide-olefin polymeric of not load, and is used for the slurry polymerization method of the carbon monoxide-olefin polymeric of load.
When homogeneous solution polymerization, generally select for use non-polar solvens such as toluene, n-hexane or normal heptane as the polymerization solvent.Because the dissolubility of major catalyst reduces, can cause active decline when using n-hexane or normal heptane as solvent, therefore preferred toluene is as solvent.The temperature of polymerisation can change in 0-40 ℃ of scope, can cause active decline under the higher temperature.Reaction time was generally 30-90 minute, and wherein activity of such catalysts can descend after 60 minutes.
When heterogeneous slurry polymerization, the experimental condition that is adopted and the condition of polymerisation in solution are similar.Aggregation test can carry out under different ethylene pressures, and the ethylene pressure that is adopted is generally the 10-50 atmospheric pressure, preferred 20 atmospheric pressure.
The invention has the advantages that: catalyst synthetic, each step from simple, cheap raw material all be easy to realize and also productive rate higher, the modifiable space of part is bigger.Can study of the influence of different part environment easily to catalytic activity.
Brief Description Of Drawings
Fig. 1 is the crystal structure of complex 3c;
Fig. 2 is the crystal structure of complex 3d;
Fig. 3 is the molecular structure of complex 3e.
Embodiment
With reference to the following embodiment that provides just to explanation, further details of the present invention and advantage will become clearer.Need to prove that these embodiment are used to limit protection scope of the present invention, protection scope of the present invention is as the criterion with appending claims.
Embodiment 1
1. the preparation of catalyst 3a: (0.123g, 0.35mmol) (0.129g 0.338mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2a with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.118g, 3a: productive rate: 67.3%.IR(KBr)：2979；1627(v C＝N)；1480；1435，1377，1345cm -1。Elementary analysis: C 22H 20Br 2NNiOP: calculated value: C, 46.86; H, 3.58; N, 2.48.Test value: C, 47.10; H, 3.70; N, 2.46.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3a (2.8mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 2.29 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 89.6%; C 6: 10.4%; C 4The content of 1-butylene is in the component: 11.0%.
Embodiment 2
1. the preparation of catalyst 3a is with embodiment 1.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3a (2.8mg, 5 μ mol) and triphenylphosphine (2.6mg, 10 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes A l/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 5.27 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 88.90%; C 6: 10.79%; C 〉=8: 0.3%.C 4The content of 1-butylene is in the component: 6.2%.
Embodiment 3
1. the preparation of catalyst 3a is with embodiment 1.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3a (11mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 5.74 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 78.90%; C 6: 7.84%; C 〉=8: 13.26%.There is not polymer to generate.
Embodiment 4
1. the preparation of catalyst 3b: (0.123g, 0.35mmol) (0.129g 0.338mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2b with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.164g, 3b: productive rate: 84.2%.IR(KBr)：2966；1613(v C＝N)；1565；1479；1436，1376，1338cm -1。Elementary analysis: C 23H 22Br 2NiOP: calculated value: C, 47.80; H, 3.84; N, 2.42.Test value: C, 47.46; H, 4.40; N, 2.56.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3b (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 7.10 * 10 4G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 99.38%; C 6: 0.62%.C 4The content of 1-butylene is in the component: 52.6%.
Embodiment 5
1. the preparation of catalyst 3b is with embodiment 4.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3b (2.9mg, 5 μ mol) and triphenylphosphine (2.6mg, 10 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 2.71 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 91.00%; C 6: 5.91%; C 〉=8: 3.09%.C 4The content of 1-butylene is in the component: 12.1%.
Embodiment 6
1. the preparation of catalyst 3b is with embodiment 4.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3b (12mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 5.42 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 45.47%; C 6: 7.24%; C 〉=8: 47.29%.There is not polymer to generate.
