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CN1566041A - Ethylene oligomerization catalysis system and preparation method and application thereof - Google Patents

Ethylene oligomerization catalysis system and preparation method and application thereof Download PDF

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CN1566041A
CN1566041A CNA031423280A CN03142328A CN1566041A CN 1566041 A CN1566041 A CN 1566041A CN A031423280 A CNA031423280 A CN A031423280A CN 03142328 A CN03142328 A CN 03142328A CN 1566041 A CN1566041 A CN 1566041A
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dimethyl
phenyl
oligopolymer
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methyl
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孙文华
张天柱
崔勇
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Institute of Chemistry CAS
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Abstract

The invention provides an ethylene oligomerization catalysis system and preparation method and application thereof, 2-di(di-(4-bromophenyl) phosphino methyl) benzene nickel dichloride, 1,3-di(di-(4-bromophenyl) phosphino methyl) benzene nickel dichloride, 8-di(di-(4-bromophenyl) phosphino methyl) quinoline nickel dichloride series complex, and the catalyst promoter employs methyl aluminium oxyalkyl (MAO).

Description

A kind of ethylene oligomerization catalysis system and its production and application
Technical field
The present invention relates to a kind of catalyst system that is used for ethylene oligomerization, promptly contain P^P (N) bitooth ligand coordinate Ni (II) and Pd (II) composition catalyst system.
The invention still further relates to the preparation method of above-mentioned catalyst system.
The invention still further relates to the purposes of above-mentioned catalyst system at ethylene oligomerization.
Background technology
The oligopolymer state of ethene and derivative thereof (alpha-olefin) generally is thick or semi-solid, and this state is given their very particular performances and purposes: 1) compare, be soluble in the organic solvent with superpolymer, and also bigger with the consistency of superpolymer; 2) compare with superpolymer, the content of end group is bigger, and function is easy to manifest; 3), therefore be convenient to molecular designing because the structure variation of oligopolymer can be carried out chemical conversion and curing reaction again; 4) in the application of oligopolymer, can not use solvent, can reduce public hazards, help the conservation of nature environment.For example the oligopolymer of ethene can be used for the dispersing of pigments agent, the modification of paraffin, the additive of printing-ink and coating, the auxiliary agent during plastic working, comonomer of production of linear new LDPE (film grade) or the like.The oligomerisation propylene also has following purposes: as the softening agent of polypropylene and ethylene-propylene rubber(EPR), lubricating oil, tackiness agent and tackifier or the like except that as the gasoline dope.
Because the polyolefin industry of China is started late, so present state of the art and outer state-owned suitable gap.With the ethylene oligomerization is example.
One of major industry purposes of ethylene oligomerization is exactly to be used for producing C 6-C 20Linear alpha-alkene.The oligopolymer of these linear ethylenes is widely used for producing washing composition, softening agent, the comonomer of lubricant and conduct preparation linear low density polyethylene (LLDPE).Linear alpha-alkene originally is all mainly from Ziegler (Alfen) prepared: at triethyl aluminum (AlEt 3) under the condition that exists, control the reaction of propagation of ethene at the ethylene pressures of 90～120 ℃ and 100bar by controlled temperature.Reduce the pressure of ethene and improve temperature of reaction, alpha-olefin just discharges from catalytic active center.Being applied in industrial catalyzer at present is alkylaluminium cpd, and promptly aluminum alkyls and early transition metal title complex (are TiCl 4) combination or contain the title complex (SHOP technology) (US patent 3686351,19720711 and US patent 3676523,19720822.) of the Ni (II) of single anion bitooth ligand P^O, its structural formula is as follows:
X＝H，SO 3Na；Y＝Aryl，OR″； L＝PR 3，Pyridine，CR 2PR′ 3
The composition catalyst that is used for the Ni that contains single anion bitooth ligand P^O (II) of ethylene oligomerization is studied widely.It should be noted that most people's such as W.Keim work.In the past few decades, people such as Keim and Cavell have studied the single anion ligand of a lot of other types, as As^O, and N^O, O^O, parts such as S^O and S^S.Generally speaking, all obtain alkyl or the halogenated compound that neutral has catalytic activity by these single anion ligands.Want oligomerizing ethylene, their all demanding temperature of reaction and pressure.As the temperature of 80～120 ℃ of SHOP processing requirements and the ethylene pressure of 100bar.Found neutral P^O part afterwards, can obtain the title complex of cationic Ni (II), oligomerizing ethylene under very low temperature and pressure by it.The title complex of similar cationic Pd (II) can two polyethylene come of age alkene (M.C.Bonnet, F.Dahan, A.Ecke, W.Keim, R.P.Schuz, I.Tkatchenko, A.G.Webb.J.Chem.Soc.Chem.Commum.1994,615; G.J.PBritovsek, W.Keim, S.Mecking, D.Sainz, T.wagner.J.Chem.Soc.Chem.Commun.1993,1632.).Recently, resemble the composition catalyst that diimine N^N and phosphine amine P^N part all can obtain active Ni of oligomerisation (II) and Pd (II) by the neutral ligand of various other types.
Nineteen ninety-five, Brookhart etc. have reported the title complex (formula as follows) (J.Am.Chem.Soc., 1995,117,6461) of a kind of diimine Ni (II).
Figure A0314232800062
(a)R＝H；Ar＝2，6-C 6H 3(i-Pr) 2 (b)R＝Me；Ar＝2，6-C 6H 3(i-Pr) 2 (c)R＝H；Ar＝2，6-C 6H 3Me 2 (d)R＝Me；Ar＝2，6-C 6H 3Me 2
Figure A0314232800063
(e)Ar＝2，6-C 6H 3(i-Pr) 2
Then soon, Brookhart and Gibson etc. has reported the Fe (II) of pyridine diimine and the title complex (formula as follows) of Co (II) (J.Am.Chem.Soc., 1998,120,4049 again simultaneously; J.Am.Chem.Soc., 1999,121,8727), by regulating the substituting group on the phenyl ring, oligomerisation or polymerising ethylene well.
M＝Fe?or?Co；R 1＝H，Me；R 2＝Me，iPr；
R 3＝H，Me，iPr；R 4＝H，Me
1994, W.Keim reported the Ni title complex of following neutrality and cationic P^O part;
Calendar year 2001, Wass etc. have reported the title complex (D) of the Ni (II) that contains the P^P bitooth ligand, and they are with Ni (COD) 2Or the MAO promotor, oligomerisation or polymerising ethylene well, its structure of above-mentioned title complex is formula as follows.
Figure A0314232800072
In recent years, owing to utilize the 1-hexene, the LLDPE of 1-octene and ethylene copolymer gained has excellent comprehensive performances, as tear-resistant, wear-resisting and tensile strength is high, so its demand is constantly increased, correspondingly the demand to high alpha-olefin also sharply increases.The external main at present production of oligomerisation method alpha-olefin, the SHOP method of aforesaid Shell Co. Ltd and the Philips method of Philips company of adopting.China can't produce at present, and all need spend a large amount of foreign exchanges and buy every year.Therefore the present invention has designed and synthesized and has contained P^P part coordinate Ni (II) and Pd (II) title complex.They have synthetic simple, with low cost, the advantage that the oligomerisation performance is good.
Summary of the invention
The object of the present invention is to provide a kind of ethylene oligomerization catalysis system.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst system.
