CN1156415C - Ethylene oligomerization after-trasition metal coordination catalyst and its application - Google Patents

Ethylene oligomerization after-trasition metal coordination catalyst and its application Download PDF

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CN1156415C
CN1156415C CNB011202149A CN01120214A CN1156415C CN 1156415 C CN1156415 C CN 1156415C CN B011202149 A CNB011202149 A CN B011202149A CN 01120214 A CN01120214 A CN 01120214A CN 1156415 C CN1156415 C CN 1156415C
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ethene
imido grpup
catalyst
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tert
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CN1394834A (en
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孙文华
王乐勇
韩玲芹
李子龙
胡友良
李秀华
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Institute of Chemistry CAS
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Abstract

The present invention discloses a transitional metal coordination catalyst after ethylene oligomerization and the application of the transitional metal coordination catalyst in the ethylene oligomerization. The transitional metal coordination catalyst has the following structural general formula, wherein R1 is isopropyl (i-Pr) or methyl, R2 is hydrogen or methyl, R3 is tertiary butyl or methyl, M is cobalt or nickel, and X is chlorine or bromine; the following conditions are met simultaneously: when R1 equals to i-Pr, R2 equals to H; when M equals to Co, X equals to Cl; when M equals to Ni, X equals to Br. The catalyst of the present invention has the advantages of simple preparation, easy purification, good compound stability, convenient preservation and good reproducibility of catalyst activity, and the catalyst is convenient for mass production.

Description

Ethylene oligomerization after-trasition metal coordination catalyst and uses thereof
Technical field:
The present invention relates to ethylene oligomerization after-trasition metal coordination catalyst and be used for the purposes of ethylene oligomerization.
Background technology:
The catalyzed ethylene oligomerisation can the scale operation normal olefine, and its product is important organic chemical industry's intermediate, has become an individual branches in the petrochemical industry.In recent years, the research of rear 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, presses for preparation C 4, C 6, C 8Oligopolymer Deng ethene.
Since the seventies, polymerization of transition metal complex homogeneous catalytic olefin and oligomerisation research are subject to people's attention, and people make great efforts to study raw catalyst and improve existing catalyzer, 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 already the report United States Patent (USP): USPatent 3686351,19720711 and US Patent 3676523,19720822, developed into SHOP (the Shell Higher OlefinProcess) technological process of shell (Shell) company based on this patented technology.This is an O-P bridging type ligand catalyst, and the ethylene oligomerization catalysis activity is approximately 10 5Gram ethene/(mole Ni hour) is toxic organic phosphine group in the catalyzer, has the character of the complicated and less stable of catalyzer synthesis step again.Multiple patents such as O-O, P-N, P-P type and N-N type coordination nickel catalyzator had been developed afterwards again, wherein the nitrogen-atoms catalyzer of doing the coordination tooth is subjected to people's extensive attention, as recent patent: Jpn.Kokai Tokkyo Koho JP11060627, A2 2 Mar 1999 Heisei:PCT Int.Appl.WO 9923096 A1 14May 1999; PCT Int.Appl.WO 9951550 A1 14 Oct 1999.Yet the synthesis step of above-mentioned catalyzer and preparation method are relatively complicated, and catalytic activity is 10 4To 10 6Gram ethene/(mole Ni hour).
Summary of the invention:
Ethylene oligomerization after-trasition metal coordination catalyst of the present invention, promptly 2,6-di-imidogen phenol derivatives Ni or Co title complex, general structure is:
Figure C0112021400041
Wherein R1 is sec.-propyl (i-Pr) or methyl (Me); R2 is hydrogen (H) or methyl (Me); R3 is the tertiary butyl (t-Bu) or Me, and M is cobalt (Co) or nickel (Ni); X is chlorine (Cl) or bromine (Br).
And should meet the following conditions simultaneously:
During R1=i-Pr, R2=H;
During M=Co, X=Cl;
During M=Ni, X=Br.
The preparation of ethylene oligomerization after-trasition metal coordination catalyst of the present invention is with 2,6-(di-imidogen) fortified phenol part and (DME) NiBr 2And CoCl 26H 2The O reaction makes ethylene oligomerization after-trasition metal coordination catalyst.