Embodiment 7
1. the preparation of catalyst 3c: (0.130g, 0.36mmol) (0.116g 0.32mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2c with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.136g, 3c: productive rate: 72.5%.IR(KBr)：2966；1617(v C＝N)；1565；1480；1435，1368，1319cm -1。Elementary analysis: C 23H 22Br 2NNiOPCH 2Cl 2: calculated value: C, 43.69; H, 3.65; N, 2.11.Test value: C, 42.89; H, 3.29; N, 2.03.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.78 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.50%; C 6: 11.59%; C 〉=8: 2.91%.C 4The content of 1-butylene is in the component: 33.1%.
Embodiment 8
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol) and triphenylphosphine (2.6mg, 10 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 2.62 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 78.70%; C 6: 20.05%; C 〉=8: 1.25%.C 4The content of 1-butylene is in the component: 4.7%.
Embodiment 9
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (28.3ml) with syringe, (1.54mol/L 1.7ml) makes Al/Ni=500, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.46 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 88.93%; C 6: 6.62%; C 〉=8: 4.45%.C 4The content of 1-butylene is in the component: 22.7%.
Embodiment 10
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (25.0ml) with syringe, (1.54mol/L 5.0ml) makes Al/Ni=1500, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.10 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 95.45%; C 6: 4.55%.C 4The content of 1-butylene is in the component: 22.9%.
Embodiment 11
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 0 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: .1.08 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 98.20%; C 6: 1.80%.C 4The content of 1-butylene is in the component: 32.2%.
Embodiment 12
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 40 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 5.40 * 10 4G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 98.48%; C 6: 1.52%.C 4The content of 1-butylene is in the component: 52.2%.
Embodiment 13
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 60 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 9.80 * 10 4(oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 91.77%; C 6: 4.79%; C 〉=8: 3.42%.C 4The content of 1-butylene is in the component: 23.6%.
Embodiment 14
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 90 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 6.00 * 10 4G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 81.88%; C 6: 15.70%; C 〉=8: 2.49%.C 4The content of 1-butylene is in the component: 15.8%.
Embodiment 15
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (0.66mol/L 1.8ml) makes Al/Ni=250, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of triethyl aluminum again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.21 * 10 5(oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 96.83%; C 6: 3.17%.C 4The content of 1-butylene is in the component: 73.5%.
Embodiment 16
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3c (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.92mol/L 0.13ml) makes Al/Ni=50, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of diethylaluminum chloride again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 6.66 * 10 5(oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 74.21%; C 6: 26.60%.C 4The content of 1-butylene is in the component: 8.5%.
Embodiment 17
1. the preparation of catalyst 3c is with embodiment 7.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3c (12mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 6.27 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 79.06%; C 6: 7.63%; C 〉=8: 13.31%.
Embodiment 18
1. the preparation of catalyst 3d: (0.121g, 0.34mmol) (0.140g 0.37mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2d with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.154g, 3d: productive rate: 76.5%.IR(KBr)：2967；1613(v C＝N)；1556；1485；1459，1370，1322cm -1。Elementary analysis: C 24H 24Br 2NNiOP: calculated value: C, 48.70; H, 4.09; N, 2.37; Test value: C, 48.22; H, 4.10; N, 2.31.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3d (3.0mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.73 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 75.72%; C 6: 21.94%; C 〉=8: 2.34%.C 4The content of 1-butylene is in the component: 19.5%.
Embodiment 19
1. the preparation of catalyst 3d is with embodiment 18.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Under nitrogen atmosphere, add catalyst 3d (3.0mg, 5 μ mol) and triphenylphosphine (2.6mg, 10 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.62 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 91.13%; C 6: 7.30%; C 〉=8: 1.57%.C 4The content of 1-butylene is in the component: 7.9%.
Embodiment 20
1. the preparation of catalyst 3d is with embodiment 18.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3d (12mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.18 * 10 6G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.34%; C 6: 9.31%; C 〉=8: 5.35%.No polymer generates.
