CN1769270A - Catalyst componemt ligand precursor, ligand compound for ethene polymerization and oligopolymerization - Google Patents

Catalyst componemt ligand precursor, ligand compound for ethene polymerization and oligopolymerization Download PDF

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CN1769270A
CN1769270A CN 200410086374 CN200410086374A CN1769270A CN 1769270 A CN1769270 A CN 1769270A CN 200410086374 CN200410086374 CN 200410086374 CN 200410086374 A CN200410086374 A CN 200410086374A CN 1769270 A CN1769270 A CN 1769270A
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ethyl
pyridine
ligand
ligand compound
ethyl formate
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陈伟
孙文华
刘东兵
唐秀波
郑刚
高铁龙
张文娟
吴彪
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a ligand compound prosoma, used in ethane polymerization and its polymerization catalyst, whose chemical name is 2- acetyl base- pyridine-6- ethyl formate, and the invention also provideds the ligand compound on the basis of the above ligand compound prosoma, used in ethane polymerization and its polymerization catalyst, whose chemical name is 6-[1- aromatic radical imines]-ethyl group- pyridine-2- ethyl formate. The complexe formed by the said ligand compound and the transient metal,such as Fe(II), Co(II) and Ni(II), can be used as active component of ethane polymerization and its polymerization catalyst.

Description

A kind of vinyl polymerization that is used for, oligomerisation close ligand precursor, the ligand compound of catalyst component
Technical field
The present invention relates to a kind of vinyl polymerization that is used for, novel ligand precursor, ligand compound of catalyst component and preparation method thereof closed in oligomerisation.
Prior art
One of major industry purposes of ethylene oligomerization is exactly to be used for producing C 6-C 20Linear alpha-alkene.Alpha-olefin has been widely used in producing washing composition, softening agent, the comonomer of lubricant and conduct preparation linear low density polyethylene (LLDPE).Linear alpha-alkene originally is 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.The catalyzer that is used for the industrial production alpha-olefin at present mainly contains: (1) aluminum alkyls and early transition metal title complex (TiCl 4Deng) many site catalysts of composition; (2) title complex (SHOP technology) (USpatent3686351,19720711 and USpatent3676523,19720822.) that contains the Ni (II) of single anion bitooth ligand [P, O] (Chart1).
Figure A20041008637400031
Chart?1
The composition catalyst that is used for the Ni (II) that contains single anion bitooth ligand [P, O] of ethylene oligomerization is studied widely.Wherein it should be noted that most people's such as 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], [S, O] and parts such as [S, S].Generally speaking, all obtain neutral by these single anion ligands the alkyl of catalytic activity or the metal complexes that halogen replaces are arranged.The composition catalyst that is used for the Ni (II) that contains single anion bitooth ligand [P, O] of ethylene oligomerization is studied widely.Wherein it should be noted that most people's such as Keim work.These catalyst ethylene oligomerizations need high temperature of reaction and ethylene pressure in the past few decades.As the temperature of 80～120 ℃ of SHOP processing requirements and the ethylene pressure of 100bar.Found afterwards to obtain the title complex of cationic Ni (II), oligomerizing ethylene under lower temperature and pressure by neutral [P, O] part.The title complex of similar cationic Pd (II) alkene (J.Chem.Soc.Chem. that can two polyethylene comes of age
Commum.1994；615.J.Chem.Soc.Chem.Commun.1993，1632.)。
Figure A20041008637400041
Chart 2 Chart 31995, Brookhart etc. have reported title complex (the Chart 2) (J.Am.Chem.Soc.1995 of a kind of diimine Ni (II), 117,6414.), then soon, Brookhart and Gibson have reported the Fe (II) of pyridine diimine and the title complex (Chart 3) of Co (II) when being equal to, by regulating the substituting group on the phenyl ring, oligomerisation or polymerising ethylene well.(J.Am.Chem.Soc.1998，120，4049.J.Am.Chem.Soc.1998，120，7143.Chem.Commun.1998，849.)。
Summary of the invention
This patent on the basis of previous work, invented a class novel be used for the ligand compound precursor that catalyzer is closed in vinyl polymerization and oligomerisation, chemical name 2-ethanoyl-pyridine-6-ethyl formate, its structural formula is
Figure A20041008637400042
Another object of the present invention is to provide to be used for the ligand compound that catalyzer is closed in vinyl polymerization and oligomerisation on the ligand compound precursor base Chu of catalyzer is closed in above-mentioned vinyl polymerization and oligomerisation, chemical name 6-[1-aromatic base imines]-ethyl]-pyridine-2-ethyl formate, it has following general formula (I):
Figure A20041008637400043
R in the formula 1, R 2Be hydrogen, C 1～C 20Alkyl, halogen atom, R wherein 1, R 2Be preferably hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine;
The synthetic route of ligand precursor and part is listed below, and experiment divides following 4 steps:
Scheme?1
Figure A20041008637400051
i)toluene，benzene，p-TsOH，reflux?for?ligands?2a-d?or?ii)toluene，benzene，p-TsOH，silica-alumina?catalyst?support，molecular?sieve，reflux?for?ligands?2e-h.
