CN1695807A - Ethylene oligomerization catalyst, preparation method and application - Google Patents

Ethylene oligomerization catalyst, preparation method and application Download PDF

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CN1695807A
CN1695807A CN 200410037932 CN200410037932A CN1695807A CN 1695807 A CN1695807 A CN 1695807A CN 200410037932 CN200410037932 CN 200410037932 CN 200410037932 A CN200410037932 A CN 200410037932A CN 1695807 A CN1695807 A CN 1695807A
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nickel
triphenyl phosphorus
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许学翔
纪洪波
景振华
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

A catalyst for oligomerizing ethene by using it in conjunction with alkyl aluminoxyane or alkayl aluminium and its preparing process are disclosed. It has higher reactive activity and better dipolymerizing and tripolymerizing performance.

Description

Ethylene oligomerization catalyst and its production and application
Technical field
The present invention is a kind of ethylene oligomerization catalyst and preparation method and application, specifically, is a kind of N^O of containing bitooth ligand coordinate Ni (II) composition catalyst and preparation method, and uses this catalyzer to carry out the method for ethylene oligomerization.
Background technology
The oligopolymer of ethene and derivative alpha-olefin thereof generally is thick or semi-solid state, 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) endgroup content than superpolymer is bigger, and function is easy to manifest; 3) the structure variation of oligopolymer can be carried out chemical conversion and curing reaction again, is convenient to molecular designing; 4) in the application of oligopolymer, can not use solvent.
The oligopolymer of ethene mainly is C 6～C 20Linear alpha-alkene.These linear alpha-alkenes are widely used in the comonomer of producing washing composition, softening agent, lubricant and conduct preparation linear low density polyethylene (LLDPE).At present, the catalyzer of industrial production ethylene oligomer is aluminum alkyls and TiCl 4Cooperate the catalyst system that forms, or be the catalyst system that Primary Catalysts forms with the title complex of the Ni (II) that contains single anion bitooth ligand P^O, be that Primary Catalysts prepares ethylene oligomer promptly as USP 3686351 and USP 3676523 with the bidentate title complex of phosphorated carboxylate salt and simple divalent nickel salt reaction formation.
The composition catalyst that is used for the Ni that contains single anion bitooth ligand P^O (II) of ethylene oligomerization is studied widely.In the decades in past, 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 can both obtain alkyl or the halogenated compound that neutral has catalytic activity by these single anion ligands.With this compounds is catalyzer when carrying out ethylene oligomerization, needs higher temperature of reaction and pressure, and the oligomerisation temperature is generally 80～120 ℃, and ethylene pressure is 10MPa.Found afterwards cationic Ni (II) title complex that obtains by neutral P^O part under very low temperature and pressure, can make ethylene oligomerization.Nearest studies show that, by the neutral ligand of various other types, also can obtain the composition catalyst of active Ni of oligomerisation (II) and Pd (II) as diimine N^N and phosphine amine P^N part.
In addition; USP5; 932; 670 disclose a kind of pyridine-2-acyl group imines dihalide nickel (2-pyridinecarboxaldimime nickel dihalide) title complex; contain two six-rings in this complex ligand, one is the phenyl ring that links to each other with the imido grpup nitrogen-atoms, and another is the azepine phenyl ring (pyridine ring) that links to each other with the imido grpup carbon atom; also can be connected with substituent R on the imido grpup carbon atom, R is the alkyl or aryl of 1～70 carbon atom.This title complex is as the Primary Catalysts of olefin oligomerization, and needing with MAO is promotor, and the oligomerisation activity is lower, and the oligomerisation activity under 1MPa pressure only is 10 4G (molNi) -1Hr -1
Summary of the invention
The purpose of this invention is to provide a kind of ethylene oligomerization catalyst and this Preparation of catalysts method and the method that is used for ethylene oligomerization.
Ethylene oligomerization catalyst provided by the invention has the structure expression of formula (I):
In the formula (I), R is selected from C 6～C 14Alkaryl, R 1, R 2Be selected from hydrogen, C respectively 1～C 6Alkyl or nitro, Ph is a phenyl.