Embodiment 21
1. the preparation of catalyst 3e: (0.107g, 0.30mmol) (0.128g 0.33mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2e with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.127g, 3e: productive rate: 69.4%.IR(KBr)：2972；1624(v C＝N)；1588；1490；1438，1368，1328cm -1。Elementary analysis: C 24H 24Br 2NNiO 2PCH 2Cl 2: calculated value: C, 43.34; H, 3.78; N, 2.02.Test value: C, 43.54; H, 3.82; N, 2.31.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3e (3.0mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.95 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 84.13%; C 6: 14.79%; C 〉=8: 1.09%.C 4The content of 1-butylene is in the component: 25.4%.
Embodiment 22
1. the preparation of catalyst 3e is with embodiment 21.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Under nitrogen atmosphere, add catalyst 3e (3.0mg, 5 μ mol) and triphenylphosphine (2.6mg, 10 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.40 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 77.12%; C 6: 21.36%; C 〉=8: 1.52%.C 4The content of 1-butylene is in the component: 6.3%.
Embodiment 23
1. the preparation of catalyst 3e is with embodiment 21.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3e (12mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 7.37 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 82.07%; C 6: 6.63%; C 〉=8: 11.30%.No polymer generates.
Embodiment 24
1. the preparation of catalyst 3f: (0.125g, 0.35mmol) (0.157g 0.38mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2f with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.198g, 3f: productive rate: 90.5%.IR(KBr)：3055；1621(v C＝N)；1532；1435；1391，1269，1120cm -1。Elementary analysis: C 27H 22Br 2NNiOPCH 2Cl 2: calculated value: C, 47.31; H, 3.40; N, 1.97.Test value: C, 47.09; H, 3.22; N, 2.09.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3f (3.1mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.34 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 82.04%; C 6: 14.47%; C 〉=8: 3.13%.C 4The content of 1-butylene is in the component: 21.3%.
Embodiment 25
1. the preparation of catalyst 3f is with embodiment 24.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Under nitrogen atmosphere, add catalyst 3f (3.1mg, 5 μ mol) and triphenylphosphine (2.6mg, 10 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.12 * 10 6G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 79.32%; C 6: 19.01%; C 〉=8: 1.67%.C 4The content of 1-butylene is in the component: 8.3%.
Embodiment 26
1. the preparation of catalyst 3f is with embodiment 24.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3f (13mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 7.99 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 90.21%; C 6: 4.36%; C 〉=8: 5.43%.No polymer generates.
Embodiment 27
1. the preparation of catalyst 3g: (0.125g, 0.35mmol) (0.142g 0.38mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2g with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.194g, 3g: productive rate: 88.6%.Elementary analysis: C 24H 24Br 2NNiOP: calculated value: C, 48.70; H, 4.09; N, 2.37.Test value: C, 49.10; H, 3.89; N, 2.24.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3g (3.0mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.04 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 80.04%; C 6: 16.47%; C 〉=8: 3.13%.C 4The content of 1-butylene is in the component: 32.3%.
Embodiment 28
1. the preparation of catalyst 3g is with embodiment 27.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3g (13mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 6.52 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 93.21%; C 6: 3.36%; C 〉=8: 3.43%.No polymer generates.
Embodiment 29
1. the preparation of catalyst 3h: (0.132g, 0.37mmol) (0.158g 0.39mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2h with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.207g, 3h: productive rate: 89.6%.Elementary analysis: C 27H 22Br 2NNiOP: calculated value: C, 51.81; H, 3.84; N, 2.24.Test value: C, 51.72; H, 3.89; N, 2.36.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3h (3.1mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.04%; C 6: 11.47%; C 〉=8: 3.13%.C 4The content of 1-butylene is in the component: 30.3%.
Embodiment 30
1. the preparation of catalyst 3h is with embodiment 29.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3h (13mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 7.36 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 92.56%; C 6: 3.36%; C 〉=8: 4.08%.No polymer generates.
