CN1401666A - Ethene oligomerization and polymerization post transition metal complex catalyst - Google Patents
Ethene oligomerization and polymerization post transition metal complex catalyst Download PDFInfo
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Abstract
A post-transition metal coordination catalyst for ethylene oligomerization and polymerization is disclosed. It is halogenated 2,9-bis(imino)-1,10-orthophenanthralloline Fe, Ni and Co complexes. Its advantages are simple preparing process, easy purification, and high stability.
Description
Technical field:
The present invention relates to a class ethylene oligomerization and polymerization post transition metal coordination catalyst.
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.Catalyzed ethylene polymerization can obtain the macromolecular material of different performance purposes.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).
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, United States Patent (USP) as oneself report morning: 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 of the present invention and polymerization post transition metal coordination catalyst, i.e. halogenation 2,9-two (imido grpup)-1,10-o-phenanthroline Fe, Ni and Co title complex, general structure is:
1.R
1=iPr, R
2=H, M=Fe, X=Cl2.R
1=Me, R
2=H, M=Fe, X=Cl3.R
1=Me, R
2=Me, M=Fe, X=Cl4.R
1=iPr, R
2=H, M=Co, X=Cl5.R
1=Me, R
2=H, M=Co, X=Cl6.R
1=Me, R
2=Me, M=Co, X=Cl7.R
1=iPr, R
2=H, M=Ni, X=Br8.R
1=Me, R
2=H, M=NI, X=Br9.R
1=Me, R
2=Me, M=Ni, X=Br
Ethylene oligomerization of the present invention and polymerization post transition metal join with the thing Preparation of catalysts be with 2,9-two (imido grpup)-1,10-o-phenanthroline part and halogenation Fe, Co, Ni reaction and obtaining.
Promotor of the present invention is an alkylaluminoxane, as methylaluminoxane (MAO) etc.
The present invention 2,9-two (imido grpup)-1, and 10-o-phenanthroline Fe, the preparation of Co and Ni composition catalyst, raw material comprises: 2,9-dimethyl-1,10-o-phenanthroline, tin anhydride, organic amine, organic solvent, iron(ic) chloride, 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 present invention 2,9-two (imido grpup)-1, and 10-o-phenanthroline Fe, the preparation of Co and Ni composition catalyst, step is carried out in the following order: 1. the preparation of catalyst ligand
2,9-two (imido grpup)-1, the 10-o-phenanthroline is by relevant document synthetic (C.J.Chandler, L.W.Deady, A.Reiss, J.Heterocyclic Chem.1981,18,599; U.L ü ning, M.M ü ller, Liebigs Ann.Chem.1989,367-374), yield reaches 90%.
The preparation of part then is by 2,9-diformazan aldehyde radical-1,10-o-phenanthroline and organic amine are in ethanolic soln, 50 ℃ of nucleophilic reactions to the reflux conditions, slough water, form the group with imine moiety that contains carbon-to-nitrogen double bon, all synthetic 2,9-two (imido grpup)-1,10-o-phenanthroline are confirmed through nuclear-magnetism, infrared, mass spectrum and ultimate analysis.2. 2,9-two (imido grpup)-1, the preparation of 10-o-phenanthroline Fe composition catalyst:
With make 2,9-two (imido grpup)-1,10-o-phenanthroline and FeCl
24H
2O (1: 1) in molar ratio is blended in 25 ℃ or heated and stirred reaction in the anhydrous tetrahydro furan, form title complex, after concentrating, add anhydrous diethyl ether and separate out solid precipitation, just obtain 2,9-(di-imidogen)-1, the iron complex catalyzer of 10-o-phenanthroline, its The Nomenclature Composition and Structure of Complexes is through hydrocarbon nitrogen ultimate analysis and FAB-MS and IR conclusive evidence.3. 2,9-two (imido grpup)-1, the cobalt complex Preparation of catalysts of 10-o-phenanthroline:
With make 2,9-two (imido grpup)-1,10-o-phenanthroline and CoCl
26H
2O (1: 1) in molar ratio is blended in 25 ℃ or heated and stirred reaction in the ethanol, forms title complex, separates out solid precipitation after concentrating, just obtain 2,9-two (imido grpup)-1, the cobalt complex catalyzer of 10-o-phenanthroline, 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 4 is confirmed through single crystal diffraction.4. 2,9-two (imido grpup)-1, the preparation of the nickel complex as catalyst agent of 10-o-phenanthroline:
With make 2,9-two (imido grpup)-1,10-o-phenanthroline and (DME) NiBr
2(1: 0.80) is blended in the dichloromethane solution 25 ℃ of stirring reactions 18 hours in molar ratio, form title complex, separate out solid precipitation after concentrating, wash with anhydrous diethyl ether, just obtain 2,9-two (imido grpup)-1, the Ni composition catalyst of 10-o-phenanthroline, it is formed through hydrocarbon nitrogen ultimate analysis and FAB-MS and IR conclusive evidence.The structure of title complex 7 is confirmed through single crystal diffraction.