Catalyzer of the present invention adopts the part with N^O double coordination, part and with the group of nickle atom bonding in all contain phenyl ring or condensed ring aromatic base, have bigger sterically hindered, can stop ethene to carry out the poly reaction in the reaction process, thereby have ethylene dimerization and trimerization selectivity preferably, and reactive behavior is higher.
Embodiment
Ligand compound is the N-pyridyl benzamide compound that Benzoyl chloride derivative and aminopyrazole derivatives condensation form in the catalyzer of the present invention.The phenyl ring of described Benzoyl chloride and the substituent R on the pyridine ring 1, R 2The preferred hydrogen of difference, C 1～C 4Alkyl or nitro, more preferably hydrogen, methyl, ethyl or nitro, the substituting group number can be 1～5.R with the nickel bonding in the catalyzer is C 6～C 14Alkaryl, the aryl in the alkaryl is selected from phenyl or naphthyl, preferred phenyl or naphthyl, alkyl is selected from C 1～C 4Alkyl, preferable methyl, ethyl, propyl group or butyl.
Preparation of catalysts method of the present invention comprises the steps:
(1) the Benzoyl chloride derivative shown in the formula (II) is dissolved in tetrahydrofuran (THF) and makes solution, 2-aminopyrazole derivatives shown in the formula (III) is dissolved in pyridine makes solution, then described tetrahydrofuran solution is added in the pyridine solution, formula (II) and formula (III) compound are fully reacted down at 20～100 ℃ by 1～1.1: 1 mol ratio, washing then, removing desolvates promptly gets N-pyridyl benzamides ligand compound, in described formula (II), the formula (III), and R 1, R 2Be selected from hydrogen, C respectively 1～C 4Alkyl or nitro,
Figure A20041003793200052
(2) with N-pyridyl benzamides ligand compound in the presence of organic medium with sodium hydride by 1: 1.0～1.5 molar ratio reaction, add toluene again and close nickel with the trans-chlorination (alkaryl) (triphenyl phosphorus) of mol ratio such as described ligand compound and continue reaction, filter then, after filtrate concentrated, add C 5～C 8Alkane, with gained solids C 5～C 8Alkane washing after drying.
In the aforesaid method, (1) step tetrahydrofuran solution concentration of Chinese style (II) compound is 0.1～1.0 mol, and the pyridine solution concentration of formula (III) compound is 0.2～0.5 mol.Preferred 10～25 ℃ of temperature of reaction.
In described (2) step, the preferred tetrahydrofuran (THF) of organic medium, concentration of reactants is 0.05～0.5 mol, preferred 10～25 ℃ of (2) step temperature of reaction.Wherein the reaction times of N-pyridyl benzamides ligand compound and sodium hydride is 0.5～3 hour, afterwards 10～25 ℃ with etc. the organic nickel compound of mol ratio continue reaction 12～36 hours, filter then, filtrate is concentrated, add the C of 3～6 times of amounts of concentrated solution volume again 5～C 8Alkane, with gained solids C 5～C 8Alkane washing after drying.Described C 5～C 8Alkane be selected from pentane, hexane, heptane or octane, preferred pentane or hexane.
The aryl that trans-chlorination (alkaryl) (triphenyl phosphorus) that above-mentioned preparation method uses is closed in the nickel is selected from phenyl or naphthyl, and alkyl is selected from C 1～C 4Alkyl, preferably trans-chlorination (phenyl) (triphenyl phosphorus) closes nickel, trans-chlorination (naphthyl) (triphenyl phosphorus) closes nickel.The preparation method that trans-chlorination (alkaryl) (triphenyl phosphorus) closes nickel is as follows:
At first prepare four (triphenylphosphine) nickel.Under nitrogen protection; make triphenylphosphine and anhydrous bis-acetylacetonate base nickel by 5.5～6.0: 1 mol ratio is suspended in the ether medium; be cooled to 0～5 ℃, drip the diethyl ether solution of triethyl aluminum gradually, reaction mixture becomes brick-red by green and has reddish-brown precipitation to generate.Drip the back 5～10 ℃ of stirring reactions 0.5～1.0 hour, 25 ℃ of stirring reactions 1～5 hour, leach throw out then,, promptly get crude product after the drying with the ether washing.