The preparation of ethylene oligomerization after-trasition metal coordination catalyst of the present invention, raw material comprises: p-tert-butylphenol, p-methyl phenol, formaldehyde, Manganse Dioxide, organic amine, organic solvent, cobalt chloride and (DME) NiBr 2And promotor trimethylammonium alumina alkane (MAO), be commercially available analytical reagent.Purifying after catalyst ligand is synthetic adopts recrystallization; The catalyzer purifying is to concentrate to separate out solid product in organic solvent, and washs with ether.
The preparation of ethylene oligomerization after-trasition metal coordination catalyst of the present invention, step is carried out in the following order:
1. the preparation of catalyst ligand: see Fig. 1.
2,6-diformazan aldehyde radical fortified phenol derivative is by relevant document (Drago, R.S.; Desmond, M.J.; Wrden, D.B.J.Am.Chem.Soc.1983,105,2287) utilize corresponding phenol and formaldehyde reaction, utilize the Manganse Dioxide oxidation then and get.
The preparation of part then is by 2, and 6-diformazan aldehyde radical phenol derivatives and organic amine carry out 50 ℃ of nucleophilic reactions to the reflux conditions in ethanolic soln, slough water, form the group with imine moiety that contains carbon-to-nitrogen double bon, promptly 2, and 6-two (imido grpup) phenol derivatives.All synthetic 2,6-two (imido grpup) phenol derivatives all are confirmed through nuclear-magnetism, infrared, mass spectrum and ultimate analysis.Wherein the crystalline structure of representational part obtains conclusive evidence by the analysis of monocrystalline x-ray diffraction.
2.2, the cobalt complex Preparation of catalysts of 6-di-imidogen phenol derivatives:
With make 2,6-di-imidogen phenol derivatives and CoCl 26H 2O (1: 1) in molar ratio is blended in 25 ℃ or heated and stirred reaction in the ethanol, form title complex, separate out solid precipitation after concentrating, just obtain 2, the cobalt complex catalyzer of 6-(di-imidogen) phenol derivatives, its The Nomenclature Composition and Structure of Complexes is through hydrocarbon nitrogen ultimate analysis and FAB-MS and IR conclusive evidence.The structure of title complex 1 is confirmed through single crystal diffraction.
3.2, the preparation of the nickel complex as catalyst agent of 6-di-imidogen phenol derivatives:
With make 2,6-two (imido grpup) phenol derivatives and (DME) NiBr 2(1: 0.80) is blended in the dichloromethane solution 25 ℃ of stirring reactions 8 hours in molar ratio, form title complex, separate out solid precipitation after concentrating, wash with anhydrous diethyl ether, just obtain 2, the Ni composition catalyst of 6-di-imidogen phenol derivatives, it is formed through hydrocarbon nitrogen ultimate analysis and FAB-MS and IR conclusive evidence.
When catalyzer of the present invention was used for ethylene oligomerization catalysis, used catalytic reaction kettle was carried out nitrogen, ethylene gas displacement successively, makes reaction system in the ethylene gas environment.Then, add solvent toluene and promotor trimethylammonium alumina alkane in turn, the catalyzer 2 that reinjects, the brill of 6-di-imidogen phenol derivatives or the complex solution of nickel carry out the reaction of ethene normal pressure oligomerization catalysis under 25 ℃ of conditions.React after 30-40 minute, add acidifying ethanol termination reaction, formed oligomerization product normal olefine is present in the toluene solvant phase.The output of ethylene oligomerization product and distribution are tested with chromatogram-mass spectrometric hyphenated technique.