Catalyst system provided by the invention comprises Primary Catalysts and promotor, and affiliated Primary Catalysts is P^P (N) type part coordinate Ni (II) or Pd (II) title complex, and its structure is shown in A formula and B formula:
In the formula:
The coordination metal M is Ni or Pd;
R and R ' are respectively the alkane substituting group;
R " be hydrogen or alkane substituting group;
The aromatic base of Ar for replacing;
X is Cl or Br;
Specifically, in structure A formula and the B formula:
R is: methylene radical, 1, the 2-ethylidene, 1,2-(methyl) ethylidene, 1,2-(ethyl) ethylidene, 1,2-(1-methyl-2-ethyl) ethylidene, 1, the 3-propylidene, 1,3-(1-methyl) propylidene, 1, the 4-butylidene, 1,4-(1-methyl) butylidene, 1, the 2-xylylene, 1, the 3-xylylene, 1,1 '-dinaphthalene-2,2 '-dimethyl, 1,2-naphthalene dimethyl, 1,3-naphthalene dimethyl, 1,4-naphthalene dimethyl, 1,7-naphthalene dimethyl, 1,8-naphthalene dimethyl, 3,4-naphthalene dimethyl, 2,3-naphthalene dimethyl, 2,4-naphthalene dimethyl, 2,2 '-biphenyl dimethyl, 3,3 '-biphenyl dimethyl, 2,5-furans dimethyl, 2,3-furans dimethyl, 2,3-cumarone dimethyl, 5,6-benzoglyoxaline dimethyl, 2,5-pyrroles's dimethyl, 2,3-pyrroles's dimethyl, 2,6-thiophene dimethyl, 4,6-thionaphthene dimethyl, 2,6-pyridine dimethyl, 2,3-pyridine dimethyl, 2,4-pyridine dimethyl, 3,4-pyridine dimethyl, 3,5-pyridine dimethyl, 2,2 '-dipyridyl-4,4 '-dimethyl, 1,1-ferrocene dimethyl, 2,3-pyrazine dimethyl, 2,4-quinoline dimethyl, 2,6-quinoxaline-dimethyl, 2,3-two (2-pyridyl) quinoxaline-6, the 7-dimethyl, 2, the 4 benzoic acid dimethyl, 1,10-phenanthroline-5,6-dimethyl, 1,10-phenanthroline-2, the 9-dimethyl, 1,2-(3-oil of mirbane) dimethyl, 1,2-(4-oil of mirbane) dimethyl, 1,3-(4-oil of mirbane) dimethyl, 1,3-(5-oil of mirbane) dimethyl, 2,3-fluorobenzene dimethyl, 3,4-chlorobenzene dimethyl, 2,3-bromobenzene dimethyl, 2,4-bromobenzene dimethyl, 3,4-bromobenzene dimethyl, 3,5-bromobenzene dimethyl, 2,3-iodobenzene dimethyl, 2,4-iodobenzene dimethyl, 3,4-iodobenzene dimethyl, 3,5-iodobenzene dimethyl, 2,3-methyl-phenoxide dimethyl, 2,4-methyl-phenoxide dimethyl, 3,4-methyl-phenoxide dimethyl, 3,5-methyl-phenoxide dimethyl, 4,5-thiazole dimethyl or 3,5-pyrazoles dimethyl;
R ' is a methyl, phenyl, 1-naphthyl;
R " be hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, phenyl, 1-naphthyl, 9-phenanthryl, 9-anthryl;
Ar is: 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 3,5-dibromo phenyl, 2,6-dibromo phenyl, 2,4-dibromo phenyl 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 3,5-diiodo-phenyl, 2,6-diiodo-phenyl, 2,4-diiodo-phenyl, 2-carboxyl phenyl, 3-carboxyl phenyl, 4-carboxyl phenyl, 3,5-dicarboxyl phenyl, 2,6-dicarboxyl phenyl or 2,4-dicarboxyl phenyl; Substituting group on the Ar base is electrophilic halogen group or carboxyl.
Promotor is methylaluminoxane (MAO), cyclooctadiene base nickel (Ni (COD) 2), trimethyl aluminium (AlMe 3), triethyl aluminum (AlEt 3), triisobutyl aluminium (Al (iso-Bu) 3), diethyl aluminum chloride (Et 2AlCl) or ethylaluminum dichloride (EtAlCl 2);
Promotor/Primary Catalysts mol ratio is 500-3000;
The temperature of reaction of above-mentioned catalyst system is-10-80 ℃;
Regulate the mol ratio or the temperature of reaction of Primary Catalysts/promotor, the corresponding variation also will take place in the distribution of gained oligopolymer, and the oligopolymer of gained comprises C 4, C 6, C 8, C 10To C 20
When adding promotor MAO, add triphenyl phosphorus again, the amount of substance of its adding is 1-10 a times of Primary Catalysts, helps to improve the catalytic performance of catalyzer, can improve catalytic activity 1-2 doubly.
Above-mentioned Primary Catalysts preparation method provided by the invention, its key step is as follows:
A) part is synthetic
With Ar 2P (O)-R-P (O) Ar 2Or 8-[two (substituted aryl) phosphinomethyl] quinoline (8-Ar 2P (O) CH 2-Quninoline) and HSiCl 3(mol ratio is 1: 5～50) is dissolved in exsiccant toluene, and (10～50mL), stirring and refluxing 5～20 hours is cooled to room temperature, uses saturated sodium bicarbonate aqueous solution (with HSiCl then 3Volume ratio be 1～2), excessive HSiCl neutralizes 3With the acid that reaction is produced, filter, with the distillation of gained filtrate decompression, obtain product A r 2P-R-PAr 2Or 8-Ar 2PCH 2-Quninoline;
B) preparation of Primary Catalysts
The part of steps A preparation is made solution 1 in the ratio that 1mmol is dissolved in 10～20mL exsiccant tetrahydrofuran (THF) (THF);
Metal halide is dissolved in CH by 0.9mmol 2Cl 2/ MeOH (10～20mL) or CH 2Cl 2(20mL) ratio in the mixed solvent is made solution 2;
Under stirring at room, solution 2 is added drop-wise in the solution 1, continue reaction 10 minutes～5 hours, boil off solvent then under the decompression and obtain precipitation, (3 * 10mL) washings obtain pure title complex with ether.
Above-mentioned metal halide is nickelous chloride (NiCl 2), Palladous chloride (PdCl 2), triphenylphosphine phenyl nickelous chloride ((PPh 3) 2PhNiCl), nickelous bromide (NiBr 2), 1 dme nickelous bromide (NiBr 2(DME)), 1,5-cyclooctadiene base Palladous chloride (PdCl 2(COD)), triphenylphosphine (1-naphthyl) nickelous bromide ((PPh 3) 2(1-naphthyl) NiBr) or acetonitrile Palladous chloride (PdCl 2(MeCN)).
Catalyst system provided by the present invention can be applied in the ethylene oligomerization:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and use N while hot 2Gas displacement 3 times.Add quantitative catalyzer and then vacuumize and with ethene displacement 3 times.Organic solvent with syringe injection 30mL adds quantitative methylaluminoxane (MAO) again, (10 ℃～80 ℃) at a certain temperature, the ethylene pressure of maintenance 1atm, vigorous stirring 30 minutes-1 hour.Use the 5% dilute hydrochloric acid termination reaction of 5～100mL at last.Measure oligopolymer with GC.