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 catalyst complexes solution that reinjects under 25 ℃ of conditions, boosts to specified pressure, carries out the ethylene oligomerization catalysis reaction.React after 30 minutes, reduce to normal pressure, add acidifying ethanol termination reaction, formed oligomerization product is present in the toluene solvant phase, and polymkeric substance is a solid.The output of ethylene oligomerization product and distribution are tested with the chromatograph-mass spectrometer coupling technology.
Catalyst system therefor 2 of the present invention, 9-two (imido grpup)-1, the iron of 10-o-phenanthroline, nickel and cobalt complex, preparation is simple, and purifying is easy, and 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.) form catalyst system, first Application has been opened up the frontier of post-transition metal ethylene polymerization catalyst in vinyl polymerization and oligomerisation.Catalyzer 2,9-two (imido grpup)-1, the iron of 10-o-phenanthroline, nickel and cobalt complex all do not have activity under normal pressure.When ethylene pressure during greater than 10atm, the better catalytic activity of nickel complex is about 10
6Gram ethene/mol catalyst hour; The catalytic activity of iron and cobalt complex is relatively poor.
Description of drawings: Fig. 1 is 2, and 9-two (imido grpup)-1,10-o-phenanthroline and Fe thereof, Ni and Co title complex Fig. 2 are the synthetic of compound 1-9.Reaction reagent and condition: I) EtOH, HAC; Ii) FeCl
2, THF; (iii) CoCl
2, EtOH; Iv) (DME) NiBr
2, CH
2Cl
2Fig. 3 is that crystalline structure Fig. 4 of title complex 4 is the crystalline structure (having acetonitrile solvent to participate in coordination on the Ni) of title complex 7
Embodiment:
Embodiment 1:
2,9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline (L
1) Preparation of catalysts:
Under nitrogen protection, with 2,9-diformyl o-phenanthroline (1.0g; 4.2mmol) dissolve in (120mL) in the ethanol solution, add 3 acetate again, be warming up to backflow then; stir in following half an hour and drip 2,6-diisopropyl aniline (4.0g, ethanol solution 20mmol) (15mL).After dropwising, continue stirring and refluxing after 5 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 1.56g, yield: 62%.m.p.269-270℃；IR(KBr)：3063(s)，2962(s)，1639(vs)，1586(s)，1550，1499，1462(m)，1383，1363，1251，1182，1086，933(m)，860，756(s).
1H?NMR(CDCl
3)：δ1.18(24H，d，J＝10.2Hz)，3.05(4H，m)，7.15-7.23(6H，m)，7.99(2H，s)，8.47(2H，d，J＝7Hz)，8.75(2H，d，J＝7Hz)，8.78(2H，s)；EI-MS(m/z)：554(M
+，?8.7％)，553(23.0％)，539(22.1％)，511(10.8％)，381(13.4％)，369(31.4％)，364(12.4％)，352(15.6％)，208(18.9％)，207(13.5％)，194(100.0％)，193(15.1％)，186(24.9％)，181(40.5％)，176(20.8％)，146(13.8％)；Anal.Calcd.For?C
38H
42N
4：C，82.27；H，7.63；N，10.10.Found：C，81.98％；H，7.90；N：9.72％.