Catalyzer of the present invention, overcome the weakness of catalyzer synthesis step complexity, preparation difficulty in the prior art, developing New O-N heteroatoms coordination catalyst system, invented 2, the nickel of 6-di-imidogen phenol ligands and derivative thereof and the composition catalyst of cobalt, preparation is simple, purifying is easy, compound stability is better, is convenient to produce in enormous quantities, and preservation and the catalyst activity reproducibility of being convenient to catalyzer are good.The present invention and promoter aluminium alkyl oxygen alkane (as methylaluminoxane (MAO) etc.) are formed catalyst system, first Application is in vinyl polymerization, dimerization, trimer and a small amount of tetramer of ethene have been obtained, open up the frontier of post-transition metal ethylene polymerization catalyst, obtained the high ethylene oligomerization result of catalytic activity.The catalytic activity of different catalysts distributes wide, and the better catalytic activity of nickel complex is about 10 5Gram ethene/mol catalyst hour; The catalytic activity of cobalt (II) title complex is relatively poor, is about 10 3Gram ethene/mol catalyst hour;
Description of drawings:
Fig. 1 is a part synthetic reaction scheme
Fig. 2 is a part 2 among the embodiment 1, the crystalline structure of 6-two (2,6-di-isopropyl phenyl imido)-4-tert.-butyl phenol
Fig. 3 is among the embodiment 12, the crystalline structure of 6-two (2,6-diisopropyl phenyl imido grpup)-4-tert.-butyl phenol cobalt complex
Embodiment:
Embodiment 1:
Part 2; 6-two (2; 6-diisopropyl phenyl imido grpup)-and 4-tert.-butyl phenol synthetic: under nitrogen protection, with the 4-tertiary butyl-2,6-diformyl phenol (1.76g; 6mmol) dissolve in (25mL) in the ethanol solution; add 3 acetate again, be warming up to 50 ℃ then, stir in following half an hour and drip 2; 6-diisopropyl aniline (2.16g, ethanol solution 13.2mmol) (15mL).After dripping off, be heated to backflow, continue to stir after 2 hours, be chilled to room temperature, remove most of solvent under reduced pressure, the product mother liquor is placed in the refrigerator and spends the night, and separates out yellow crystals 2.8g, yield: 70%.m.p.192.5-193℃.IR(KBr)：3414(m)，3063(m)，2963，2869(s)，1629，1586(vs)，1540(s)，1460(s)，1360，1313，1282，1227，1179(s)，819，758(s)； 1H?NMR(CDCl 3)：δ1.27(24H，d，J＝6.8Hz)，1.49(9H，s)，3.04-3.14(4H，m)，7.24(6H，m)，7.5(1H，br)，8.37-8.80(3H，br)；EI-MS(m/z)：524(M +，7.8％)，509(5.1％)，349(23.6％)，348(100％)，319(5.5％)；176(12.3％)；Anal.Calcd.For?C 36H 48N 2O：C，82.39；H，9.22；N，5.34。Found：C，82.10；H，9.29；N，5.12％。This organic absolute structure obtains conclusive evidence through the analysis of monocrystalline x-ray diffraction.
2,6-two (diisopropyl phenyl imido grpup)-4-tert.-butyl phenol cobalt complex (1) Preparation of catalysts:
2, (104mg 0.2mmol) is dissolved in the 10mL dehydrated alcohol 6-two (2,6-di-isopropyl phenyl imido)-4-tert.-butyl phenol, is warming up to 50 ℃, stirs down and drips CoCl in the 10mins 26H 2O (47.6 milligrams, ethanolic soln 0.2mmol) dropwises, and continues reaction after 2 hours, remove excess ethanol under reduced pressure, add the 5mL anhydrous diethyl ether, the solid filtering of separating out is with ether washing (3 * 2mL), vacuum-drying gets 138 milligrams in green solid powder, yield: 76%.m.p.＞300℃.IR(KBr)：3427(br，s)，2964(s)，1638(vs)，1591(s)，1537(s)，1463(m)，1388，1363，1328，1289，1225，1127(m)，1059(m)； 1H?NMR(CDCl 3)：δ1.45(9H，s)，2.22(12H，s)，2.34(6H，s)，6.95(4H，s)，8.63(2H，s)；FAB-MS(m/z)：618(M +-Cl)，582(M +-2Cl)，525(M +-CoCl 2)；Anal.Calcd.for?C 36H 48N 2OCoCl 2·2H 2O：C，62.61；H，7.59；N，4.06。Found：C，62.37；H，7.19；N，3.80％。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry down 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 10 milliliters of MAO (1.4mol/1), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,6-diisopropyl phenyl imido grpup)-and the toluene solution of 4-tert.-butyl phenol cobalt complex (1) (13.7mg, 20 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 2 * 10 3Gram ethene/(mole Co hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 100%.