Organic solvent comprises toluene, tetrahydrofuran (THF), chlorobenzene, methylene dichloride, 1,2-ethylene dichloride, pentane, normal hexane or Trimethylmethane.
Catalyst system provided by the invention has following feature:
1. the used Preparation of Catalyst of the present invention is simple, and raw material is easy to get, and stability is good, and is nonflammable.
2. catalyst system provided by the present invention is to ethylene oligomerization, and the distribution of resulting oligopolymer can realize by ratio and the oligomerisation temperature that changes the MAO/ Primary Catalysts, thereby can make the ethylene oligomer that can satisfy different demands and purposes.
3. in catalyst system, be the promotor, add the triphenyl phosphorus that 1-10 doubly measures in addition again and can improve catalytic activity significantly except adding MAO.
4. the field of activity of catalyst system provided by the present invention is 1 * 10 3-8.1 * 10 5Between g oligopolymer/mol catalyst.
Embodiment
Embodiment one
1, Preparation of catalysts:
1, the preparation of 2-two [two (4-bromophenyl) phosphinomethyl] benzene part
Under the nitrogen protection; in the two neck round-bottomed flasks of a 50mL, add α successively; α '-1; 2-two [two (4-bromophenyl) phosphoryl methyl] benzene (205.5mg, 0.25mmol), trichlorosilane (339mg; 2.5mmol); triethylamine (380mg, 2.75mmol) and toluene (10mL) then behind 120 ℃ of stirring and refluxing 5h. cool to room temperature, add the saturated NaHCO of 0.5mL 3The aqueous solution.This mixture at room temperature continues to stir 5min, removes by filter precipitation, and precipitates 3 times with toluene drip washing, each 15mL.Rotary evaporation removes to desolvate and obtains 1 of white, 2-two [two (4-bromophenyl) phosphinomethyl] benzene 177.8mg, productive rate 90%. 1H NMR (300MHz, CDCl 3, TMS); 8=7.36～7.23 (m, 16H), 7.02～6.97 (t, 2H), 6.72 (d, J=6.0Hz, 2H), 3.68 (d, J=14.1,2H); 31P NMR (121.5MHz, CDCl 3): δ=-16.7ppm (H 3PO 4Be external standard).Ultimate analysis (C 32H 24Br 4P 2): theoretical value (%): C 48.64, and H 3.06; Measured value (%): C 48.41, and H 2.79.
1, the preparation of 2-two [two (4-bromophenyl) phosphinomethyl] benzene Nickel Chloride
With NiCl 26H 2(42.8mg 0.18mmol) is dissolved in the 10mL methyl alcohol O, is added drop-wise to 1 then, and (158.0mg is in 10mL THF solution 0.2mmol) for 2-two [two (4-bromophenyl) phosphinomethyl] benzene.This mixture at room temperature continues to stir 2h.Except that after desolvating, (3 * 15mL) washing precipitations, then dry in a vacuum 2h obtains solid phase prod russet (135.7mg, 82%) at last with ether. 31P NMR (CDCl 3): δ=-16.1ppm (H 3PO 4Be external standard); MALDI-TOF MS isotropic substance calculated value (C 32H 24 79Br 4P 2Ni[M-2Cl] 2+) 844.5, measured value: 844.6.Ultimate analysis (C 32H 24Br 4Cl 2NiP 2) theoretical value (%): C 41.79, and H 2.63; Measured value (%): C 41.44, H2.70.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.8mg (4.1 * 10 that adds step 1 gained -6Mol) and then vacuumize and with ethene displacement 3 times.Inject 30mL toluene with syringe, add 1.3mL methylaluminoxane (MAO) again, make Al/Ni=500.Under 30 ℃ steady temperature, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 8.0 * 10 3G oligomers/molNih.Oligopolymer distributes: C 4: 37%, C 6: 24%, C 8: 38%, C 12: 1%.Wherein alpha-olefin accounts for 92%.
Embodiment two
1, Preparation of catalysts: the preparation method is with embodiment one.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.8mg (4.1 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.0 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 55%, C 6: 12%, C 8: 33%.Wherein alpha-olefin accounts for 94%.
Embodiment three
1, Preparation of catalysts: the preparation method is with embodiment one.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.5mg (4.9 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 5mL methylaluminoxane (MAO) again, make Al/Ni=1500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.0 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 80%, C 6: 11%, C 8: 8%, C 12: 1%.Wherein alpha-olefin accounts for 97%.
Embodiment four
1, Preparation of catalysts: the preparation method is with embodiment one.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.8mg (4.1 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 5.9mL methylaluminoxane (MAO) again, make Al/Ni=2000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.6 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 84%, C 8: 16%.Wherein alpha-olefin accounts for 94%.
Embodiment five
1, Preparation of catalysts: the preparation method is with embodiment one.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.0mg (4.3 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 7.8mL methylaluminoxane (MAO) again, make Al/Ni=2500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.8 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 79%, C 6: 21%.Wherein alpha-olefin accounts for 95%.
Embodiment six
1, Preparation of catalysts: the preparation method is with embodiment one.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.4mg (4.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 10.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.6 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 79%, C 8: 21%.Wherein alpha-olefin accounts for 94%.
Embodiment seven
1, Preparation of catalysts: the preparation method is with embodiment one.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL normal hexane with syringe, add 3.1mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 0 ℃ of steady temperature, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 5.0 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 82%, C 8: 17%, C 10: 1%.Wherein alpha-olefin accounts for 90%.
Embodiment eight
1, Preparation of catalysts:
1, the preparation of 2-two [two (4-bromophenyl) phosphinomethyl] benzene part is with embodiment one.
1,2-two [two (4-bromophenyl) phosphinomethyl] benzene Nickel Bromide synthetic
The Schlenk pipe that magneton is housed vacuumized fill N 2Gas, so triplicate.At N 2Under the gas shiled, add 1 successively, 2-two [two (4-bromophenyl) phosphinomethyl] benzene part (158.0mg, 0.2mmol) (preparation is with embodiment one) and NiBr 2(dme) (dme=1,2-glycol dimethyl ether) (61.7mg 0.2mmol), adds 20mL CH then 2Cl 2(through sufficient deoxygenation and dewater).At room temperature stirred then 20 hours.In the reaction process, the color of solution becomes sorrel.Rotary evaporation is removed CH 2Cl 2After obtain oily precipitation, with Skellysolve A washing 3 times, each 10mL.Drying is 5 hours under vacuum, obtains solid phase prod 141mg russet at last, productive rate 70%. 31P NMR (121.5MHz, CDCl 3): δ=-34.3ppm (H 3PO 4Be external standard); MALDI-TOF MS theoretical value (C 32H 24 79Br 4P 2Ni[M-2Cl] 2+) 844.5, measured value: 844.7.Ultimate analysis (C 32H 24Br 6NiP 2) theoretical value (%): C 38.11, and H 2.40; Measured value (%): C 38.38, and H 2.81.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.8mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.1 * 10 5G oligomers/mol Nih.Oligopolymer distributes: C 4: 40%, C 6: 23%, C 8: 37%.Wherein alpha-olefin accounts for 89%.
Embodiment nine
1, Preparation of catalysts:
1, the preparation of 2-two [two (4-bromophenyl) phosphinomethyl] benzene part is with embodiment one.