2,9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline iron complex (1) Preparation of catalysts:
2,9-two (2,6-di-isopropyl phenyl imido)-1, (197mg 0.33mmol) is dissolved among the anhydrous THF of 10mL the 10-o-phenanthroline, is warming up to 60 ℃, stirs down and drips FeCl in the 10mins
24H
2O (60mg, anhydrous THF solution 0.30mmol) dropwises, and continues reaction after 18 hours, remove excessive THF under reduced pressure, add the 5mL anhydrous diethyl ether, the solid filtering of separating out is with ether washing (3 * 10mL), vacuum-drying gets 138 milligrams in green solid powder, yield: 66%.m.p.＞320℃.IR(KBr)：3441(br)，2963(s)，2868(m)，1633，1503，1461(s).；FAB-MS(m/z)：680(M
+)，646(M
+-Cl)，610(M
+-2Cl)；Anal.Calcd.For?C
38H
42N
4·FeCl
2·H
2O：C，65.24；H，6.34；N，8.01.Found：C，65.12％；H，6.38；N，7.80％.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, 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, 9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline iron complex (1) (5.9mg, 8.4 toluene solution μ mol) (5mL), after boosting to 23atm, polyreaction added hydrochloric acid-ethanolic soln termination reaction of 10% after 30 minutes.Active 4.4 * 10
5Gram ethene/(mole Fe hour).
Products distribution: the toluene solution of product, through the chromatograph analysis, find: C
8, 0.48g; C
10, 0.89g; C
12, 0.50g.
Embodiment 2:
Part 2,9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline (L
2) preparation: utilize synthetic ligands 2 in the EXAMPLE l, 9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline (L
1) method, 2,9-diformyl o-phenanthroline and 2,6-xylidine reaction obtains yellow solid 2; 9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline, yield: 58%.m.p.132-133 ℃ .IR (KBr): 3449m 3325 (m); 3018 (m), 2969,2918 (m), 1636 (vs); 1591,1550 (s), 1500; 1474,1442 (s), 1192; 1088 (s), 861,762 (s).
1H NMR (CDCl
3) δ 2.18 (12H, s), 6.94-7.14 (6H, m), 8.05 (2H, s), 8.42-8.52 (2H, d), 8.75-8.86 (4H, m); EI-MS (m/z): 442 (M
+, 100%), 441 (39.5%), 427 (14.9%), 424 (16.7%), 337 (28.4%), 324 (18.2%), 323 (53.2%), 322 (14.1%), 311 (25.2%), 310 (64.7%), 309 (14.3%), 308 (11.4%), 296 (14.1%), 295 (10.5%), 132 (13.5%); Anal.Calcd.For C
30H
26N
41/2H
2O:C, 79.79; H, 6.03; N, 12.41.Found:C, 79.86%; H, 6.41; N, 12.13%.
2,9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline iron complex (2) Preparation of catalysts:
Utilize embodiment 1 Synthetic 2,6-two (2,6-isopropyl benzene imido grpup)-1, the method for 10-o-phenanthroline iron is utilized part 2,6-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline (L
2) and FeCl
24H
2The O reaction obtains green solid, yield: 87%.m.p.＞320 ℃ .IR:3403 (br), 2959 (s), 1641,1617 (vs), 1508,1468 (s), 1381,1304 (s), 1223,1177 (s), 862,776 (s); FAB-MS (m/z): 534 (M
+-Cl), 498 (M
+-2Cl) .Anal.Calcd.For C
30H
26N
4FeCl
2H
2O:C, 50.46; H, 3.95; N, 7.85.Found:C, 50.86%; H, 3.65; N, 7.44%.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, add 50 milliliters of the toluene handled successively, 8 milliliters of MAO (1.4mol/L) stir after 10 minutes, stir and add catalyzer 2 down, 9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline iron complex (2) (9.4mg, 16 μ mol) toluene solution (5mL), after boosting to 20atm, polyreaction added hydrochloric acid-ethanolic soln termination reaction of 10% after 30 minutes.Absorb ethene 3g, active 3.75 * 10
5Gram ethene/(mole Fe hour).Products distribution: obtain solid 80mg.Other is an oligopolymer.