Embodiment 2:
Synthesizing of part with embodiment 1
2,6-two (2,6-diisopropyl phenyl imido grpup)-4-tert.-butyl phenol nickel complex (2) Preparation of catalysts:
Under nitrogen protection, in 30 milliliters of Schlenk pipes, add 2,6-two (2,6-diisopropyl phenyl imido grpup)-4-tert.-butyl phenol (167mg, 0.32mmol), (DME) NiBr 2(77 milligrams, 0.25mmol), inject the methylene dichloride of newly handling (10mL) then, stirred 18 hours at 25 ℃, steam and remove excessive methylene dichloride, add the 5mL anhydrous diethyl ether, the solid filtering of separating out is with ether washing (3 * 2mL).Vacuum-drying gets sap green pressed powder 124mg, yield: 73%.m.p.238℃(dec.).IR(KBr)：3389(br)，2964(m)，1637(s)，1538(s)，1463(m)，1390(m)，1363，1328，1289，1234，1177(m)，1060(m)；FAB-MS(m/z)：663(M +-Br)，582(M +-2Br)，525(M +-NiBr 2)；Anal.Calcd.for?C 36H 48N 2ONiBr 2·H 2O：C，56.80；H，6.62；N，3.68。Found：C，56.80；H，6.37；N，3.52％。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,6-di-isopropyl phenyl imido)-and the toluene solution of 4-tert.-butyl phenol nickel complex (2) (3.8mg, 5 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 1.2 * 10 5Gram ethene/(mole Ni hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 49.5%, C 6, 28.2%; C 8, 14.6%; C 10, 3.4%; C 12, 1.9%; C 14, 1.4%; C 16, 1.0%.
Embodiment 3:
Part 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-and 4-tert.-butyl phenol synthetic: utilize synthetic ligands 2 among the embodiment 1,6-two (2,6-diisopropyl phenyl imido grpup)-and the method for 4-tert.-butyl phenol, obtain yellow solid 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-and the 4-tert.-butyl phenol, yield: 79%.m.p:162.5-163 ℃.IR(KBr)：3368(Br)，2962(s)，1630，1588(s)，1469(s)，1369(s)，1310，1284，1263，1232，1190(m)，1091，1034，1006(m)，858，765(m)； 1HNMR(CDCl 3)：δ1.44(9H，s)，2.24(12H，s)，6.95-7.14(6H，m)，7.3-8.60(4H，br)；EI-MS(m/z)：412(M +，6.6％)，411(4.4％)，292(100％)，291(85.4％)，290(8.3％)，277(6.6％)，206(5.1％)，132(8.2％)，120(6.9％)，105(10.1％)；Anal.Calcd.for?C 28H 32N 2O：C，81.51；H，7.82；N，6.79。Found：C，81.22；H，8.21；N，6.34％。
2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-tert.-butyl phenol cobalt complex (3)
Preparation of catalysts:
Utilize embodiment 1 Synthetic 2,6-two (2,6-isopropyl phenyl imido grpup)-4-tert.-butyl phenol CoCl 2Method, utilize part 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-tert.-butyl phenol and CoCl 2Reaction obtains green solid, yield: 75%.m.p.＞300℃.IR(KBr)：3434(m)，2963(s)，1638(s)，1620(s)，1539(s)，1471(m)，1397，1381，1363，1327，1290(w)，1236，1184(m)；FAB-MS(m/z)：541(M +)，506(M +-Cl)，470(M +-2Cl)，412(M +-CoCl 2)；Anal.Caicd.forC 28H 32N 2O·CoCl 2：C，62.00；H，5.95；N，5.16。Found：C，61.65；H，5.89；N，4.90。
Ethene normal pressure oligomerisation: put into the stirring magneton in dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 10 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,6-3,5-dimethylphenyl imido grpup)-and the toluene solution of 4-tert.-butyl phenol cobalt complex (3) (11.5mg, 20 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 3 * 10 3Gram ethene/(mole Co hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 100%.