Embodiment 31
1. the preparation of catalyst 3i: (0.123g, 0.35mmol) (0.133g 0.37mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2i with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with Schl enk method, vacuum drying obtains complex 0.186g, 3i: productive rate: 92.1%.Elementary analysis: C 23H 22Br 2NNiOP: calculated value: C, 47.80; H, 3.84; N, 2.42.Test value: C, 47.65; H, 3.68; N, 2.36.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3i (2.9mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.04%; C 6: 11.47%; C 〉=8: 3.13%.C 4The content of 1-butylene is in the component: 30.3%.
Embodiment 32
1. the preparation of catalyst 3i is with embodiment 31.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3i (12mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 6.21 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.23%; C 6: 9.11%; C 〉=8: 5.66%.No polymer generates.
Embodiment 33
1. the preparation of catalyst 3j: (0.138g, 0.39mmol) (0.136g 0.41mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2j with 2-methoxy ethyl ether nickelous bromide 2Replace after three times, add treated carrene (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.188g, 3j: productive rate: 87.5%.Elementary analysis: C 21H 18Br 2NNiOP: calculated value: C, 45.87; H, 3.30; N, 2.55.Test value: C, 45.68; H, 3.22; N, 2.41.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 3j (2.7mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.04%; C 6: 11.47%; C 〉=8: 3.13%.C 4The content of 1-butylene is in the component: 30.3%.
Embodiment 34
1. the preparation of catalyst 3j is with embodiment 33.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 3j (11mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.31 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 86.24%; C 6: 9.38%; C 〉=8: 4.38%.No polymer generates.
Embodiment 35
1. the preparation of catalyst 4a: (0.050g, 0.38mmol) (0.140g 0.40mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2a with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.162g, 4a: productive rate: 91.0%.Elementary analysis: C 22H 20Cl 2NNiOP: calculated value: C, 55.63; H, 4.24; N, 2.95.Test value: C, 55.41; H, 3.98; N, 2.61.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4a (2.4mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 0.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 91.50%; C 6: 6.07%; C 〉=8: 2.43%.C 4The content of 1-butylene is in the component: 19.4%.
Embodiment 36
1. the preparation of catalyst 4a is with embodiment 35.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4a (9.5mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.05 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 89.86%; C 6: 6.16%; C 〉=8: 3.98%.No polymer generates.
Embodiment 37
1. the preparation of catalyst 4b: (0.050g, 0.38mmol) (0.143g 0.40mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2b with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.169g, 4b: productive rate: 89.2%.Elementary analysis: C 23H 22Cl 2NNiOP: calculated value: C, 56.49; H, 4.53; N, 2.86.Test value: C, 56.31; H, 4.29; N, 2.71.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4b (2.4mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 0.86 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 90.50%; C 6: 6.07%; C 〉=8: 3.43%.C 4The content of 1-butylene is in the component: 21.5%.
Embodiment 38
1. the preparation of catalyst 4b is with embodiment 38.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4b (9.8mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 2.68 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 87.86%; C 6: 7.16%; C 〉=8: 3.98%.No polymer generates.
Embodiment 39
1. the preparation of catalyst 4c: (0.043g, 0.33mmol) (0.126g 0.35mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2c with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.150g, 4c: productive rate: 93.2%.Elementary analysis: C 23H 22Cl 2NNiOP: calculated value: C, 56.49; H, 4.53; N, 2.86.Test value: C, 56.53; H, 4.38; N, 2.79.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4c (2.4mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 0.92 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 88.20%; C 6: 8.90%; C 〉=8: 2.90%.C 4The content of 1-butylene is in the component: 21.5%.
Embodiment 40
1. the preparation of catalyst 4c is with embodiment 39.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4c (9.8mg, 20 μ mol) successively, (1.54mol/L, 13ml), the cumulative volume that makes toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.62 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.31%; C 6: 10.71%; C 〉=8: 3.98%.No polymer generates.