Embodiment 3:
Part 2,9-two (2,4,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline (L
3) preparation: utilize synthetic ligands 2 among the embodiment 1,9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline (L
1) method, 2, the reaction of 9-diformyl o-phenanthroline and 2 obtains yellow solid, yield: 77%.m.p.166-167℃；IR(KBr)：3394(br)，1724(s)，1633(vs)，1553(m)，1499，1480(s)，1208(s)，854(s)；
1H?NMR(CDCl
3)：δ2.06(12H，s)，2.23(6H，s)，6.85(4H，m)，7.90(2H，s)，8.38(2H，d)；8.43-8.86(4H，m)；FAB-MS(m/z)：471(M
++1)；Anal.Calcd.For?C
32H
30N
4H
2O·H
2O：C，78.66；H，6.60；N，11.47.Found：C，78.29％；H，6.31；N，11.06％.
2,9-two (2,4,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline iron complex (3) Preparation of catalysts: utilize embodiment 1 Synthetic 2,9-two (2,6-di-isopropyl phenyl imido)-1, the method of 10-o-phenanthroline iron, utilize part 2,9-two (2,4,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline and FeCl
24H
2The O reaction obtains green solid, yield: 91%yield.m.p.＞320 ℃ .IR:1610 (s), 1570 (s), 1502,1479 (s), 862 (s); FAB-MS:561 (M
+-Cl), 526 (M
+-2Cl); Anal.Calcd.For C
32H
30N
4FeCl
2H
2O:C, 62.46; H, 5.24; N, 9.10.Found:C, 62.04%; H, 4.90; N, 8.65%.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/L), stir after 10 minutes, stir adding catalyzer 2 down, 9-two (2,4,6-Three methyl Benzene imido grpup)-1, the toluene solution (5mL) of 10-o-phenanthroline iron complex (3) (6.1mg, 10 μ mol), boost to 23atm after, after the polyreaction 30 minutes, add hydrochloric acid-ethanolic soln termination reaction of 10%.Absorb ethene 2g, active 4 * 10
5Gram ethene/(mole Fe hour).
Embodiment 4:
Ligand L
1Preparation with embodiment 1
2,9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline cobalt complex (4) Preparation of catalysts:
2,9-two (2,6-di-isopropyl phenyl imido)-1, (179mg 0.30mmol) is dissolved in the 10mL dehydrated alcohol 10-o-phenanthroline, is warming up to 60 ℃, stirs down and drips CoCl in the 10mins
24H
2O (70mg, ethanol solution 0.30mmol) dropwises, and continues reaction after 18 hours, remove excess ethanol under reduced pressure, add the 5mL anhydrous diethyl ether, the solid filtering of separating out is with ether washing (3 * 10mL), vacuum-drying gets 130 milligrams in green solid powder, yield: 60%.m.p.＞320℃.IR(KBr)：2961，2866(s)，1639，1615，1586，1566(s)，1505，1461(s)；FAB-MS：648(M
+-Cl)，614(M
+-2Cl)；Anal.Calcd.ForC
38H
42N
4·CoCl
2：C，66.67；H，6.18；N，8.18.Found：C，66.22％；H，5.71；N，8.10％.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, add 50 milliliters of the toluene handled successively, 8 milliliters of MAO (1.4mol/L) stir after 10 minutes, stir and add catalyzer 2 down, 9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline cobalt complex (4) (6.83mg, 10 μ mol) toluene solution (5mL), after boosting to 13atm, polyreaction added hydrochloric acid-ethanolic soln termination reaction of 10% after 30 minutes.Absorb ethene 3.5g, active 7 * 10
5Gram ethene/(mole Co hour).