The crude product of gained four (triphenylphosphine) nickel can be purified as follows: at 50～70 ℃, with concentration is the benzole soln extraction crude product of the triphenylphosphine of 10～12 quality %, add heptane then in extracting solution, the add-on of heptane is 0.2～0.5 times of extracting liquid volume.Filter the precipitation that generates, with heptane and ether washing, get the sorrel crystallisate respectively, it is dry under 90 ℃ of decompressions, promptly get pure four (triphenylphosphine) nickel.
Under nitrogen protection; four (triphenylphosphine) nickel is suspended in the toluene; 20～40 ℃ add the chloro alkylaromatic hydrocarbon; the mol ratio of described chloro alkylaromatic hydrocarbon and four (triphenylphosphine) nickel is 1～1.1: 1, and stirring reaction obtains homogeneous solution, solution left standstill 0.5～4 hour; separate out the tawny crystallization; leach crystallization, use petroleum ether, be drying to obtain trans-chlorination (alkaryl) (triphenyl phosphorus) under the decompression and close nickel.Gained filtrate can add the further trans-chlorination (alkaryl) (triphenyl phosphorus) of extracting wherein of an amount of sherwood oil and close nickel.React preferred benzene of aromatic hydrocarbons in the used chloro alkylaromatic hydrocarbon or naphthalene, the preferred C of alkyl 1～C 4Alkyl.
Ethylene oligomerization method provided by the invention is to be Primary Catalysts with the described title complex of formula (I), is promotor with alkylaluminoxane, aluminum alkyls, makes ethene carry out oligomerisation reaction.Suitable oligomerisation reaction temperature is that 0～80 ℃, pressure are 0.1～0.3MPa, and the mol ratio of promotor and Primary Catalysts is 100～3000 during reaction, preferred 100～1500.
Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta in the described promotor, the preferred trimethyl aluminium of aluminum alkyls, triethyl aluminum, triisobutyl aluminium, diethyl aluminum chloride or ethylaluminum dichloride.When adding promotor, can add the catalytic performance that triphenyl phosphorus improves catalyzer in system during reaction, the triphenyl phosphorus of adding and the mol ratio of Primary Catalysts are 1～20, preferred 1～5.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare trans-chlorination (phenyl) (triphenyl phosphorus) and close nickel.
Under nitrogen gas stream, 125 gram (0.4883mol) triphenylphosphines (Beijing chemical reagent work) and 21.3 gram (0.083mol) anhydrous bis-acetylacetonate base nickel (STREM company) are suspended in 800 milliliters of ether, mixture is chilled to 0 ℃ with ice-methanol bath, slowly drips 100 milliliters of diethyl ether solutions that contain 28 gram triethyl aluminums.In the dropping process, reaction mixture becomes brick-red by green and has reddish-brown precipitation to generate.Drip the back and stirred 30 minutes at 5～10 ℃, 25 ℃ were stirred 2 hours, leached throw out, with 40 milliliters of ether washings 2 times, 25 ℃ of vacuum-drying 4 hours, 81.2 restrain four (triphenylphosphine) nickel, 123～128 ℃ of fusing points.
Under the nitrogen protection; 0.9 gram (0.81mmol) four (triphenylphosphine) nickel is suspended in 10 milliliters of toluene; 20 ℃ add the 0.83mmol chlorobenzene, stir 20 minutes, obtain homogeneous solution; with solution left standstill one day; scarlet disappears, and separates out the tawny crystallization, leaches crystallization; with 10 milliliters of petroleum ether, drying under reduced pressure 2 hours.Will be in the filtrate add 10 milliliters of sherwood oils, fractional crystallization thing, and drying under reduced pressure 2 hours.Front and back obtain 0.42 gram trans-chlorination (phenyl) (triphenyl phosphorus) altogether and close nickel, 122～123 ℃ of fusing points.