1,2-two [two (4-bromophenyl) phosphinomethyl] benzene palladium chloride
With PdCl 2(MeCN) 2(130.0mg 0.5mmol) is dissolved in 10mLCH 2Cl 2(fully deoxygenation and dewater) obtains solution (1).With 1,2-two [two (4-bromophenyl) phosphinomethyl] benzene part (434.6mg, 0.55mmol) (preparation with embodiment one) be dissolved among the 10mLTHF (fully deoxygenation and dewater), obtain solution (2).Then solution (1) is added drop-wise in the solution (2), at room temperature fully stirred 3 hours, rotary evaporation is removed CH 2Cl 2, obtain filemot solid complexes 416mg behind THF and the MeCN, productive rate 86%. 31P NMR (121.5MHz, CDCl 3): δ=-35.4ppm (H 3PO 4Be external standard); MALDI-TOF MS (C 32H 24 79Br 4P 2Pd[M-2Cl] 2+), theoretical value: 892.2, measured value: 892.1.Ultimate analysis (C 32H 24Br 4Cl 2P 2Pd): theoretical value (%): C 39.73, and H 2.50; Measured value (%): C 39.53, and H 2.74.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.7mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Pd=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.1 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 40%, C 6: 23%, C 8: 37%.Wherein alpha-olefin accounts for 86%.
Embodiment ten
1, Preparation of catalysts:
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] benzene part
Under the nitrogen protection; in the two neck round-bottomed flasks of a 50mL, add α successively; α '-1; 3-two [two (4-bromophenyl) phosphoryl methyl] benzene (205.5mg, 0.25mmol), trichlorosilane (339mg; 2.5mmol); triethylamine (380mg, 2.75mmol) and toluene (10mL) then behind 120 ℃ of stirring and refluxing 5h. cool to room temperature, add the saturated NaHCO of 0.5mL 3The aqueous solution.This mixture at room temperature continues to stir 5min, filters the elimination precipitation, and precipitates 3 times with toluene drip washing, each 15mL.Rotary evaporation removes to desolvate and obtains the α of white, α '-1,3-two [two (4-bromophenyl) phosphinomethyl] benzene (179.7mg, productive rate 91%). 1H NMR (300MHz, CDCl 3): δ=7.67～7.44 (m, 16H), 7.34～6.82 (m, 4H), 3.56 (d, J=13.8,4H); 31P NMR (121.5MHz, CDCl 3): δ=-12.0ppm (H 3PO 4Be external standard).Ultimate analysis (C 32H 24Br 4P 2): theoretical value (%): C 48.64, and H 3.06; Measured value (%): C 48.55, and H 3.14.
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] benzene Nickel Chloride
With NiCl 26H 2O (42.8mg, 0.18mmol) be dissolved in the methyl alcohol of 10mL after, be added drop-wise to 1,3-two [two (4-bromophenyl) phosphinomethyl] benzene (158.0, in 10mL THF solution 0.2mmol).This mixture continues to stir 2h in room temperature.Except that after desolvating, (3 * 15mL) washing precipitations and dry in a vacuum 2h obtain title complex russet (155.6mg, productive rate 90%) at last with ether. 31PNMR (121.5MHz, CDCl 3): δ=-11.3ppm (H 3PO 4Be external standard); MALDI-TOF MS theoretical value (C 32H 24 79Br 4P 2Ni[M-2Cl] 2+) 844.5, measured value: 844.6.Ultimate analysis (C 32H 20 79Br 8P 2NiCl 2THF): theoretical value (%): C:43.60%, H 3.25%; Experimental value (%): C 43.84%, and H 3.60%.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 1.4mL methylaluminoxane (MAO) again, make Al/Ni=500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 484%, C 6: 8%, C 8: 8%.Wherein alpha-olefin accounts for 89%.
Embodiment 11
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 2.7mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.GC measures oligopolymer.Oligomerisation activity: 1.6 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 6 7%, C 6: 9%, C 8: 24%.Wherein alpha-olefin accounts for 91%.
Embodiment 12
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 4.1mL methylaluminoxane (MAO) again, make Al/Ni=1500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.1 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 88%, C 6: 4%, C 8: 8%.Wherein alpha-olefin accounts for 87%.
Embodiment 13
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 5.4mL methylaluminoxane (MAO) again, make Al/Ni=2000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.0 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 78%, C 6: 4%, C 8: 18%.Wherein alpha-olefin accounts for 93%.
Embodiment 14
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 6.8mL methylaluminoxane (MAO) again, make Al/Ni=2500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.4 * 10 5G oligomers/molNi/h.Oligopolymer distributes: C 4: 87%, C 6: 2%, C 8: 11%.Wherein alpha-olefin accounts for 92%.
Embodiment 15
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 0.9 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 96%, C 6: 3%, C 8: 1%.Wherein alpha-olefin accounts for 90%.
Embodiment 16
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL tetrahydrofuran (THF) with syringe, add 9.5mL methylaluminoxane (MAO) again, make Al/Ni=3500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 5.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 80%, C 6: 13%, C 8: 7%.Wherein alpha-olefin accounts for 94%.
Embodiment 17
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under-10 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 4.8 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 85%, C 6: 6%, C 8: 8%, C 12: 1%.Wherein alpha-olefin accounts for 96%.
Embodiment 18
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6Mol) and then vacuumize and with ethene displacement 3 times.Inject 30mL toluene with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 0 ℃ of steady temperature, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.6 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 79%, C 8: 21%.Wherein alpha-olefin accounts for 91%.
Embodiment 19
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 50 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.2 * 10 5G oligomers/molNi/h.Oligopolymer distributes: C 4: 81%, C 6: 1%, C 8: 18%.Wherein alpha-olefin accounts for 90%.
Embodiment 20
1, Preparation of catalysts: the preparation method is with embodiment ten.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.5mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 70 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 7.6 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 100%.Wherein alpha-olefin accounts for 85%.
Embodiment 21
1, Preparation of catalysts:
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] benzene part is with embodiment ten.
1,3-two [two (4-bromophenyl) phosphinomethyl] benzene Nickel Bromide synthetic
A Schlenk pipe that magneton is housed vacuumized fill N 2Gas, triplicate.At N 2Under the gas shiled, add 1 successively, 3-two [two (4-bromophenyl) phosphinomethyl] benzene part (158.0mg, 0.2mmol) (preparation is with embodiment eight) and NiBr 2(dme) (dme=1,2-glycol dimethyl ether) (61.7mg 0.2mmol), adds 20mL CH then 2Cl 2(through sufficient deoxygenation and dewater).At room temperature stirred then 20 hours.In the reaction process, the color of solution becomes sorrel.Rotary evaporation is removed CH 2Cl 2After obtain oily precipitation, with Skellysolve A washing 3 times, each 10mL.Drying is 5 hours under vacuum, obtains solid phase prod 167mg russet at last, productive rate 83%. 31P NMR (121.5MHz, CDCl 3): δ=-36.2ppm (H 3PO 4Be external standard); MALDI-TOF MS (C 32H 24 79Br 4P 2Ni[M-2Cl] 2+): theoretical value, 844.5, measured value, 844.4.Ultimate analysis (C 32H 24Br 6NiP 2): theoretical value (%): C 38.11, and H 2.40; Measured value (%): C 38.43, and H 2.67.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.8mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 5.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 78%, C 6: 13%, C 8: 9%.Wherein alpha-olefin accounts for 84%.
Embodiment 22
1, Preparation of catalysts:
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] benzene part is with embodiment ten.