(1) 2,6-lutidine is in acidic medium, and potassium permanganate carries out oxidizing reaction under existing, and obtains pyridine-2, the 6-dioctyl phthalate;
(2) pyridine-2,6-dioctyl phthalate and ethanol carry out esterification and obtain pyridine-2,6-dioctyl phthalate ethyl ester;
(3); Pyridine-2,6-dioctyl phthalate ethyl ester carries out acylation reaction with ethyl acetate in the presence of sodium ethylate, obtain 2-ethanoyl-pyridine-6-ethyl formate;
(4) reaction of 2-ethanoyl-pyridine-6-ethyl formate and substituted aniline obtains 6-[1-aromatic base imines]-ethyl]-pyridine-2-ethyl formate.
By the synthetic 6-[1-aromatic base imines that obtains of above-mentioned route]-ethyl]-title complex that pyridine-2-ethyl formate and transition-metal Fe (II), Co (II) and Ni (II) form can be used as vinyl polymerization and the activity of such catalysts component is closed in oligomerisation.
Reaction raw materials comprises 2,6-lutidine, potassium permanganate, first water, the vitriol oil, dehydrated alcohol, methylene dichloride, sodium carbonate solution, sodium Metal 99.5, petrol ether/ethyl acetate, 2,6-xylidine, tosic acid, toluene, 2,4,6-trimethylaniline, 2,6-Diethyl Aniline, 2,6-diisopropyl aniline, 2,6-difluoroaniline, 2,4,6-trichloroaniline, 2,6-dibromo aniline etc.
Embodiment
Embodiment 1
1, pyridine-2, the preparation of 6-dioctyl phthalate
In the 1000mL three neck round-bottomed flasks that reflux condensing tube is housed, add potassium permanganate (53.3g, 0.34mol), add the 500mL first water then, be warming up to about 90 ℃, magnetic agitation drips 2,6-lutidine (16.7g to dissolving, 0.156mol), progressively be warming up to backflow then.React after 2 hours, temperature is reduced to about 90 ℃, in reaction system, add potassium permanganate (53.3g, 0.34mol) and the 200mL first water, be warming up to backflow after, continue reaction 2.5 hours.After reaction stops, filtering, with solution concentration to about 200mL, drip the vitriol oil (98%, 18.7mL), have a large amount of white precipitates to generate, filtration obtains white solid product 22.9g, productive rate: 87.8% after the drying.Fusing point: 254～256 ℃, literature value is 250 ℃.
2, pyridine-2, the preparation of 6-dioctyl phthalate ethyl ester
In the two neck flasks of the 500mL that water-and-oil separator and reflux condensing tube are housed, add pyridine-2 successively, and the 6-dioctyl phthalate (22.0g, 0.13mol), dehydrated alcohol 250mL, vitriol oil 6.5mL and benzene 10mL.After being warming up to backflow, reacting and began branch water, coreaction 24 hours in 6 hours.After reaction stopped, decompression steamed remaining second alcohol and water, and the sodium carbonate solution with 15% is neutralized to about pH=7.(organic phase is collected in 4 * 30mL) extractions, and after 12 hours, methylene dichloride is removed in decompression, obtains pure product pyridine-2,6-dioctyl phthalate ethyl ester 20.5g with anhydrous sodium sulfate drying with methylene dichloride.Productive rate: 70.6%.Fusing point: 41.0-41.5 ℃, literature value: 41-42 ℃.