Example 2
Press method preparation four (triphenylphosphine) nickel of example 1, to wash the crude product that obtains after the drying with ether, dissolve crude products at 60 ℃ with 400 milliliters of benzene that contain 40 gram triphenylphosphines, in solution, add 200 milliliters of heptane, filter, the gained solid is distinguished washed twice with 200 milliliters of heptane and 180 milliliters of ether.Repeat aforesaid operations, the sorrel crystallization, crystallization under 90 ℃ of decompressions dry 16 hours, pure four (triphenylphosphine) nickel of 50 grams, 123～128 ℃ of fusing points.
Under the nitrogen protection; 0.9 gram (0.81mmol) four (triphenylphosphine) nickel is suspended in 10 milliliters of toluene; 20 ℃ add the 0.83mmol naphthalene chloride, stir 20 minutes, obtain homogeneous solution; with solution left standstill one day; scarlet disappears, and separates out the tawny crystallization, leaches crystallization; with 10 milliliters of petroleum ether, drying under reduced pressure 2 hours.Will be in the filtrate add 10 milliliters of sherwood oils, fractional crystallization thing, and drying under reduced pressure 2 hours.Front and back obtain the 0.45 trans-chlorination of gram (1-naphthyl) (triphenyl phosphorus) altogether and close nickel.
Example 3
Prepare catalyzer of the present invention: 1-naphthyl (N-2-pyridine benzamide) triphenyl phosphorus closes nickel.
(1) preparation ligand compound: N-2-pyridine benzamide.
0.94 gram (10mmol) 2-aminopyridine is dissolved in 20 milliliters of exsiccant pyridines, splash into 10 milliliters of tetrahydrofuran solutions that contain 1.41 gram (10mmol) Benzoyl chlorides, 25 ℃ were stirred 10 hours, pour into again in 500 milliliters of deionized waters and stirred 1 hour, filter, with deionized water washing 3 times, 60 ℃ of dryings 2 hours obtain white solid N-2-pyridine benzamide (C with the gained solid 12H 10N 2O), productive rate 63 quality %, 68～70 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3170(br)，1674(s)，1580(s)，1531(s)，1435(s)，1305(s)，777(m)，722(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝7.09(t，1H，J＝6.10Hz)，7.45?7.62(m，3H)，7.78(t，1H，J＝7.47Hz)，7.95(d，2H，J＝7.48Hz)，8.30(d，1H，J＝4.72Hz)，8.42(d，1H，J＝8.33Hz)，8.69(bs，1H，NH)。
Ultimate analysis theory (mensuration) value, quality %:C 72.71 (72.88), and H 5.08 (5.05), N14.13 (13.83).
(2) preparation catalyzer.
198 milligrams of (1mmol) N-2-pyridine benzamide are dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, the NaH that adds 1.5mmo1,25 ℃ were stirred 1 hour, decompression dry 1 hour down, add 746 milligrams (1mmol) trans-chlorination (1-naphthyl) (triphenyl phosphorus) closes nickel and 40 milliliters of toluene, stirred 24 hours.Filter, filtrate is concentrated into 10 milliliters, add 40 milliliters of pentanes.With the gained sedimentation and filtration, with 5 milliliters of pentane washings, decompression dry 2 hours down, obtain 509 milligrams of tawny powder: 1-naphthyl (N-2-pyridine benzamide) triphenyl phosphorus closes nickel (C 40H 31N 2NiOP), be designated as catalyst A, productive rate 79 quality %, 200～202 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3429(br)，3051(w)，1559(m)，1504(m)，1436(s)，1393(m)，781(m)，696(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.19(t，1H，J＝6.54Hz)，6.81(t，1H，J＝7.43Hz)，6.91(d，1H，J＝6.60Hz)，7.00(t，2H，J＝7.61Hz)，7.08-7.97(m，25H)，9.58(d，1H，J＝8.06Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝28.25。
Ultimate analysis theory (mensuration) value, quality %:C 74.44 (74.98), and H 4.84 (5.22), and N 4.34 (4.20).