1,3-two [two (4-bromophenyl) phosphinomethyl] benzene palladium chloride synthetic
With PdCl 2(MeCN) 2(130.0mg 0.5mmol) is dissolved in 10mLCH 2Cl 2In (fully deoxygenation and dewater), obtain solution (1).With 1,3-two [two (4-bromophenyl) phosphinomethyl] benzene part (434.6mg, 0.55mmol) (preparation with embodiment eight) be dissolved among the 10mLTHF (fully deoxygenation and dewater), obtain solution (2).Then solution (1) is added drop-wise in the solution (2), at room temperature fully stirred 3 hours, rotary evaporation is removed CH 2Cl 2, obtain filemot solid complexes 435mg behind THF and the MeCN, productive rate 90%. 31P NMR (121.5MHz, CDCl 3): δ=-30.4ppm (H 3PO 4Be external standard); MALDI-TOF MS (C 32H 24 79Br 4P 2Pd[M-2Cl] 2+): theoretical value: 892.2, measured value: 892.3.Ultimate analysis (C 32H 24Br 4Cl 2P 2PdTHF): theoretical value (%): C 41.59, and H 3.10; Measured value (%): C 41.72, and H 2.99.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 3.7mg (3.8 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 8.2mL methylaluminoxane (MAO) again, make Al/Pd=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.1 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 40%, C 6: 23%, C 8: 37%.Wherein alpha-olefin accounts for 88%.
Embodiment 23
1, Preparation of catalysts:
1, the preparation of 2-two [two (3, the 5-dibromo phenyl) phosphinomethyl] benzene part
Under the nitrogen protection; in the two neck round-bottomed flasks of a 50mL, add 1 successively; 2-two [two (3; the 5-dibromo phenyl) phosphoryl methyl] and benzene (284.4mg, 0.25mmol), trichlorosilane (339mg; 2.5mmol); triethylamine (380mg, 2.75mmol) and toluene (10mL) then behind 120 ℃ of stirring and refluxing 5h. cool to room temperature, add the saturated NaHCO of 0.5mL 3The aqueous solution.This mixture at room temperature continues to stir 5min, removes by filter precipitation, and precipitates 3 times with toluene drip washing, each 15mL.Rotary evaporation removes to desolvate and obtains 1 of white, 2-two [two (3, the 5-dibromo phenyl) phosphinomethyl] benzene 248.8mg, productive rate 90%. 1H NMR (300MHz, CDCl 3, TMS); δ=7.40～7.60 (m, 12H), 7.02～6.95 (t, 2H), 6.72 (d, J=6.0Hz, 2H), 3.26 (d, J=14.1,2H); 31P NMR (121.5MHz, CDCl 3): δ=-18.1ppm (H 3PO 4Be external standard).Ultimate analysis (C 32H 20Br 8P 2): theoretical value (%): C 34.76, and H 1.82; Measured value (%): C 34.56, and H 1.77.
1,2-two [two (3, the 5-dibromo phenyl) phosphinomethyl] benzene Nickel Chloride synthetic
With NiCl 26H 2(42.8mg 0.18mmol) is dissolved in the 10mL methyl alcohol O, is added drop-wise to 1 then, and (221.1mg is in 10mL THF solution 0.2mmol) for benzene for 2-two [two (3, the 5-dibromo phenyl) phosphinomethyl].This mixture at room temperature continues to stir 2h.Except that after desolvating, (3 * 15mL) washing precipitations, then dry in a vacuum 2h obtains solid phase prod russet (195.7mg, productive rate 88%) at last with ether. 31P NMR (CDCl 3): δ=-29.4ppm (H 3PO 4Be external standard); MALDI-TOF MS (C 32H 20 79Br 8P 2Ni[M-2Cl] 2+): theoretical value: 1154.32, measured value: 1154.22.Ultimate analysis (C 32H 20 79Br 8P 2NiCl 2THF): theoretical value (%): C 33.07, and H 2.16%; Experimental value (%): C 33.19%, and H 2.02%.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 5.1mg (4.1 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 8.8mL methylaluminoxane (MAO) again, make Al/Ni=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 0.8 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 37%, C 6: 24%, C 8: 38%, C 12: 1%.Wherein alpha-olefin accounts for 86%.
Embodiment 24
1, change the preparation of agent:
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] propane part
Under the nitrogen protection; in the two neck round-bottomed flasks of a 50mL, add 1 successively; 3-two [two (4-bromophenyl) phosphoryl methyl] propane (103.6mg, 0.136mmol), trichlorosilane (0.20mL; 2.0mmol); triethylamine (0.3mL, 2.2mmol) and toluene (15mL), then at 120 ℃ of stirring and refluxing 5h; behind the cool to room temperature, add the saturated NaHCO of 0.5mL 3The aqueous solution.Then this mixture at room temperature stirs 5min again, filters the elimination precipitation, and precipitates 3 times with toluene drip washing, each 15mL.Rotary evaporation removes to desolvate and obtains 1 of white, 3-two [two (4-bromophenyl) phosphinomethyl] propane (179.7mg, productive rate 91%). 1H NMR (300MHz, CDCl 3): δ=7.67～7.44 (m, 16H), 4.34～4.82 (m, 2H), 3.56 (t, 4H); 31P NMR (121.5MHz, CDCl 3): δ=-10.0ppm (H 3PO 4Be external standard).Ultimate analysis (C 27H 22Br 4P 2): theoretical value (%): C 44.54, H3.05; Measured value (%): C 44.62, and H 3.29.
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] propane Nickel Chloride
With NiCl 26H 2O (23.8mg, 0.10mmol) be dissolved in the methyl alcohol of 10mL after, be added drop-wise to 1, (76.6mg is in 10mL THF solution 0.11mmol) for 3-two [two (4-bromophenyl) phosphinomethyl] propane.This mixture continues to stir 2h in room temperature.Except that after desolvating, (3 * 15mL) washing precipitations and dry in a vacuum 2h obtain title complex b russet (68.6mg, 90%) at last with ether. 31PNMR (121.5MHz, CDCl 3): δ=-11.3ppm (H 3PO 4Ext.reference); MALDI-TOFMS (C 27H 22P 2 79Br 4Ni) [M-2Cl] 2+: theoretical value: 782.73, experimental value: 782.72.Ultimate analysis (C 27H 22P 2Br 4NiCl 21/2THF): theoretical value C:38.93%, H 2.91%; Experimental value: C 38.67%, H 2.84%.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.5mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL1 with syringe, the 2-ethylene dichloride adds 10.7mL methylaluminoxane (MAO) again, makes Al/ Ni=3000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 4.1 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 75%, C 6: 25%.Wherein alpha-olefin accounts for 81%.
Embodiment 25
1, Preparation of catalysts:
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] propane part: method is with embodiment 24.
1, the preparation of 3-two [two (4-bromophenyl) phosphinomethyl] propane Nickel Bromide
With NBr 2(DME) (30.8mg 0.10mmol) directly is added to 1, and (76.6mg is in 20mL dichloromethane solution 0.11mmol) for propane for 3-two [two (4-bromophenyl) phosphinomethyl].This mixture continues to stir 2h in room temperature.Except that after desolvating, (3 * 15mL) washing precipitations and dry in a vacuum 2h obtain title complex russet (68.6mg, 90%) at last with ether.IR(KBr，ν/cm -1)：3371，3048，2974，2939，2740，2678，2492，2355，1916，1633，1572，1478，1434，1384，1304，1263，1185，1171，1100，1069，1036，1009，971，806，732，702，661，571。 31P NMR (121.5MHz, CDCl 3): δ=-11.3ppm (H 3PO 4Ext.reference); MALDI-TOF MS (C 27H 22P 2 79Br 4Ni) [M-2Br] 2+: calculated value: 782.73, experimental value: 782.72.Ultimate analysis (C 27H 22Br 6NiP 2NEt 3) theoretical value (%): C 37.80, and H 3.53, and N 1.34; Experimental value (%): C 38.22, and H 3.94, and N 1.42.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 9.5mg (10 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.24 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 95%, C 65%.Wherein alpha-olefin accounts for 79%.