3, Synthetic 2-ethanoyl-pyridine-6-ethyl formate
At N 2Protection down, in the three-necked flask of thorough drying 250mL, add sodium Metal 99.5 (1.8g, 0.078mol); at room temperature drip the dehydrated alcohol of treated mistake then, treat that vacuum is removed excess ethanol after the sodium complete reaction; 60 ℃ of following vacuum-dryings 3 hours, be cooled to room temperature after, drip pyridine-2; 6-dioctyl phthalate ethyl ester (15.2g, ethyl acetate 0.068mol) (60mL) solution is after adding; be warming up to backflow; reacted 12 hours, and be cooled to room temperature, standing over night.After adding 35mL hydrochloric acid, continue to reflux 8 hours, stopped reaction adds the 50mL first water, with the sodium-chlor that generates in the solubilizing reaction.(4 * 30mL) extractions merge organic phase to mixed solution, wash (3 * 20mL) with 5% sodium carbonate solution again with methylene dichloride.Water use again dichloromethane extraction (3 * 15mL), organic phase is merged, with anhydrous sodium sulfate drying after about 10 hours, decompression is removed solvent down, obtain red liquid, carry out column chromatography with the leacheate of petrol ether/ethyl acetate (8 1) and separate (long 80cm, the silicagel column of internal diameter 2.5cm).Obtain product 2-ethanoyl-pyridine-6-ethyl formate (compound 1) 5.2g, productive rate: 59.6%.Fusing point: 50.0～51 ℃. 1H?NMR(300Hz，CDCl 3)：δ8.27(dd，1H，J 1＝1.2Hz，J 2＝6.6Hz，Py-Hm)；8.20(d，1H，J 1＝1.2Hz，J 2＝6.6Hz，Py-Hm)；7.99(t，1H，J＝7.8Hz，Py-Hp)；4.50(q，2H)；2.81(s，3H)；1.47(t，3H)。 13C?NMR(75MHz，CDCl 3)：δ199.72；164.70；153.61；147.85；138.01；128.16；124.43；62.12；25.71；14.33。IR(cm -1，KBr)：2988；1727；1704；1585；1474；1455；1321；1367；1237；1155。Anal.(C 10H 11NO 3)Calcd：C，62.17；H，5.74；N，7.25。Found：C，62.14；H，5.75；N，7.17。
Embodiment 2
6-[1-(2,6-3,5-dimethylphenyl imines) ethyl] pyridine-2-ethyl formate] (2a) synthetic
In the three-necked flask of the 50mL that reflux condensing tube and water-and-oil separator are housed, add 2-ethanoyl-pyridine-6-ethyl formate (0.386g successively; 2mmol) (compound 1); 2; 6-xylidine (0.267g; 2.2mmol), the tosic acid of catalytic amount (be about two kinds of raw material total masses 5%) and 20mL toluene, be warming up to backflow.React after 24 hours, carry out column chromatography with the leacheate of petrol ether/ethyl acetate (15: 1) and separate (long 60cm, the silicagel column of internal diameter 2cm).Obtain yellow solid product ethyl-6-[1-(2,6-3,5-dimethylphenyl imines) ethyl] pyridine-2-ethyl formate] (2a) 0.41g, productive rate: 69.5%.Fusing point: 63-64 ℃. 1H?NMR(300MHz，CDCl 3)：δ8.58(d，1H，J＝7.9Hz，Py-Hm)；8.20(d，1H，J＝7.6Hz，Py-Hm)；7.95(t，1H，J＝7.9Hz，Py-Hp)；7.07(d，2H，J＝7.4HzAr-H)；6.95(t，1H，J＝7.4HzAr-H)；4.49(q，2H)；2.26(s，3H)；2.03(s，6H)，1.46(t，3H，J＝7.1)。 13C?NMR(77.10MHz，CDCl 3)：δ166.98；165.15；156.45；148.57；147.39；137.32；126.16；125.27；124.33；123.18；61.88；17.92；16.51；14.31。IR(cm -1，KBr)：1720；1640；1587；1469；1370；1324。Anal.(C 18H 20N 2O 2)Calcd：C，72.95；H，6.80；N，9.45。Found：C，72.46；H，6.77；N，9.29。