Example 4
Preparation catalyzer 1-naphthyl [N-2-(4-picoline) benzamide] triphenyl phosphorus closes nickel.
Method by 3 (1) steps of example prepares ligand compound, different is to replace the 2-aminopyridine to react with 1.08 gram (10mmol) 2-amino-4-picolines, obtain 1.05 gram white solids after the drying, be ligand compound N-2-(4-picoline) benzamide (C 13H 12N 2O), productive rate 50 quality %, 106～108 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3308(s)，1661(s)，1535(s)，1411(s)，1301(s)，1164(m)，705(s)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝2.44(s，3H，CH 3)，6.93(d，1H，J＝5.03Hz)，7.50?7.63(m，3H)，7.96(d，2H，J＝7.28Hz)，8.14(d，1H，J＝5.10Hz)，8.28(s，1H)，8.74(bs，1H，NH)。
Ultimate analysis theory (mensuration) value, quality %:C 73.56 (73.74); H 5.70 (5.73); N13.20 (12.84).
212 milligrams of (1mmol) N-2-(4-picoline) benzamide is dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 1mmol trans-chlorination (1-naphthyl) (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain 430 milligrams of xanchromatic powder after process, washing, the drying, for 1-naphthyl [N-2-(4-picoline) benzamide] triphenyl phosphorus closes nickel (C 40H 31N 2NiOP), be designated as catalyst B, productive rate 65 quality %, 134～136 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3432(br)，3052(w)，1556(m)，1500(m)，1441(s)，1379(m)，697(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝2.14(s，3H，CH 3)，6.03(d，1H，J＝6.40Hz)，6.74(d，1H，J＝6.55Hz)，6.78(t，1H，J＝7.45Hz)，6.97(t，3H，J＝7.55Hz)，7.06-7.56(m，23H)，9.55(d，1H，J＝8.04Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝28.82。
Ultimate analysis theory (mensuration) value, quality %:C 74.68 (75.13); H 5.04 (5.14); N4.25 (4.03).
Example 5
Preparation catalyzer 1-naphthyl [N-2-(5-nitropyridine) benzamide] triphenyl phosphorus closes nickel.
Method by 3 (1) steps of example prepares ligand compound, different is to replace the 2-aminopyridine to react with 1.39 gram (10mmol) 2-amino-5-nitropyridines, obtain 2.32 gram white solids after the drying, be ligand compound N-2-(5-nitropyridine) benzamide (C 12H 9N 3O 3), productive rate 96 quality %, 165～167 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3347(m)，1689(s)，1601(s)，1514(s)，1395(m)，1343(s)，1234(s)，1120(s)，852(m)，716(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝7.55(t，2H，J＝7.49Hz)，7.64(t，1H，J＝7.21Hz)，7.95(d，2H，J＝7.61Hz)，8.58(m，2H)，8.94(bs，1H，NH)，9.16(s，1H)。
Ultimate analysis theory (mensuration) value, quality %:C 59.26 (59.22); H 3.73 (3.72); N17.28 (16.91).
243 milligrams of (1mmol) N-2-(5-picoline) benzamide is dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 1mmol trans-chlorination (1-naphthyl) (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain the powder of 520 milligrams of redness after process, washing, the drying, for 1-naphthyl [N-2-(5-nitropyridine) benzamide] triphenyl phosphorus closes nickel (C 40H 30N 3NiO 3PC 7H 8), be designated as catalyzer C, productive rate 62 quality %, 156～158 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3053(w)，1570(m)，1490(m)，1459(m)，1433(s)，1331(s)，696(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.64(t，1H，J＝7.41Hz)，6.79-7.70(m，27H)，8.03(d，1H，J＝8.80Hz)，9.35(d，1H，J＝7.64Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝28.20。
Ultimate analysis theory (mensuration) value, quality %:C 72.14 (71.81); H 4.89 (4.93), N5.37 (5.40).
Example 6
Preparation catalyzer 1-naphthyl (N-2-pyridine-4-nitrobenzamide) triphenyl phosphorus closes nickel.