Embodiment 26
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 10.4mg (10 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 7.2mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.3 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 40%, C 6: 50%, C 8: 10%.Wherein alpha-olefin accounts for 82%.
Embodiment 27
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 10.5mg (10 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 10.5mL methylaluminoxane (MAO) again, make Al/Ni=1500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 21%, C 6: 60%, C 8: 19%.Wherein alpha-olefin accounts for 81%.
Embodiment 28
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 10.5mg (10 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 14.0mL methylaluminoxane (MAO) again, make Al/Ni=2000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4.36%, C 6: 34%, C 8: 30%.Wherein alpha-olefin accounts for 80%.
Embodiment 29
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 10.5mg (10 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 17.5mL methylaluminoxane (MAO) again, make Al/Ni=2500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 5.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 67%, C 6: 23%, C 8: 10%.Wherein alpha-olefin accounts for 77%.
Embodiment 30
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 5.2mg (5 * 10 that adds step 1 gained -6Mol) and triphenyl phosphorus (2.6mg, 1 * 10 -5Mol), the amount of substance of triphenyl phosphorus is 2 times of title complex.And then vacuumize and replace 3 times with ethene.Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 5.0 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 40%, C 6: 5%, C 8: 34%, C 10: 26%.Wherein alpha-olefin accounts for 78%.
The embodiment hentriaconta-
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 5.2mg (5 * 10 that adds step 1 gained -6Mol) and triphenyl phosphorus (7.8mg, 3 * 10 -5Mol), the amount of substance of triphenyl phosphorus is 6 times of title complex.And then vacuumize and replace 3 times with ethene.Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.9 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 20%, C 6: 25%, C 8: 12%, C 10: 43%.Wherein alpha-olefin accounts for 85%.
Embodiment 32
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 5.2mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 0 ℃ of steady temperature, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.1 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 12%, C 6: 23%, C 8: 55%.Wherein alpha-olefin accounts for 81%.
Embodiment 33
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 5.2mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 50 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.6 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 61%, C 6: 20%, C 8: 19%.Wherein alpha-olefin accounts for 86%.
Embodiment 34
1, Preparation of catalysts: method is with embodiment 25.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 5.2mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 70 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.0 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 37%, C 6: 26%, C 8: 10%, C 10: 27%.Wherein alpha-olefin accounts for 88%.
Embodiment 35
1, Preparation of catalysts:
8-[two (4-bromophenyl) phosphine methyl]-preparation of quinoline part
Under the nitrogen protection; in the two neck round-bottomed flasks of a 50mL, add 8-[two (4-bromophenyl) phosphine oxygen methyl successively]-quinoline (0.4378g; 0.87mmol); trichlorosilane (0.90mL; 8.7mmol), triethylamine (1.3mL, 9.6mmol) and toluene (15mL); behind 120 ℃ of stirring and refluxing 5h. cool to room temperature, add the saturated NaHCO of 0.5mL then 3The aqueous solution.Then this mixture at room temperature stirs 5min again, filters the elimination precipitation, and precipitates 3 times with toluene drip washing, each 15mL.Rotary evaporation removes to desolvate and obtains 8-[two (4-bromophenyl) the phosphine methyl of white]-quinoline (0.16g, productive rate 38%). 1H?NMR(300MHz，CDCl 3)：δ＝7.2～8.01(m，14H)，2.66(s，2H)。 31P NMR (121.5MHz, CDCl 3): δ=-43.2ppm (H 3PO 4Be external standard).Ultimate analysis (C 22H 16Br 2NP): theoretical value (%): C 54.46, and H 3.32, and N 2.89; Measured value (%): C 54.66; H 3.29; N 2.71.
8-[two (4-bromophenyl) phosphine methyl]-quinoline NiCl 2Preparation
With NiCl 26H 2O (23.8mg, 0.10mmol) be dissolved in the methyl alcohol of 10mL after, be added to 8-[two (4-bromophenyl) phosphine methyl]-quinoline part (48.5mg, 20mLCH 0.1mmol) 2Cl 2In (through abundant deoxygenation and dewater) solution, at room temperature fully stirred 3 hours, rotary evaporation is removed CH 2Cl 2After, obtain solid complexes, with anhydrous diethyl ether washing three times, each 10mL obtains brown straight product 58.4mg, productive rate 95%.IR (KBr, ν cm -1): 3369,2374,1629,1586,1471,1433,1384,1300,1255,1170,1121,1075,1060,1032,1001,946,804,733,664.MALDI-TOF MS (C 22H 16 79Br 2NNiP) [M-2Cl] 2+: calculated value: 543.65, experimental value: 543.66.Ultimate analysis (C 22H 16Br 2Cl 2NniP) theoretical value (%): C 42.98; H 2.62; N 2.28; Measured value (%): C 43.14, and H 2.71, and N 2.09.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.1mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 1.8mL methylaluminoxane (MAO) again, make Al/Ni=500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.9 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 45%, C 6: 45%, C 8: 10%.Wherein alpha-olefin accounts for 78%.
Embodiment 36
1, Preparation of catalysts:
8-[two (4-bromophenyl) phosphine methyl]-preparation of quinoline part: with embodiment 35.
8-[two (4-bromophenyl) phosphine methyl]-quinoline NiBr 2Preparation
With NBr 2(DME) (30.8mg 0.10mmol) directly is added to 8-[two (4-bromophenyl) phosphine methyl]-quinoline part (48.5mg, 20mLCH 0.1mmol) 2Cl 2In (through abundant deoxygenation and dewater) solution, at room temperature fully stirred 3 hours, rotary evaporation is removed CH 2Cl 2After, obtain solid complexes, with anhydrous diethyl ether washing three times, each 10mL obtains straight product 335mg, productive rate 95%.IR(KBr，ν/cm -1)：3372，2371，1631，1576，1478，1437，1385，1299，1262，1169，1123，1098，1069，1038，1009，936，814，743，700，630。MALDI-TOF MS (C 22H 16 79Br 2NNiP) [M-2Br] 2+: calculated value: 543.65, experimental value: 543.66. ultimate analysis (C 22H 16Br 4NNiP2CH 2Cl 2): theoretical value (%): C 33.00, and H 2.31, and N 1.60; Measured value (%): C 33.29%, and H 2.08%, and N 1.73%.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 1.8mL methylaluminoxane (MAO) again, make Al/Ni=500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.5 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 75%, C 6: 15%, C 8: 10%.Wherein alpha-olefin accounts for 66%.
Embodiment 37
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 8.7mg (10 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 7.2mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.8 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 44%, C 6: 29%, C 8: 27%.Wherein alpha-olefin accounts for 68%.
Embodiment 38
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 5.4mL methylaluminoxane (MAO) again, make Al/Ni=1500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 4.3 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 48%, C 6: 6%, C 8: 46%.Wherein alpha-olefin accounts for 71%.