Embodiment 3
6-[1-(2,4,6-trimethylphenyl imines) ethyl] pyridine-2-ethyl formate] (2b) synthetic synthetic method is with embodiment 2, just changes raw material into 2,4, the 6-xylidine; Ethyl-the 6-[1-that obtains (2,4,6-trimethylphenyl imines) ethyl] pyridine-2-ethyl formate] (2b) be yellow solid, productive rate: 73.0%.Fusing point: 74-76 ℃. 1H?NMR(300MHz，CDCl 3)：δ8.57(d，1H，J＝8.1Hz，Py-Hm)；8.19(d，1H，J＝7.7Hz，Py-Hm)；7.92(t，1H，J＝7.8Hz，Py-Hp)；6.89(s，2H，Ar-H)；4.49(q，2H)；2.29(s，3H)；2.26(s，3H)；1.99(s，6H)，1.49(t，3H，J＝7.1Hz)。 13C?NMR(77.00MHz，CDCl 3)：δ167.17；165.18；156.58；147.34；146.08；137.27；132.36；128.60；12.12；124.33；61.87；20.74；17.85；16.45；14.31。IR(cm -1，KBr)：1715；1644；1571；1477；1453；1369；1325。Anal.(C 19H 22N 2O 2)Calcd：C，73.52；H，7.14；N，9.03。Found：C，73.29；H，7.15；N，9.0
Embodiment 4
6-[1-(2,6-diethyl phenyl imines) ethyl] pyridine-2-ethyl formate] (2c) synthetic
Synthetic method just changes raw material into 2, the 6-Diethyl Aniline with embodiment 2; Ethyl-the 6-[1-that obtains (2,6-diethyl phenyl imines) ethyl] pyridine-2-ethyl formate] (2c) be yellow solid, productive rate: 68.2%.Fusing point: 86-88 ℃. 1H?NMR(300MHz，CDCl 3)：δ8.49(d，1H，J＝7.8Hz，Py-Hm)；8.12(d，1H，J＝7.5Hz，Py-Hm)；7.87(t，1H，J＝7.8Hz，Py-Hp)；7.15(d，2H，J＝7.5Hz，Ar-H)；6.96(t，1H，J＝6.3Hz，Ar-H)；4.42(q，2H)；2.71(m，4H)；2.18(s，3H)；1.39(t，3H)；1.05(t，6H)。 13CNMR(75MHz，CDCl 3)：δ166.66；165.17；156.43；147.57；147.38；137.31；131.03；126.11；125.94；124.26；123.45；61.87；24.54；16.81；14.29；13.67。IR(cm -1，KBr)：1742；1640；1580；1540；1454；1394。Anal.(C 20H 24N 2O 2)Calcd：C，74.04；H，7.46；N，8.64。Found：C，73.95；H，7.49；N，8.52。Tested the crystalline structure of this compound with X-ray diffraction.
Embodiment 5
6-[1-(2,6-diisopropyl phenyl imines) ethyl] pyridine-2-ethyl formate] (2d) synthetic
Synthetic method just changes raw material into 2 with embodiment 2,6-diisopropyl aniline, the ethyl-6-[1-that obtains (2,6-diisopropyl phenyl imines) ethyl] pyridine-2-ethyl formate] (2d) be yellow solid, productive rate: 71.5%.Fusing point: 110-111 ℃. 1H?NMR(300MHz，CDCl 3)：δ8.56(d，1H，J＝7.8Hz，Py-Hm)；8.19(d，1H，J＝7.5Hz，Py-Hm)；7.93(t，1H，J＝7.8Hz，Py-Hp)；7.15(dd，1H，J 1＝6.3Hz，J 2＝2.1Hz，Ar-H)；7.10(dd，1H，J 1＝6.0Hz，J 2＝3.0Hz，Ar-H)；7.04(t，1H，J＝7.8Hz，Ar-H)；4.48(q，2H)；2.71(m，2H)；2.28(s，3H)；1.45(t，3H)；1.36(t，12H)； 13C?NMR(75MHz，CDCl 3)：δ166.67；165.19；156.40；147.39；146.24；137.31；135.64；126.10；124.31；123.71；123.00；61.87；28.24；23.22；17.11；14.28。IR(cm -1，KBr)：1748；1722；1643；1584；1548；1460；1368。Anal.(C 22H 28N 2O 2)Calcd：C，74.97；H，8.01；N，7.95。Found：C，74.71；H，7.99；N，7.69。Tested the crystalline structure of this compound with X-ray diffraction.