Embodiment 4:
Synthesizing of part with embodiment 3
2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-tert.-butyl phenol nickel complex (4) Preparation of catalysts:
Utilize embodiment 2 Synthetic 2s, 6-two (2,6-isopropyl phenyl imido grpup)-4-tert.-butyl phenol NiBr 2Method, utilize part 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-tert.-butyl phenol and (DME) NiBr 2Reaction obtains garnet solid, yield: 85%.m.p.208℃(Dec.).IR(KBr)：3391(br)，2961(m)，1640(s)，1535(s)，1472(s)，1400，1364，1334，1292(w)，1238，1182(m)；FAB-MS(m/z)：551(M +-Br)，471(M +-2Br)，414(M +-NiBr 2)；Anal.Calcd.for?C 28H 32N 2ONiBr 2·H 2O：C，51.81；H，5.28；N，4.32。Found：C，51.47；H，5.62；N，3.97。
Ethene normal pressure oligomerisation: under 120 ℃ of conditions, put into the stirring magneton in dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2,6-two (2, the 6-imino dimethyl benzene)-4-tert.-butyl phenol nickel complex (4) (3.2mg down, 5 μ mol) toluene solution utilizes malleation manual or automatic air supply device maintenance ethene in the polymerization process.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Live 1.9 * 10 5Gram ethene/(mole Ni hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 72%; C 6, 28%.
Embodiment 5:
Part 2,6-two (2,4,6-trimethylphenyl imido grpup)-and 4-tert.-butyl phenol synthetic: utilize synthetic ligands 2 among the embodiment 1, the method for 6-two (2,6-diisopropyl phenyl imido grpup)-4-tert.-butyl phenol, obtain yellow solid 2,6-two (2,4,6-trimethylphenyl imido grpup)-4-tert.-butyl phenol yield: 89%.m.p.106.5-107℃.IR(KBr)：3432(br)，2964，2914(m)，1630(vs)，1592(s)，1479(s)，1373，1206，1146，1005，856(s)，819，758(s)； 1H?NMR(CDCl 3)：δ1.45(9H，s)，2.22(12H，s).2.34(6H，s)，6.95(4H，s)，8.63(2H，s)；EI-MS(m/z)：440(M +，12.4％)，307(19.0％)，306(89.8％)，305(100％)，304(10.4％)， 220(10.0％)，135(9.6％)；Anal.Calcd.For?C 30H 36N 2O：C，81.78；H，8.24；N，6.36。Found：C，81.49；H，8.43；N，6.74。
2,6-two (2,4,6-trimethylphenyl imido grpup)-4-tert.-butyl phenol cobalt complex (5) Preparation of catalysts:
Utilize embodiment 1 Synthetic 2,6-two (2,6-isopropyl phenyl imido grpup)-4-tert.-butyl phenol CoCl 2Method, obtain green solid, yield: 45%.m.p.＞300℃.IR(KBr)：3435(br，s)，2960，2915(m)，1638(s)，1591(s)，1539(m)，1479(m)，1239，1201，1148(m)，1063，1028(m)；FAB-MS(m/z)：534(M +-Cl)，498(M +-2Cl)，441(M +-CoCl 2)；Anal.Calcd.for?C 30H 36N 2O·CoCl 2：C，63.16；H，6.36；N，4.91。Found：C，62.80；H，6.23；N，4.91。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry down 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 7 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,4,6-trimethylphenyl imido grpup)-4-tert.-butyl phenol cobalt complex (5) (11.4mg, 20 μ mol) toluene solution utilizes malleation manual or automatic air supply device maintenance ethene in the polymerization process.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 10 3Gram ethene/(mole Co hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 100%.