Method by 3 (1) steps of example prepares ligand compound, and different is to replace Benzoyl chloride to react with 1.86 gram (10mmol) gram 4-nitrobenzoyl chlorides, obtains 1.34 gram white solids after the drying, is ligand compound N-2-pyridine-4-nitrobenzamide (C 12H 9N 3O 3), productive rate 55 quality %, 236～238 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3347(m)，1679(s)，1584(s)，1515(s)，1438(m)，1312(s)，853(m)，790(m)，716(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝7.11(t，1H，J＝6.10Hz)，7.78(t，1H，J＝7.89Hz)，8.07(d，2H，J＝8.46Hz)，8.33(t，4H，J＝7.71Hz)，8.58(bs，1H，NH)。
Ultimate analysis theory (mensuration) value, quality %:C 59.26 (59.23), and H 3.73 (3.73), N17.28 (17.23).
243 milligrams of (1mmol) N-2-pyridine-4-nitrobenzamides are dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 1mmol trans-chlorination (1-naphthyl) (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain 463 milligrams of xanchromatic powder after process, washing, the drying, for 1-naphthyl (N-2-pyridine-4-nitrobenzamide) triphenyl phosphorus closes nickel (C 40H 30N 3NiO 3P), be designated as catalyzer D, productive rate 68 quality %, 200～202 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3051(w)，1566(s)，1523(s)，1457(s)，1432(s)，1344(s)，696(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.25(t，1H，J＝6.51Hz)，6.81(t，1H，J＝7.37Hz)，6.92(d，1H，J＝7.37Hz)，7.09-7.57(m，24H)，7.82(d，2H，J＝8.62Hz)，9.53(d，1H，J＝8.62Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝28.57。
Ultimate analysis theory (mensuration) value, quality %:C 69.59 (69.80), and H 4.38 (4.40), N6.09 (6.23).
Example 7
Preparation catalyzer 1-naphthyl [N-2-(4-picoline)-4-nitrobenzamide] triphenyl phosphorus closes nickel.
Method by 3 (1) steps of example prepares ligand compound, different is to react with 1.08 gram (10mmol) 2-amino-4-picolines and 1.86 gram (10mmol) gram 4-nitrobenzoyl chlorides, obtain 2.31 gram white solids after the drying, be ligand compound N-2-pyridine-4-nitrobenzamide (C 13H 11N 3O 3), productive rate 90 quality %, 182～184 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3347(m)，1659(s)，1606(m)，1533(s)，1349(m)，1300(m)，854(m)，717(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝2.43(s，3H，CH 3)，6.95(d，1H，J＝4.95Hz)，7.88??8.25(m，4H)，8.35(d，2H，J＝8.63Hz)，8.81(bs，1H，NH)。
Ultimate analysis theory (mensuration) value, quality %:C 60.70 (59.90), and H 4.31 (4.17), N16.33 (15.81).
257 milligrams of (1mmol) N-2-(4-picoline)-4-nitrobenzamide is dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 1mmol trans-chlorination (1-naphthyl) (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain 475 milligrams of xanchromatic powder after process, washing, the drying, for 1-naphthyl [N-2-(4-picoline)-4-nitrobenzamide] triphenyl phosphorus closes nickel (C 41H 32N 3NiO 3P), be designated as catalyzer E, productive rate 68 quality %, fusing point＞196 ℃.
FT-IR(KBr?disc，cm -1)：3429(br)，3051(w)，1577(m)，1522(m)，1455(s)，1330(s)，1105(m)，695(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝2.17(s，3H，CH 3)，6.11(d，1H，J＝6.09Hz)，6.79-7.53(m，25H)，7.83(d，2H，J＝8.71Hz)，9.54(d，1H，J＝8.05Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝28.69。
Ultimate analysis theory (mensuration) value, quality %:C 69.91 (69.19), and H 4.58 (4.53), N5.97 (5.97).
Example 8
Preparation catalyzer 1-naphthyl [N-2-(5-nitropyridine)-4-nitrobenzamide] triphenyl phosphorus closes nickel.