Embodiment 6
6-[1-(2,6-difluorophenyl imines) ethyl] pyridine-2-ethyl formate] (2e) synthetic
In the three-necked flask of the 100mL that reflux condensing tube and water-and-oil separator are housed, add 2-ethanoyl-pyridine-6-ethyl formate (0.700g successively; 3.62mmol), 2; 6-difluoroaniline (0.575g; 4.34mmol), the silica gel-alumina supporter catalyzer of the tosic acid of catalytic amount (be about two kinds of raw material total masses 5%), catalytic amount (be about two kinds of raw material total masses 10%), 4 molecular sieves and 30mL toluene, be warming up to backflow.React after 24 hours, carry out column chromatography with the leacheate of petrol ether/ethyl acetate (6: 1) and separate (long 60cm, the silicagel column of internal diameter 2cm).Obtain yellow heavy-gravity oily product ethyl-6-[1-(2,6-difluorophenyl imines) ethyl] pyridine-2-ethyl formate] (2e) (0.49g, productive rate: 44.5%. 1HNMR(300MHz，CDCl 3)：δ8.52(d，1H，J＝7.8Hz，Py-Hm)；8.21(d，1H，J＝7.5Hz，Py-Hm)；7.94(t，1H，J＝7.8Hz，Py-Hp)；6.9-7.1(m，3H，Ar-H)；4.49(q，2H)；2.47(s，3H)；1.46(t，3H)。 13C?NMR(75.45MHz，CDCl 3)：δ172.47；165.06；155.98；147.509；145.490；137.58；128.25；126.70；125.07；124.53；124.45；61.98；17.60；14.31。IR(cm -1，KBr)：1742；1721；1647；1583；1471；1425；1369。Anal.(C 16H 14F 2N 2O 2)Calcd：C，63.15；H，4.64；N。Found：C，63.06；H，4.52；N，9.10。
Embodiment 7
6-[1-(2,6-dichlorophenyl imines) ethyl] pyridine-2-ethyl formate) (2f) synthetic
Synthetic method just changes raw material into 2, the 6-dichlorphenamide bulk powder with embodiment 6; Ethyl-6-[1-(2,6-dichlorophenyl imines) ethyl] pyridine-2-ethyl formate) (2f) be yellow heavy-gravity oily matter, productive rate: 34.4%. 1H?NMR(300MHz，CDCl 3)：δ8.58(d，1H，J＝7.8Hz，Py-Hm)；8.23(d，1H，J＝7.8Hz，Py-Hm)；7.96(t，1H，J＝7.8Hz，Py-Hp)；7.57(d，2H，J 1＝8.1Hz，Ar-H)；7.00(t，1H，J＝8.0Hz，Ar-H)；4.50(q，2H)；2.38(s，3H)；1.46(t，3H)。13C?NMR(75.45MHz，CDCl 3)：δ171.19；165.06；155.62；147.509；145.490；137.58；128.25；126.70；125.07；124.53；124.45；61.98；17.60；14.31。IR(cm -1，KBr)：1739；1721；1655；1580；1556；1437；1368。Anal.(C 16H 14Cl 2N 2O 2)Calcd：C，56.99；H，4.18；N，8.31。Found：C，56.84；H，4.40；N，7.99。
Embodiment 8
6-[1-(2,4,6-trichlorophenyl imines) ethyl] pyridine-2-ethyl formate] (2g) synthetic
Synthetic method just changes raw material into 2,4, the 6-trichloroaniline with embodiment 6; Ethyl-the 6-[1-that obtains (2,4,6-trichlorophenyl imines) ethyl] pyridine-2-ethyl formate] (2g) be yellow solid, productive rate: 65.2%.Fusing point: 85-86 ℃. 1H?NMR(300MHz，CDCl 3)：δ8.53(d，1H，J＝5.9Hz，Py-Hm)；8.21(d，1H，J＝5.8Hz，Py-Hm)；7.95(t，1H，J＝5.9Hz，Py-Hp)；7.37(s，2H，Ar-H)；4.48(q，2H)；2.71(m，4H)；2.37(s，3H)；1.45(t，3H，J＝5.3Hz)。 13C?NMR(77.00MHz，CDCl 3)：δ171.78；164.87；155.26；147.50；144.24；137.50；128.76；128.08；126.70；124.94；124.87；61.89；17.64；14.23。IR(cm -1，KBr)：1740；1721；1649；1575；1545；1442；1368。Anal.(C 16H 13C 13N 2O 2)Calcd：C，51.71；H，3.53；N，7.54。Found：C，51.78；H，3.67；N，7.45。