Embodiment 6:
Synthesizing of part with embodiment 5
2,6-two (2,4,6-trimethylphenyl imido grpup)-4-tert.-butyl phenol nickel complex (6) Preparation of catalysts:
Utilize embodiment 2 Synthetic 2s, 6-two (2,6-isopropyl phenyl imido grpup)-4-tert.-butyl phenol NiBr 2Method, utilize part 2,6-two (2,4,6-trimethylphenyl imido grpup)-4-tert.-butyl phenol and (DME) NiBr 2Reaction obtains garnet solid, yield: 85%.m.p.202℃(Dec).IR(KBr)：3380(br)，2960(m)，1638(s)，1536(s)，1364，1330，1292(w)，1239，1200(m)，1143(w)，1064，1024(s)，853(s)；FAB-MS(m/z)：579(M +-Br)，498(M +-2Br)，441(M +-NiBr 2)：Anal.Calcd.for?C 30H 36N 2ONiBr 2·H 2O：C，53.21；H，5.66；N，4.14。Found：C，53.58；H，5.29：N，4.48％。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,4,6-trimethylphenyl imido grpup)-4-tert.-butyl phenol nickel complex (6) (3.4mg, 5 μ mol) toluene solution utilizes malleation manual or automatic air supply device maintenance ethene in the polymerization process.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 2.1 * 10 5Gram ethene/(mole Ni hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 69%; C 6, 31%.
Embodiment 7:
Part 2; synthesizing of 6-two (2,6-diisopropyl phenyl imido grpup)-4-methylphenol: under nitrogen protection, 4-methyl-2; 6-diformyl phenol (704mg; 4.29mmol) join in the dehydrated alcohol (25mL), add 3 acetate again, be warming up to 50 ℃ then; stir down; drip 2 in half an hour, 6-diisopropyl aniline (1.90g, ethanol solution 10.73mmol) (15mL); after dripping off; be heated to backflow, continue to stir after 2 hours, be chilled to room temperature; remove most of solvent under reduced pressure; place refrigerator overnight, obtain yellow crystals 1.17g, yield: 56%.m.p.165-166℃。 1HNMR(CDCl 3)：δ1.27(27H，s)，2.48(3H，s)，3.08(4H.m)，7.23(6H，s)，8.17-8.59(4H，br)，13.43(1H，s)；EI-MS482(M -，3.0％)，307(21.9％)，306(100％)，292(5.0％)，250(5.9％)，176(20.9％)，32(6.0％)；IR(KBr)：3427(br，m)，3065(m)，2962(vs)，2869(m)，1630(vs)，1589(vs)，1462(vs)，1257(vs)，1183(vs)，1158(m)，1104(m)，1038，761，699；Anal.Calcd.for?C 33H 42ON 2：C，82.11；H，8.77：N，5.80。Found：C，82.44；H，8.83；N，5.85。
2,6-two (2,6-diisopropyl phenyl imido grpup)-4-methylphenol cobalt complex (7) Preparation of catalysts:
Utilize embodiment 1 Synthetic 2,6-two (2,6-diisopropyl phenyl imido grpup)-4-tertiary butyl base phenol CoCl 2Method, utilize part 2,6-two (2,6-isopropyl phenyl imido grpup)-4-methylphenol and CoCl 2Reaction obtains green solid, yield 56.1%.M.p.＞300℃(Dec)。FAB-MS(m/z)：612(M +)，576(M +-Cl)，539(M +-2Cl)，483(M +-CoCl 2)；IR(KBr)，3422(br，m)，2964(vs)，1637(vs)，1541(vs)，1230(s)，801，523；Anal.Calcd.for?C 33H 42N 2OCoCl 2：：C，64.71％；H，6.91；N，4.57。Found?C，64.73；H，6.96；N，5.03。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 10 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,6-isopropyl phenyl imido grpup)-and the toluene solution of 4-methylphenol cobalt complex (3) (12.4mg, 20 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 1.1 * 10 3Gram ethene/(mole Co hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 100%.