Embodiment 41
1. the preparation of catalyst 4d: (0.047g, 0.36mmol) (0.142g 0.38mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2d with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.164g, 4d: productive rate: 90.6%.Elementary analysis: C 24H 24Cl 2NNiOP: calculated value: C, 57.30; H, 4.81; N, 2.78.Test value: C, 57.61; H, 5.02; N, 2.84.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4d (2.5mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.95 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 89.10%; C 6: 8.00%; C 〉=8: 2.90%.C 4The content of 1-butylene is in the component: 29.8%.
Embodiment 42
1. the preparation of catalyst 4d is with embodiment 41.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4d (10mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 75.30%; C 6: 20.72%; C 〉=8: 3.98%.No polymer generates.
Embodiment 43
1. the preparation of catalyst 4e: (0.047g, 0.36mmol) (0.147g 0.38mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2e with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.158g, 4e: productive rate: 84.6%.Elementary analysis: C 24H 24Cl 2NNiO 2P: calculated value: C, 57.30; H, 4.81; N, 2.78.Test value: C, 57.61; H, 5.02; N, 2.84.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4e (2.5mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.95 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 89.10%; C 6: 8.00%; C 〉=8: 2.90%.C 4The content of 1-butylene is in the component: 29.8%.
Embodiment 44
1. the preparation of catalyst 4e is with embodiment 43.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4e (10mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 75.30%; C 6: 20.72%; C 〉=8: 3.98%.No polymer generates.
Embodiment 45
1. the preparation of catalyst 4f: (0.047g, 0.36mmol) (0.155g 0.38mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2f with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.175g, 4f: productive rate: 90.5%.Elementary analysis: C 27H 22Cl 2NNiOP: calculated value: C, 60.38; H, 4.13; N, 2.62.Test value: C, 60.51; H, 4.35; N, 2.79.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4f (2.7mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.70 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 90.12%; C 6: 7.23%; C 〉=8: 2.65%.C 4The content of 1-butylene is in the component: 16.9%.
Embodiment 46
1. the preparation of catalyst 4f is with embodiment 45.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4f (11mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.94 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 78.30%; C 6: 17.02%; C 〉=8: 4.68%.No polymer generates.
Embodiment 47
1. the preparation of catalyst 4g: (0.050g, 0.39mmol) (0.153g 0.41mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2g with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.170g, 4g: productive rate: 86.2%.Elementary analysis: C 24H 24Cl 2NNiOP: calculated value: C, 57.30; H, 4.81; N, 2.78.Test value: C, 57.61; H, 4.64; N, 2.59.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4g (2.5mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.02 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 89.12%; C 6: 8.23%; C 〉=8: 2.65%.C 4The content of 1-butylene is in the component: 21.9%.
Embodiment 48
1. the preparation of catalyst 4g is with embodiment 47.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4g (10mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.68 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 88.30%; C 6: 7.02%; C 〉=8: 4.68%.No polymer generates.
Embodiment 49
1. the preparation of catalyst 4h: (0.050g, 0.39mmol) (0.167g 0.41mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2h with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.194g, 4h: productive rate: 92.5%.Elementary analysis: C 27H 22Cl 2NNiOP: calculated value: C, 60.38; H, 4.13; N, 2.61.Test value: C, 60.07; H, 4.54; N, 2.57.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4h (2.7mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.68 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.27%; C 6: 11.75%; C 〉=8: 2.98%.C 4The content of 1-butylene is in the component: 20.5%.
Embodiment 50
1. the preparation of catalyst 4h is with embodiment 49.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4h (11mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 7.21 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 85.30%; C 6: 9.02%; C 〉=8: 5.68%.No polymer generates.