Method by 3 (1) steps of example prepares ligand compound, different is to react with 1.39 gram (10mmol) 2-amino-5-picolines and 1.86 gram (10mmol) gram 4-nitrobenzoyl chlorides, obtain 2.49 gram white solids after the drying, be ligand compound N-2-(5-nitropyridine)-4-nitrobenzamide (C 12H 8N 4O 5), productive rate 87 quality %, 216～218 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3394(m)，1691(s)，1606(s)，1513(s)，1350(s)，1299(s)，1225(m)，1118(m)，850(m)，714(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.94(d，1H，J＝4.78Hz)，7.87?8.24(m，4H)，8.35(d，2H，J＝8.46Hz)，8.72(bs，1H，NH)。
Ultimate analysis theory (mensuration) value, quality %:C 50.01 (49.82), and H 2.80 (2.57), N19.44 (19.67).
288 milligrams of (1mmol) N-2-(5-nitropyridine)-4-nitrobenzamide is dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 1mmol trans-chlorination (1-naphthyl) (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain the powder of 422 milligrams of redness after process, washing, the drying, 1-naphthyl [N-2-(5-nitropyridine)-4-nitrobenzamide] triphenyl phosphorus closes nickel (C 41H 32N 3NiO 3P), be designated as catalyzer F, productive rate 53 quality %, 230～232 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3429(br)，3051(w)，1577(m)，1522(m)，1455(s)，1330(s)，1130(s)，1105(m)，695(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.92(t，1H，J＝7.39Hz)，7.15-7.74(m，24H)，7.87(d，2H，J＝8.33)，8.18(d，1H，J＝9.05Hz)，9.40(d，1H，J＝7.69Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝28.42。
Ultimate analysis theory (mensuration) value, quality %:C 65.33 (64.98), and H 3.98 (3.85), N7.62 (7.76).
Example 9
Preparation catalyzer phenyl [N-2-(5-nitropyridine) benzamide] triphenyl phosphorus closes nickel.
243 milligrams of (1mmol) N-2-(5-nitropyridine) benzamide is dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 696 milligrams (1mmol) trans-chlorination phenyl (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain the powder-product of 371 milligrams of redness after process, washing, the drying, for phenyl [N-2-(5-nitropyridine) benzamide] triphenyl phosphorus closes nickel, be designated as catalyzer G (C 36H 28N 3NiO 3P), productive rate 58 quality %, 174 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3445(br)，3053(w)，1568(m)，1492(m)，1433(s)，1328(s)，1107(m)，698(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.71(m，3H)，7.04-7.60(m，24H)，7.99(s，1H)，8.19(dd，1H，J＝9.15Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝29.22。
Ultimate analysis theory (mensuration) value, quality %:C 67.53 (67.82), and H 4.41 (4.48), N6.56 (6.76).
Example 10
Preparation catalyzer phenyl [N-2-(5-nitropyridine)-4-nitrobenzamide] triphenyl phosphorus closes nickel.
288 milligrams of (1mmol) N-2-(5-nitropyridine)-4-nitrobenzamide is dissolved in 10 milliliters of exsiccant tetrahydrofuran (THF)s, after making it NaH reaction with 1.5mmol by the method in example 3 (2) step, again with 696 milligrams (1mmol) trans-chlorination phenyl (triphenyl phosphorus) closes nickel stirring reaction 24 hours in the presence of 40 milliliters of toluene, obtain the powder-product of 418 milligrams of redness after process, washing, the drying, for phenyl [N-2-(5-nitropyridine)-4-nitrobenzamide] triphenyl phosphorus closes nickel (C 36H 27N 4NiO 5P), be designated as catalyzer H, productive rate 61 quality %, 180 ℃ of fusing points.
FT-IR(KBr?disc，cm -1)：3431(br)，3053(w)，1578(m)，1523(m)，1456(s)，1328(s)，1107(m)，696(m)。
1H?NMR(300MHz，CDCl 3，TMS)：δ＝6.62(m，3H)，7.08-7.76(m，21H)，7.95(s，1H)，8.17(d，1H，J＝7.58Hz)。
31P?NMR(toluene，H 3PO 4)：δ＝29.45。
Ultimate analysis theory (mensuration) value, quality %:C 63.10 (63.25), and H 3.97 (3.98), N8.18 (8.07).