Embodiment 39
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 7.2mL methylaluminoxane (MAO) again, make Al/Ni=2000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 1.04 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 27%, C 6: 30%, C 8: 43%.Wherein alpha-olefin accounts for 76%.
Embodiment 40
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 9.0mL methylaluminoxane (MAO) again, make Al/Ni=2500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 2.04 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 27%, C 6: 30%, C 8: 43%.Wherein alpha-olefin accounts for 73%.
Embodiment 41
1, Preparation of catalysts: method is with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6Mol) and triphenyl phosphorus (2.6mg, 1 * 10 -5Mol), the amount of substance of triphenyl phosphorus is 2 times of title complex.And then vacuumize and replace 3 times with ethene.Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.9 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 33%, C 6: 42%, C 8: 2%, C 10: 23%.Wherein alpha-olefin accounts for 62%.
Embodiment 42
1, Preparation of catalysts: method is with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6Mol) and triphenyl phosphorus (7.8mg, 3 * 10 -5Mol), the amount of substance of triphenyl phosphorus is 6 times of title complex.And then vacuumize and replace 3 times with ethene.Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 5.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 86%, C 6: 14%.Wherein alpha-olefin accounts for 77%.
Embodiment 43
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 0 ℃ of steady temperature, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.2 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 17%, C 6: 33%, C 8: 20%, C 10: 30%.Wherein alpha-olefin accounts for 72%.
Embodiment 44
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 50 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 4.1 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 31%, C 6: 32%, C 8: 10%, C 10: 27%.Wherein alpha-olefin accounts for 69%.
Embodiment 45
1, Preparation of catalysts: with embodiment 36.
2, the oligomerisation of ethene: the 250mL three neck round-bottomed flasks that magnetic stick will be housed are 130 ℃ of successive dryings 6 hours, vacuumize while hot and with nitrogen replacement 3 times.The catalyzer 4.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 70 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 30 minutes.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.1 * 10 4G oligomers/molNih.Oligopolymer distributes: C 4: 11%, C 6: 38%, C 8: 40%, C 10: 11%.Wherein alpha-olefin accounts for 63%.
Embodiment 46
1, Preparation of catalysts
8-[two (4-bromophenyl) phosphine methyl]-preparation of quinoline part: with embodiment 35.
8-[Bis (4-bromophenyl) phosphinomethyl]-quninolineNiCl (1-Naphthyl) (PPh 3) preparation
With NiCl (1-Naphthyl) (PPh 3) 2(373.0mg 0.5mmol) is dissolved in 10mLCH 2Cl 2In (through abundant deoxygenation and dewater), obtain solution (1).With 8-[two (4-bromophenyl) phosphine methyl]-(267.0mg 0.55mmol) is dissolved in 20mLCH to the quinoline part 2Cl 2In (through abundant deoxygenation and dewater), obtain solution (2).Then solution (1) is added drop-wise in the solution (2), at room temperature fully stirred 3 hours, rotary evaporation is removed CH 2Cl 2After, obtain solid complexes, with anhydrous diethyl ether washing three times, each 10mL obtains straight product 335mg, productive rate 95%.IR (KBr, ν/cm -1): 3373,1635,1542,1444,1437,1326,1310,1226,1217,1069,1004,937,814,724,689; MALDI-TOF MS (C 32H 23 79Br 2NNiP) [M-Cl] +Theoretical value: 667.15, measured value: 667.13.Ultimate analysis (C 32H 23Br 2ClNNiP): theoretical value (%): C 54.40, and H 3.28, and N 1.98; Measured value (%): C 54.29, and H 3.08, and N 1.73.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.5mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 10%, C 6: 13%, C 8: 21%, C 10: 34%, C 12: 22%.Wherein alpha-olefin accounts for 91%.
Embodiment 47
1, Preparation of catalysts: with implementing 46.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.5mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject 30mL toluene with syringe, add 7.2mL methylaluminoxane (MAO) again, make Al/Ni=2000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 8.1 * 10 5G oligomers/molNi/h.Oligopolymer distributes: C 4: 11%, C 6: 9%, C 8: 20%, C 10: 34%, C 12: 26%.Wherein alpha-olefin accounts for 90%.
Embodiment 48
1, Preparation of catalysts:
8-[two (4-bromophenyl) phosphine methyl]-preparation of quinoline part: with embodiment 35.
8-[Bis (4-bromophenyl) phosphinomethyl]-quninolineNiCl (phenyl) (PPh 3) preparation
With NiCl (Phenyl) (PPh 3) 2(347.9mg 0.5mmol) is dissolved in 10mLCH 2Cl 2In (through abundant deoxygenation and dewater), obtain solution (1).With 8-[two (4-bromophenyl) phosphine methyl]-(267.0mg 0.55mmol) is dissolved in 20mLCH to the quinoline part 2Cl 2In (through abundant deoxygenation and dewater), obtain solution (2).Then solution (1) is added drop-wise in the solution (2), at room temperature fully stirred 3 hours, rotary evaporation is removed CH 2Cl 2After, obtain solid complexes, with anhydrous diethyl ether washing three times, each 10mL obtains straight product 312mg, productive rate 95%.IR (KBr, ν/cm -1): 3363,1625,1538,1451,1420,1311,1298,1204,1069,997,943,825,722,643; MALDI-TOFMS (C 28H 21 79Br 2NNiP) [M-Cl] +Theoretical value: 618.43, measured value: 618.47.Ultimate analysis (C 28H 21Br 2ClNNiP): theoretical value (%): C 51.23, and H 3.22, and N 2.13; Measured value (%): C51.49, H 3.06, and N 1.89.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 4.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 17%, C 6: 41%, C 8: 19%, C 10: 10%, C 12: 13%.Wherein alpha-olefin accounts for 94%.
Embodiment 49
1, Preparation of catalysts: with embodiment 48.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 5.4mL methylaluminoxane (MAO) again, make Al/Ni=1500.Under 30 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 6.2 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 19%, C 6: 39%, C 8: 13%, C 10: 16%, C 12: 13%.Wherein alpha-olefin accounts for 90%.
Embodiment 50
1, Preparation of catalysts: with embodiment 48.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 0 ℃ of steady temperature, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.5 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 11%, C 6: 47%, C 8: 15%, C 10: 15%, C 12: 14%.Wherein alpha-olefin accounts for 95%.
Embodiment 51
1, Preparation of catalysts: with embodiment 48.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 50 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 4.2 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 22%, C 6: 39%, C 8: 16%, C 10: 33%.Wherein alpha-olefin accounts for 97%.
Embodiment 52
1, Preparation of catalysts: with embodiment 48.
2, the oligomerisation of ethene:
250mL three neck round-bottomed flasks that magnetic stick is housed 130 ℃ of successive dryings 6 hours, are vacuumized and while hot with nitrogen replacement 3 times.The catalyzer 3.3mg (5 * 10 that adds step 1 gained -6And then vacuumize and with ethene displacement 3 times mol).Inject the 30mL methylene dichloride with syringe, add 3.6mL methylaluminoxane (MAO) again, make Al/Ni=1000.Under 70 ℃ of steady temperatures, keep the ethylene pressure of 1atm, vigorous stirring 1 hour.Use 5% dilute hydrochloric acid termination reaction at last.GC measures oligopolymer.Oligomerisation activity: 3.9 * 10 5G oligomers/molNih.Oligopolymer distributes: C 4: 11%, C 6: 34%, C 8: 19%, C 10: 34%.Wherein alpha-olefin accounts for 91%.