Embodiment 51
1. the preparation of catalyst 4i: (0.044g, 0.34mmol) (0.129g 0.36mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2i with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.158g, 4i: productive rate: 95.4%.Elementary analysis: C 23H 22Cl 2NNiOP: calculated value: C, 56.49; H, 4.53; N, 2.86.Test value: C, 56.21; H, 4.62; N, 2.95.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4i (2.4mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 0.93 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 79.96%; C 6: 14.43%; C 〉=8: 7.61%.C 4The content of 1-butylene is in the component: 19.2%.
Embodiment 52
1. the preparation of catalyst 4i is with embodiment 51.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4i (9.8mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.65 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 81.03%; C 6: 14.30%; C 〉=8: 4.67%.No polymer generates.
Embodiment 53
1. the preparation of catalyst 4j: (0.045g, 0.35mmol) (0.122g 0.37mmol) adds in the Schlenk bottle, vacuumizes logical N with corresponding phosphine- azoles quinoline part 2j with anhydrous chlorides of rase nickel 2Replace after three times, add treated ethanol (10ml), stirred 3 hours under the room temperature, concentrate the back and add n-hexane (20ml), have red precipitate to separate out, after filtering with the Schlenk method, vacuum drying obtains complex 0.157g, 4j: productive rate: 91.8%.Elementary analysis: C 21H 18Cl 2NNiOP: calculated value: C, 54.72; H, 3.94; N, 3.04.Test value: C, 55.01; H, 4.02; N, 3.12.
2. ethylene oligomerization: the 250ml polymerization bottle that magnetic stick will be housed vacuumizes and uses N while hot 130 ℃ of continuous dryings 6 hours 2Gas displacement 3 times.Add catalyst 4j (2.3mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (26.7ml) with syringe, (1.54mol/L 3.3ml) makes Al/Ni=1000, under 25 ℃, keeps the ethylene pressure of 1atm, vigorous stirring 30 minutes to add the toluene solution of MAO (MAO) again.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 1.65 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 81.23%; C 6: 9.13%; C 〉=8: 9.64%.C 4The content of 1-butylene is in the component: 19.2%.
Embodiment 54
1. the preparation of catalyst 4j is with embodiment 53.
2. ethylene oligomerization: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add toluene solution and a certain amount of toluene of catalyst 4j (9.2mg, 20 μ mol) successively, (1.54mol/L 13ml) makes Al/Ni=1000, and the cumulative volume of toluene is 150ml to add a certain amount of MAO at last.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 3.68 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 86.32%; C 6: 10.44%; C 〉=8: 3.24%.No polymer generates.
Embodiment 55
1. catalyst 3a load process: in the atmosphere of high pure nitrogen with silica dioxide granule 600 ℃ of following roasts 4 hours, under the atmosphere of high pure nitrogen, be cooled to room temperature then.The average pore size of used silica is 55 microns, and specific area is 309 meters squared per gram.The silica of getting 1 gram process roast joins (volume of toluene is 50 milliliters) in the toluene solution that contains 7 mM MAOs under nitrogen atmosphere.After mixed liquor at room temperature stirred 16 hours, suspension is concentrated into 15 milliliters, filters then, with toluene wash 5 times, each washing is with 15 milliliters of toluene.After the silica process vacuum drying that MAO is handled, join in the toluene solution of the complex 3a catalyst that contains 0.5 mM, after the mixed liquor that obtains at room temperature stirs 14 hours, under nitrogen atmosphere, filter, after 60 milliliters of toluene wash three times, dry in a vacuum, just obtain the 3a catalyst of loadization.Through emission of ions spectrum-mass spectrometric measurement analysis, the middle aluminium quality percentage composition of supported catalyst is 16.2%.The quality percentage composition of nickel is 0.72%.
2. the ethylene oligomerization of supported catalyst 3a: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add the slurries of supported catalyst 3a (wherein the consumption of nickel is 20 μ mol), the cumulative volume of toluene is 150ml.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 2.96 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 69.84%; C 6: 20.43%; C 〉=8: 9.73%.No polymer generates.