Embodiment 9
6-[1-(2,6-dibromo phenyl imines) ethyl] pyridine-2-ethyl formate) (2h) synthetic
Synthetic method just changes raw material into 2, the 6-dibromo aniline with embodiment 6; Ethyl-the 6-[1-that obtains (2,6-dibromo phenyl imines) ethyl] pyridine-2-ethyl formate) (2h) be yellow heavy-gravity oily matter, productive rate: 63.8%. 1H?NMR(300MHz，CDCl 3)：δ8.59(d，1H，J＝7.8Hz，Py-Hm)；8.23(d，1H，J＝6.9Hz，Py-Hm)；7.97(t，4H，J＝7.8Hz，Py-Hp)；7.57(dd，2H，J 1＝7.5Hz，J 2＝0.6Hz，Ar-H)；6.88(t，1H，J＝7.8Hz，Ar-H)；4.49(m，2H)；2.37(s，3H)；1.46(t，3H)。 13C?NMR(75MHz，CDCl 3)：δ170.89；164.98；155.49；147.87；147.48；135.51；131.93；126.67；125.36；125.01；113.40；61.90；17.55；14.24。IR(cm -1，KBr)：1739；1720；1654；1582；1548；1430；1368。Anal.(C 16H 14Br 2N 2O 2)Calcd：C，45.10；H，3.31；N，6.57。Found：C，45.12；H，3.37；N，6.34。

Claims (3)

1, a kind ofly be used for the ligand compound precursor that catalyzer is closed in vinyl polymerization and oligomerisation, chemical name 2-ethanoyl-pyridine-6-ethyl formate, its structural formula is
Figure A2004100863740002C1
2, a kind ofly be used for the ligand compound that catalyzer is closed in vinyl polymerization and oligomerisation, it is characterized in that chemical name 6-[1-aromatic base imines]-ethyl]-pyridine-2-ethyl formate, it has following general formula (I):
R in the formula 1, R 2Be hydrogen, C 1～C 20Alkyl, halogen atom.
3, the ligand compound that is used for olefin polymerization catalysis according to claim 2,6-[1-aromatic base imines]-ethyl]-pyridine-2-ethyl formate, it is characterized in that, wherein R 1, R 2Be hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine.
CN 200410086374 2004-10-27 2004-10-27 Catalyst componemt ligand precursor, ligand compound for ethene polymerization and oligopolymerization Pending CN1769270A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875459A (en) * 2012-09-27 2013-01-16 爱斯特（成都）生物制药有限公司 Synthetic method of 6-acetyl-2-pyridine formic ester
CN103497152A (en) * 2013-10-11 2014-01-08 河北汇华药业有限公司 Method for preparing pyridine-2,6-dicarboxylic acid via liquid phase catalytic oxidation
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
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875459A (en) * 2012-09-27 2013-01-16 爱斯特（成都）生物制药有限公司 Synthetic method of 6-acetyl-2-pyridine formic ester
CN103497152A (en) * 2013-10-11 2014-01-08 河北汇华药业有限公司 Method for preparing pyridine-2,6-dicarboxylic acid via liquid phase catalytic oxidation
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
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
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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