Claims (7)

1, a kind of ethylene oligomerization catalysis system comprises Primary Catalysts and promotor, and described Primary Catalysts is the Ni (II) or Pd (II) title complex of P^P (N) double coordination, and its structure is respectively shown in A formula and B formula:
In the formula:
The coordination metal M is Ni or Pd;
R and R ' are respectively the alkane substituting group;
R " be hydrogen or alkane substituting group;
The aromatic base of Ar for replacing;
X is Cl or Br;
Described promotor is methylaluminoxane (MAO), cyclooctadiene base nickel (Ni (COD) 2), trimethyl aluminium (AlMe 3), triethyl aluminum (AlEt 3), triisobutyl aluminium (Al (iso-Bu) 3), diethyl aluminum chloride (Et 2AlCl) or ethylaluminum dichloride (EtAlCl 2);
Promotor/Primary Catalysts mol ratio is 500-3000;
The temperature of reaction of above-mentioned catalyst system is-10-80 ℃.
2, catalyst system as claimed in claim 1 is characterized in that, also adds triphenyl phosphorus in the described catalyst system, and the amount of substance of its adding is 1-10 a times of Primary Catalysts.
3, catalyst system as claimed in claim 1 is characterized in that, in structure A formula and the B formula:
R is: methylene radical, 1, the 2-ethylidene, 1,2-(methyl) ethylidene, 1,2-(ethyl) ethylidene, 1,2-(1-methyl-2-ethyl) ethylidene, 1, the 3-propylidene, 1,3-(1-methyl) propylidene, 1, the 4-butylidene, 1,4-(1-methyl) butylidene, 1, the 2-xylylene, 1, the 3-xylylene, 1,1 '-dinaphthalene-2,2 '-dimethyl, 1,2-naphthalene dimethyl, 1,3-naphthalene dimethyl, 1,4-naphthalene dimethyl, 1,7-naphthalene dimethyl, 1,8-naphthalene dimethyl, 3,4-naphthalene dimethyl, 2,3-naphthalene dimethyl, 2,4-naphthalene dimethyl, 2,2 '-biphenyl dimethyl, 3,3 '-biphenyl dimethyl, 2,5-furans dimethyl, 2,3-furans dimethyl, 2,3-cumarone dimethyl, 5,6-benzoglyoxaline dimethyl, 2,5-pyrroles's dimethyl, 2,3-pyrroles's dimethyl, 2,6-thiophene dimethyl, 4,6-thionaphthene dimethyl, 2,6-pyridine dimethyl, 2,3-pyridine dimethyl, 2,4-pyridine dimethyl, 3,4-pyridine dimethyl, 3,5-pyridine dimethyl, 2,2 '-dipyridyl-4,4 '-dimethyl, 1,1-ferrocene dimethyl, 2,3-pyrazine dimethyl, 2,4-quinoline dimethyl, 2,6-quinoxaline-dimethyl, 2,3-two (2-pyridyl) quinoxaline-6, the 7-dimethyl, 2, the 4 benzoic acid dimethyl, 1,10-phenanthroline-5,6-dimethyl, 1,10-phenanthroline-2, the 9-dimethyl, 1,2-(3-oil of mirbane) dimethyl, 1,2-(4-oil of mirbane) dimethyl, 1,3-(4-oil of mirbane) dimethyl, 1,3-(5-oil of mirbane) dimethyl, 2,3-fluorobenzene dimethyl, 3,4-chlorobenzene dimethyl, 2,3-bromobenzene dimethyl, 2,4-bromobenzene dimethyl, 3,4-bromobenzene dimethyl, 3,5-bromobenzene dimethyl, 2,3-iodobenzene dimethyl, 2,4-iodobenzene dimethyl, 3,4-iodobenzene dimethyl, 3,5-iodobenzene dimethyl, 2,3-methyl-phenoxide dimethyl, 2,4-methyl-phenoxide dimethyl, 3,4-methyl-phenoxide dimethyl, 3,5-methyl-phenoxide dimethyl, 4,5-thiazole dimethyl or 3,5-pyrazoles dimethyl;
R ' is a methyl, phenyl, 1-naphthyl;
R " be hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, phenyl, 1-naphthyl, 9-phenanthryl, 9-anthryl;
Ar is: 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 3,5-dibromo phenyl, 2,6-dibromo phenyl, 2,4-dibromo phenyl 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 3,5-diiodo-phenyl, 2,6-diiodo-phenyl, 2,4-diiodo-phenyl, 2-carboxyl phenyl, 3-carboxyl phenyl, 4-carboxyl phenyl, 3,5-dicarboxyl phenyl, 2,6-dicarboxyl phenyl or 2,4-dicarboxyl phenyl; Substituting group on the Ar base is electrophilic halogen group or carboxyl.
4, catalyst system as claimed in claim 1 is characterized in that, regulates the mol ratio or the temperature of reaction of Primary Catalysts/promotor, and corresponding the variation also will be taken place in the distribution of gained oligopolymer, and the oligopolymer of gained comprises C 4, C 6, C 8, C 10To C 20
5, a kind of method for preparing above-mentioned Primary Catalysts, its key step is as follows:
A) part is synthetic
With Ar 2P (O)-R-P (O) Ar 2Or 8-[two (substituted aryl) phosphinomethyl] quinoline (8-Ar 2P (O) CH 2-Quninoline) and HSiCl 3(mol ratio is 1: 5～50) is dissolved in exsiccant toluene, and (10～50mL), stirring and refluxing 5～20 hours is cooled to room temperature, uses saturated sodium bicarbonate aqueous solution (with HSiCl then 3Volume ratio be 1～2), excessive HSiCl neutralizes 3With the acid that reaction is produced, filter, with the distillation of gained filtrate decompression, obtain product A r 2P-R-PAr 2Or 8-Ar 2PCH 2-Quninoine;
B) preparation of Primary Catalysts
The part of steps A preparation is made solution 1 in the ratio that 1mmol is dissolved in 10～20mL exsiccant tetrahydrofuran (THF) (THF);
Metal halide is dissolved in CH by 0.9mmol 2Cl 2/ MeOH (10～20mL) or CH 2Cl 2(20mL) ratio in the mixed solvent is made solution 2;
Under stirring at room, solution 2 is added drop-wise in the solution 1, continue reaction 10 minutes～5 hours, boil off solvent then under the decompression and obtain precipitation, (3 * 10mL) washings obtain pure title complex with ether.
6, method as claimed in claim 5 is characterized in that, the metal halide described in the step B is nickelous chloride (NiCl 2), Palladous chloride (PdCl 2), triphenylphosphine phenyl nickelous chloride ((PPh 3) 2PhNiCl), nickelous bromide (NiBr 2), 1 dme nickelous bromide (NiBr 2(DME)), 1,5-cyclooctadiene base Palladous chloride (PdCl 2(COD)), triphenylphosphine (1-naphthyl) nickelous bromide ((PPh 3) 2(1-naphthyl) NiBr) or acetonitrile Palladous chloride (PdCl 2(MeCN)).
7, the described catalyst body of above-mentioned each claim ties up to the application in the ethylene oligomerization reaction.
CNA031423280A 2003-06-13 2003-06-13 Ethylene oligomerization catalysis system and preparation method and application thereof Pending CN1566041A (en)

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