Products distribution: other is oligopolymer to obtain solid 30mg..
Embodiment 5:
Ligand L
2Preparation with embodiment 2
2,9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline cobalt complex (5) Preparation of catalysts: utilize embodiment 4 Synthetic 2s, 6-two (2,6-isopropyl benzene imido grpup)-1, the method of 10-o-phenanthroline cobalt (II) is utilized part 2, and 6-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline (L
2) and CoCl
26H
2O reaction obtains green solid, yield: 73%.m.p.＞320 ℃; IR (KBr): 1604,1574 (vs), 1381 (vs), 1064 (s); FAB-MS:536 (M
+-Cl), 501 (M
+-2Cl); Anal.Calcd.For C
30H
26N
4CoCl
2: C, 62.95%; H, 4.58%; N 9.79%.Found:C, 62.72%; H, 4.67%; N 9.34%.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, add 50 milliliters of the toluene handled successively, 8 milliliters of MAO (1.4mol/L) stir after 10 minutes, stir and add catalyzer 2 down, 9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline cobalt complex (5) (5.89mg, 10 μ mol) toluene solution (5mL), after boosting to 10atm, polyreaction added hydrochloric acid-ethanolic soln termination reaction of 10% after 30 minutes.Active 7.1 * 10
5Gram ethene/(mole Co hour).
Products distribution: other is oligopolymer to obtain solid 480mg., is followed successively by: C
4: 2.54g; C
6: 0.24g.Embodiment 6:
Ligand L
3Preparation with embodiment 3
2,9-two (2,4,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline cobalt complex (6) Preparation of catalysts: utilize embodiment 4 Synthetic 2s, 9-two (2,6-di-isopropyl phenyl imido)-1, the method of 10-o-phenanthroline cobalt, utilize part 2,9-two (2,4,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline and CoCl
26H
2O reaction obtains green solid, yield: 73%.m.p.＞320 ℃; IR:3425 (br), 1612 (s), 1564,1502,1477 (s); FAB-MS:564 (M
+-Cl), 529 (M
+-2Cl); Anal.Calcd.For C
32H
30N
4CoCl
2H
2O:C, 62.15%; H, 5.22%; N 9.06%.Found:C, 62.30%; H, 4.98%; N, 8.90%.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, add 50 milliliters of the toluene handled successively, 8 milliliters of MAO (1.4mol/L), stir after 10 minutes, stir adding catalyzer 2 down, 9-two (2,4,6-Three methyl Benzene imido grpup)-1, the toluene solution (5mL) of 10-o-phenanthroline cobalt complex (6) (6.18mg, 10 μ mol), boost to 20atm after, after the polyreaction 30 minutes, add hydrochloric acid-ethanolic soln termination reaction of 10%.Active 9.3 * 10
5Gram ethene/(mole Co hour).
Products distribution: other is oligopolymer to obtain solid 30mg., and distribution is followed successively by: C
4: 4.2g; C
6, 0.26g; C
8, 0.18g.
Embodiment 7:
Ligand L
1Preparation with embodiment 1
2,9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline nickel complex (7) Preparation of catalysts:
Under nitrogen protection, in 30 milliliters of Schlenk pipes, add 2,9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline (L
1) (179mg, 0.30mmol), (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, with ether washing (3 * 10mL). vacuum-drying, reddish yellow pressed powder 124mg, yield: 90%.m.p.＞320℃；IR(KBr)：3407(Br)，2963(s)，1631，1608，1584(s)，1503，1401(s)；FAB-MS(m/z)：693(M
+-Br)，612(M
+-2Br)；Anal.Calcd.For?C
38H
42N
4NiBr
2·CH
2Cl
2：C，54.58；H，5.17；N，6.53.Found：C，54.09％；H，4.86；N，6.23％.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, 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, 9-two (2,6-di-isopropyl phenyl imido)-1,10-o-phenanthroline nickel complex (7) (20mg, 22 μ mol) toluene solution (5mL), after boosting to 20atm, polyreaction added hydrochloric acid-ethanolic soln termination reaction of 10% after 30 minutes.Active 2.1 * 10
6Gram ethene/(mole Ni hour).