Embodiment 56
1. catalyst 3a load process: in the atmosphere of high pure nitrogen, the spherical magnesium chloride granules of 1 gram is joined (volume of toluene is 50 milliliters) in the toluene solution that contains 7 mM MAOs, after its mixed liquor at room temperature stirs 6 hours, decompression is removed most of solvent to 20 milliliters of total amount of liquid, filter then, with toluene wash 5 times, each washing is with 15 milliliters of toluene.After the spherical magnesium chloride process vacuum drying that MAO is handled, join in the toluene solution of the complex 3a catalyst that contains 0.5 mM, after the mixed liquor that obtains at room temperature stirs 6 hours, decompression remove most of solvent to the reactant liquor volume at 20 milliliters, under nitrogen atmosphere, filter, divide four washings with 60 milliliters of toluene, dry in a vacuum, just obtain the 3a catalyst of loadization.
2. the ethylene oligomerization of supported catalyst 3a: the stainless steel still that the 1L of mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.After the cool to room temperature, add the slurries of supported catalyst 3a (wherein the consumption of nickel is 20 μ mol), the cumulative volume of toluene is 150ml.The pressure of ethene is increased to 20 atmospheric pressure, 25 ℃ of following vigorous stirring 30 minutes.With watery hydrochloric acid neutralization MAO wherein, the toluene layer that takes a morsel is behind anhydrous sodium sulfate drying, with the content and the distribution of gas Chromatographic Determination oligomer under 0 ℃.Oligomerisation activity: 4.37 * 10 5G (oligomer) mol -1(Ni) h -1Atm -1Oligomer distributes: C 4: 48.56%; C 6: 34.35%; C 〉=8: 17.09%.

Claims (20)

1, a kind of 2-(2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide complex with following structural formula:
Figure C2004100817110002C1
Wherein:
R 1-R 5Be selected from hydrogen independently of one another, contain alkyl, aryl, alkaryl, aralkyl or the alkoxyl of 1-6 carbon atom;
X is a halogen.
2, according to the complex of claim 1, R wherein 1-R 5Be selected from hydrogen independently of one another, methyl, ethyl, propyl group, methoxyl group, ethyoxyl, propoxyl group or phenyl.
3, according to the complex of claim 1, wherein X is a chlorine or bromine.
4, according to the complex of claim 1, wherein said complex is to be selected from following complex:
3a：R 1＝R 2＝R 3＝R 4＝H，R 5＝CH 3，X＝Br； 4a：R 1＝R 2＝R 3＝R 4＝H，R 5＝CH 3，X＝Cl；
3b：R 1＝R 2＝R 3＝R 4＝H，R 4＝C 2H 5，X＝Br； 4b：R 1＝R 2＝R 3＝R 5＝H，R 4＝C 2H 5，X＝Cl；
3c：R 1＝R 2＝R 5＝H，R 3＝R 4＝CH 3，X＝Br； 4c：R 1＝R 2＝R 5＝H，R 3＝R 4＝CH 3，X＝Cl；
3d：R 1＝R 3＝R 4＝CH 3，R 2＝R 5＝H，X＝Br； 4d：R 1＝R 3＝R 4＝CH 3，R 2＝R 5＝H，X＝Cl；
3e：R 1＝R 5＝H，R 2＝OCH 3，R 3＝R 4＝CH 3，X＝Br； 4e：R 1＝R 5＝H，R 2＝OCH 3，R 3＝R 4＝CH 3，X＝Cl；
3f：R 1＝R 2＝R 3＝R 5＝H，R 4＝Ph，X＝Br； 4f：R 1＝R 2＝R 3＝R 5＝H，R 4＝Ph，X＝Cl；
3g：R 1＝R 2＝R 3＝R 5＝H，R 4＝CH(CH 3) 2，X＝Br； 4g：R 1＝R 2＝R 3＝R 5＝H，R 4＝CH(CH 3) 2，X＝Cl；
3h：R 1＝R 2＝R 3＝R 4＝H，R 5＝Ph，X＝Br； 4h：R 1＝R 2＝R 3＝R 4＝H，R 5＝Ph，X＝Cl；
3i：R 1＝R 2＝R 3＝H，R 4＝R 5＝CH 3，X＝Br； 4i：R 1＝R 2＝R 3＝H，R 4＝R 5＝CH 3，X＝Cl；
3j:R 1=R 2=R 3=R 4=R 5=H, X=Br; Or 4j:R 1=R 2=R 3=R 4=R 5=H, X=Cl.