Embodiment 8
Synthesizing of part with embodiment 7
2, the preparation of 6-two (2,6-isopropyl phenyl imido grpup)-4-methylphenol nickel complex as catalyst agent (8):
Utilize embodiment 2 Synthetic 2s, 6-two (2,6-isopropyl phenyl imido grpup)-4-tert.-butyl phenol NiBr 2Method, utilize part 2,6-two (2,6-isopropyl phenyl imido grpup)-4-methylphenol and (DME) NiBr 2Reaction obtains garnet solid, yield: 50%.FAB-MS(m/z)：483(M +-NiBr 2)；IR3380(br，m)，2966(vs)，1638(vs)，1588(s)，1548(s)，1547(s)，1502，1343，1058，827，737，501，397。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,6-diisopropyl phenyl imido grpup)-and the toluene solution of 4-methylphenol nickel complex (4) (3.5mg, 5 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 1.4 * 10 5Gram ethene/(mole Ni hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 53%; C 6, 31%; C 8, 12%; C 10, 3%; C 12, 1%.
Embodiment 9:
Part 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-methylphenol synthetic
Utilize synthetic ligands 2 among the embodiment 7, the method for 6-two (2,6-isopropyl phenyl imido grpup)-4-methylphenol obtains red solid 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-methylphenol.Yield: 50.8%.m.p.155-156℃. 1H?NMR(CDCl 3)：δ2.15(12H，s)，2.27(6H，s)，2.38(3H，s)，6.89(4H，s)，8.49-8.53(4H，br)，13.57(1H，s)；EI-MS(m/z)：398(M +，9.9％)，399(M ++1，3.3％)，279(6.4％)，265(18.9％)，264(84.2％)，262(16.6％)，249(9.9％)，221(5.2％)，199(8.4％)，146(10.0％)，135(12.8％)，134(8.2％)，131(7.3％)，119(7.1％)，91(10.2％)，77(6.5％)，41(5.1％)，32(7.7％)；IR(KBr)：3444(br，m)，2917(s)，1630(vs)，1593(m)，1478(s)，1462(s)，855；Anal.Calcd.for?C 27H 30?N 2O：C，81.40；H，7.59；N，7.03。Found：C，82.24；H，7.68；N，6.87。
2, the preparation of 6-two (2,6-3,5-dimethylphenyl imido grpup)-4-methylphenol cobalt complex catalyzer (9):
Utilize embodiment 1 Synthetic 2,6-two (2,6-diisopropyl phenyl imido grpup)-4-methylphenol CoCl 2Method, utilize part 2,6-two (2,6-3,5-dimethylphenyl imido grpup)-4-methylphenol and CoCl 2Reaction obtains sap green solid, yield: 62.4%.m.p.264℃(Dec).FAB-MS(m/z)：500(M +)，464(M +-Cl)，371(M +-2Cl)；IR(KBR)：3442(br，m)，2972(m)，1634(s)，1541(vs)，1471(s)，1233(s)，1184，775；Anal.Calcd.for?C 25H 26N 2O·CoCl 2：C，60.02；H，5.24；N，5.60。Found：C，60.33；H，5.77；N，5.22。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 10 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,6-3,5-dimethylphenyl imido grpup)-and the toluene solution of 4-methylphenol cobalt complex (9) (11.8mg, 20 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 3 * 10 3Gram ethene/(mole Co hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 100%.
Embodiment 10
Synthesizing of part with embodiment 9
2, the preparation of 6-two (2,6-3,5-dimethylphenyl imido grpup)-4-methylphenol nickel complex as catalyst agent:
Utilize embodiment 2 Synthetic 2s, 6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol NiBr 2Method, obtain the garnet solid, yield: 98%.
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (3,5-3,5-dimethylphenyl imido grpup)-and the toluene solution of 4-methylphenol nickel complex (4) (3.2mg, 5 μ mol), utilize in the polymerization process manually or automatic air supply device keeps the malleation of ethene.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 1.5 * 10 5Gram ethene/(mole Ni hour)
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 71%; C 6, 39%.