Products distribution: obtain solid 250mg.Dsc and analyze: 120 ℃ of fusing points.The toluene solution of product is analyzed through chromatography-mass spectroscopy Conjoint Analysis instrument, is followed successively by: C
4: 4.0g, C
6: 11.06g; C
8: 5.36g; C
8: 2.0g.
Embodiment 8:
Ligand L
2Preparation with embodiment 2
2,9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline nickel complex (8) Preparation of catalysts: utilize embodiment 7 Synthetic 2s, 9-two (2, the 6-imino dimethyl benzene)-1, the method of 10-o-phenanthroline nickel is utilized part 2, and 9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline (L
2) and DMENiCl
2Reaction obtains the reddish yellow solid, yield: 78%..m.p.＞320 ℃; FAB-MS:582 (M
+-Br), 501 (M
+-2Br) .Anal.Calcd.ForC
30H
26N
4NiBr
2CH
2Cl
2: C, 49.91; H, 3.78; N, 7.51.Found:C, 49.95%; H, 3.51; N, 7.50%.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, 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, 9-two (2, the 6-imino dimethyl benzene)-1,10-o-phenanthroline nickel (II) title complex (8) (13mg, 17 μ mol) toluene solution (5mL), after boosting to 20atm, polyreaction added hydrochloric acid-ethanolic soln termination reaction of 10% after 30 minutes.Active 2.1 * 10
6Gram ethene/(mole Ni hour).
Products distribution: be oligopolymer, be followed successively by: C
4: 11g; C
6: 5.8g; C
8: 0.96g.
Embodiment 9:
Ligand L
3Preparation with embodiment 3
2,9-two (2,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline nickel complex (9) Preparation of catalysts: utilize embodiment 7 Synthetic 2s, 9-two (2,6-di-isopropyl phenyl imido)-1, the method for 10-o-phenanthroline nickel is utilized part 2,9-two (2,4,6-Three methyl Benzene imido grpup)-1,10-o-phenanthroline (L3) and DMENiCl
2Reaction obtains reddish yellow solid, yield: 78%; ℃ m.p.＞320; IR (KBr): 1629 (vs), 1569 (s) .FAB-MS:609 (M
+-Br), 528 (M
+-2Br); Anal.Calcd.For C
32H
30N
4NiBr
2CH
2Cl
2: C, 51.21; H, 4.17; N, 7.24.Found:C, 49.95%; H, 3.57; N, 7.52%.