5, according to the preparation method of 2-(2-(diphenylphosphine) phenyl) the  azoles quinoline nickel halogenide complex of claim 1, it comprises:
(1) the  isoxazoline compound of synthetic halogen replacement;
(2)  isoxazoline compound that replaces with the halogen that obtains in the step (1) and diphenylphosphine lithium or diphenylphosphine potassium react, and obtain phosphine- azoles quinoline part;
(3) can obtain complex with resulting phosphine in the step (2)- azoles quinoline part and 2-methoxy ethyl ether nickel halogenide or the reaction of anhydrous nickel halogenide.
6, according to the preparation method of claim 5, wherein the proportioning of the  isoxazoline compound that diphenylphosphine lithium or diphenylphosphine potassium and halogen replace in step (2) is 1.2-2.0.
7, according to the preparation method of claim 6, wherein the proportioning of the  isoxazoline compound that diphenylphosphine lithium or diphenylphosphine potassium and halogen replace in step (2) is 1.5.
8, according to the preparation method of claim 5, wherein the proportioning of phosphine- azoles quinoline part and 2-methoxy ethyl ether nickel halogenide or anhydrous nickel halogenide reaction is 1.1-1.2 in step (3).
9, a kind of carbon monoxide-olefin polymeric, it comprises:
(1) major catalyst, it is each 2-(2-(diphenylphosphine) phenyl)  azoles quinoline nickel halogenide complex among the claim 1-4;
(2) co-catalyst, it is selected from aikyiaiurnirsoxan beta or alkyl aluminum compound.
10, claim 9 carbon monoxide-olefin polymeric, wherein said aikyiaiurnirsoxan beta are selected from MAO, modified methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.
11, the carbon monoxide-olefin polymeric of claim 10, wherein said aikyiaiurnirsoxan beta are MAO.
12, according to the carbon monoxide-olefin polymeric of claim 9, wherein said alkyl aluminum compound is trialkylaluminium or chlorination alkyl aluminum.
13, according to the carbon monoxide-olefin polymeric of claim 12, wherein said trialkylaluminium is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; And described chlorination alkyl aluminum is selected from diethylaluminum chloride or ethylaluminium dichloride.
14, according to each carbon monoxide-olefin polymeric among the claim 9-13, the mol ratio of the metallic aluminium in the wherein said major catalyst in metallic nickel and the co-catalyst is 200 to 2000.
15, according to the carbon monoxide-olefin polymeric of claim 15, the mol ratio of the metallic aluminium in the wherein said major catalyst in metallic nickel and the co-catalyst is 800-1500.
16, according to the carbon monoxide-olefin polymeric of claim 9, it further comprises the assistant ligand triphenylphosphine.
17, according to the carbon monoxide-olefin polymeric of claim 9, wherein said carbon monoxide-olefin polymeric is loaded on the carrier.
18, according to the carbon monoxide-olefin polymeric of claim 17, wherein said carrier is silica or ball-type magnesium chloride.
19, each the application of carbon monoxide-olefin polymeric in ethylene oligomerization among the claim 9-18.
20, a kind of method of ethylene oligomerization, it comprises makes that each carbon monoxide-olefin polymeric contacts among ethene and the claim 9-18 under polymerizing condition.
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