Embodiment 11:
Part 2,6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol synthetic:
Utilize synthetic ligands 2 among the embodiment 7, the method for 6-two (2,6-isopropyl phenyl imido grpup)-4-methylphenol obtains yellow crystals 2,6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol, yield: 73.13%.m.p.155-156℃。IR(KBr)：3444(m)，2917(s)，1630(vs)，1593(s)，1478(s)，1462，1206，855； 1HNMR(CDCl 3)：δ2.15(12H，s)，2.27(6H，s)，2.38(3H，s)，6.89(4H，s)，8.49-8.53(4H，br)，13.57(1H，s)；EI-MS(m/z)：398(M +，9.9)，399(M ++1，3.3％)，279(6.4％)，265(18.9％)，264(84.2％)，262(16.6％)，249(9.9％)，221(5.2％)，199(8.4％)，146(10.0％)，135(12.8％)，134(8.2％)，131(7.3％)，119(7.1％)，91(10.2％)；IR(KBr)：3444(br，m)，2917(s)，1630(vs)，1593(m)，1478(s)，1462(s)，855(s)；Anal.Calcd.for?C 27H 30N 2O：C，81.40；H，7.59；N，7.03。Found：C，82.24；H，7.68；N，6.87。
2, the preparation of 6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol cobalt complex catalyzer (11):
2, (2,4,6-trimethylphenyl imido grpup)-(0.16mg 0.42mmol) is dissolved in the 10mL dehydrated alcohol 4-methylphenol 6-two.Be warming up to 50 ℃, stir down, inwardly drip CoCl 26H 2(0.29 milligram of O, 1.25mmol) ethanolic soln, about 10mins of dropping time continued reaction after 2 hours, removed excess ethanol under reduced pressure, add the 5mL anhydrous diethyl ether, the solid filtering of separating out, with ether washing (3 * 2mL), vacuum-drying, get 170 milligrams in green solid powder, yield: 61.1%.Mp＞300℃(Dec).FAB-MS(m/z)：528(M +)，492(M +-Cl)399(M +-CoCl 2)；IR(KBr)：3420(br，m)，2921(m)，1634(s)，1541(vs)，1479，1069，554；Anal.Calcd.for?C 27H 30N 2OCoCl 2：C，61.37；H，5.72；N，5.30。Found?C，61.05；H，5.60；N，5.30。
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 7 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol cobalt complex (11) (10mg, 20 μ mol) toluene solution utilizes malleation manual or automatic air supply device maintenance ethene in the polymerization process.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Activity is 3 * 10 3Gram ethene/(mole Co hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 100%.
Embodiment 12
Synthesizing of part with embodiment 11
2, the preparation of 6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol nickel complex as catalyst agent:
Under nitrogen protection, in 30 milliliters of Schlenk pipes, add 2,6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol (153mg, 0.38mmol), (DME) NiBr 2(225 milligrams, 0.73mmol), inject the methylene dichloride 10mL that newly handled then, stirred 18 hours at 25 ℃, steam and remove excessive methylene dichloride, add the 5mL anhydrous diethyl ether, the solid filtering of separating out, with ether washing (3 * 2mL). vacuum-drying, 321 milligrams of garnet pressed powders, yield: 98%.
Ethene normal pressure oligomerisation: put into the stirring magneton in 120 ℃ of dry 250 milliliters of three-necked bottles crossing, sealing, vacuum nitrogen filling gas displacement three times, replace secondary with ethene then, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/l), stir after 10 minutes, stir and add catalyzer 2 down, 6-two (2,4,6-trimethylphenyl imido grpup)-4-methylphenol nickel complex (4) (3.1mg, 5 μ mol) toluene solution utilizes malleation manual or automatic air supply device maintenance ethene in the polymerization process.Oligomerisation was closed reaction after 30 minutes, added hydrochloric acid-ethanolic soln termination reaction of 10%.Live 2.4 * 10 5Gram ethene/(mole Ni hour).
Products distribution: the toluene solution of product, analyze through chromatography-mass spectroscopy Conjoint Analysis instrument, find: C 4, 72%; C 6, 28%.

Claims (2)

1. ethylene oligomerization after-trasition metal coordination catalyst, its general structure is:
Figure C0112021400021
Wherein R1 is sec.-propyl or methyl; R2 is hydrogen or methyl; R3 is the tertiary butyl or methyl, and M is cobalt or nickel; X is a chlorine or bromine;
And should meet the following conditions simultaneously:
During the R1=sec.-propyl, R2=H;
During M=Co, X=Cl;
During M=Ni, X=Br.
2. the application of the ethylene oligomerization after-trasition metal coordination catalyst of claim 1 in ethylene oligomerization.
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