Ethylene oligomerization: put into the stirring magneton in 120 ℃ of dry 100 milliliters of stainless steel steel cylinders crossing, sealing, vacuumized about 4 hours, the inflated with nitrogen displacement is three times then, replace secondary with ethene again, add 50 milliliters of the toluene handled successively, 6 milliliters of MAO (1.4mol/L), stir after 10 minutes, stir adding catalyzer 2 down, 9-two (2,4,6-Three methyl Benzene imido grpup)-1, the toluene solution (5mL) of 10-o-phenanthroline nickel complex (9) (7.72mg, 10 μ mol), boost to 11atm after, after the polyreaction 30 minutes, add hydrochloric acid-ethanolic soln termination reaction of 10%.Active 2.0 * 10
6Gram ethene/(mole Ni hour).Products distribution: other is oligopolymer to obtain solid 105mg., is followed successively by: C
4: 3.60g; C
6: 5.2g; C
8: 1.23g
Claims (1)
1. ethylene oligomerization and polymerization post transition metal coordination catalyst, its general structure is:
1.R
1=iPr, R
2=H, M=Fe, X=Cl2.R
1=Me, R
2=H, M=Fe, X=Cl3.R
1=Me, R
2=Me, M=Fe, X=Cl4.R
1=iPr, R
2=H, M=Co, X=Cl5.R
1=Me, R
2=H, M=Co, X=Cl6.R
1=Me, R
2=Me, M=Co, X=Cl7.R
1=iPr, R
2=H, M=Ni, X=Br8.R
1=Me, R
2=H, M=NI, X=Br9.R
1=Me, R
2=Me, M=Ni, X=Br
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372609C (en) * | 2005-04-22 | 2008-03-05 | 中国科学院化学研究所 | Catalyst for oligomerization of ethylene, its preparing method and use |
| CN102432415A (en) * | 2011-09-09 | 2012-05-02 | 中国科学院化学研究所 | Preparation method of ethylene-propylene copolymer |
| CN102850168A (en) * | 2012-09-19 | 2013-01-02 | 浙江大学 | Ethylene oligomerization process capable of preventing or reducing adhesive substance formation on inner wall of reactor |
| WO2017161466A1 (en) * | 2016-03-22 | 2017-09-28 | 亚培烯科技(嘉兴)有限公司 | New linear alpha olefin catalyst and preparation and application thereof |
| WO2020147372A1 (en) | 2019-01-15 | 2020-07-23 | 中国石油化工股份有限公司 | Halogen-containing compound and use thereof as catalyst ligand in ethylene oligomerization |
| WO2020147373A1 (en) | 2019-01-15 | 2020-07-23 | 中国石油化工股份有限公司 | Halogen-containing compound and use thereof, catalyst composition, and ethylene oligomerization, trimerization and tetramerization methods |
-
2001
- 2001-08-17 CN CN 01124240 patent/CN1401666A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372609C (en) * | 2005-04-22 | 2008-03-05 | 中国科学院化学研究所 | Catalyst for oligomerization of ethylene, its preparing method and use |
| CN102432415A (en) * | 2011-09-09 | 2012-05-02 | 中国科学院化学研究所 | Preparation method of ethylene-propylene copolymer |
| CN102432415B (en) * | 2011-09-09 | 2013-12-04 | 中国科学院化学研究所 | Preparation method of ethylene-propylene copolymer |
| CN102850168A (en) * | 2012-09-19 | 2013-01-02 | 浙江大学 | Ethylene oligomerization process capable of preventing or reducing adhesive substance formation on inner wall of reactor |
| CN102850168B (en) * | 2012-09-19 | 2015-02-25 | 浙江大学 | Ethylene oligomerization process capable of preventing or reducing adhesive substance formation on inner wall of reactor |
| WO2017161466A1 (en) * | 2016-03-22 | 2017-09-28 | 亚培烯科技(嘉兴)有限公司 | New linear alpha olefin catalyst and preparation and application thereof |
| WO2020147372A1 (en) | 2019-01-15 | 2020-07-23 | 中国石油化工股份有限公司 | Halogen-containing compound and use thereof as catalyst ligand in ethylene oligomerization |
| WO2020147373A1 (en) | 2019-01-15 | 2020-07-23 | 中国石油化工股份有限公司 | Halogen-containing compound and use thereof, catalyst composition, and ethylene oligomerization, trimerization and tetramerization methods |
| US11306040B2 (en) | 2019-01-15 | 2022-04-19 | China Petroleum & Chemical Corporation | Halogen-containing compound and use thereof, catalyst composition, and ethylene oligomerization, trimerization and tetramerization methods |
| US11826743B2 (en) | 2019-01-15 | 2023-11-28 | China Petroleum & Chemical Corporation | Halogen-containing compound and use thereof as catalyst ligand in ethylene oligomerization |
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