Example 11
250 milliliter of three neck round-bottomed flask that magnetic stick is housed 130 ℃ of successive dryings 6 hours, vacuumized and while hot with nitrogen replacement 3 times.Add 3.3 milligram (5 * 10 -6Mol) catalyst B, an amount of triphenyl phosphorus, and then vacuumize and replace 3 times with ethene.Inject 30 milliliters of toluene with syringe, add the toluene solution that concentration is the methylaluminoxane of 10 quality % again, making the Al/Ni mol ratio is 1000.Vigorous stirring is 0.5 hour under 30 ℃, the condition of 0.1MPa ethylene pressure.With 5% dilute hydrochloric acid termination reaction.The gas Chromatographic Determination oligopolymer, different P/Ni see Table 1 than catalyst activity under the condition and products distribution.Table 1 result demonstration, behind the adding auxiliary agent triphenyl phosphorus, C in the oligomerization product 6Component concentration obviously increases.
Example 12
The oligomerisation performance of this example evaluate catalysts.
250 milliliter of three neck round-bottomed flask that magnetic stick is housed 130 ℃ of successive dryings 6 hours, vacuumized and while hot with nitrogen replacement 3 times.The catalyzer that adds the present invention's preparation vacuumizes then and replaces 3 times with ethene.Inject 30 milliliters of toluene with syringe, add the toluene solution that concentration is the methylaluminoxane of 10 quality % again, under the temperature of regulation, keep the ethylene pressure of 0.1MPa, the vigorous stirring reaction regular hour.Use 5% dilute hydrochloric acid termination reaction at last.Oligopolymer with the gas Chromatographic Determination generation.Each catalyzer sees Table 2 in the catalytic activity and the products distribution of differential responses condition.
Table 1
P/Ni, mol ratio The oligomerisation activity, gram oligopolymer/(mole Ni hour) Oligomerization product, quality %
????C4 ????C6
??1 ????4.82×10 5 ????75.5 ????24.5
??2 ????4.36×10 5 ????77.9 ????22.1
??5 ????3.63×10 5 ????85.8 ????14.2
??10 ????1.71×10 5 ????91.9 ????9.1
??20 ????1.39×10 5 ????95.1 ????4.9
Table 2
The catalyzer numbering Reaction conditions The oligomerisation activity restrains oligopolymer/mole Ni hour Oligomerization product, quality %
Temperature, ℃ Time, hour Al/Ni, mol ratio
????C4 ????C6
??A ????25 ????0.5 ????100 ????0.74×10 5 ????93.6 ????6.4
????25 ????0.5 ????300 ????2.81×10 5 ????87.9 ????12.1
????25 ????0.5 ????500 ????2.33×10 5 ????91.6 ????8.4
????25 ????0.5 ????1000 ????2.69×10 5 ????90.6 ????9.4
????25 ????0.5 ????1500 ????2.47×10 5 ????91.5 ????8.5
????25 ????0.5 ????2000 ????2.87×10 5 ????90.3 ????9.7
????25 ????0.5 ????2500 ????2.64×10 5 ????90.4 ????9.6
????25 ????0.5 ????3000 ????2.35×10 5 ????90.3 ????9.7
????0 ????0.5 ????1000 ????1.87×10 5 ????97.0 ????3.0
????40 ????0.5 ????1000 ????3.33×10 5 ????84.0 ????16.0
????60 ????0.5 ????1000 ????1.23×10 5 ????81.8 ????18.2
????80 ????0.5 ????1000 ????0.95×10 5 ????80.0 ????20.0
??B ????22 ????0.5 ????100 ????0.08×10 5 ????92.8 ????7.2
????22 ????0.5 ????300 ????1.09×10 5 ????92.3 ????7.7
????22 ????0.5 ????500 ????4.19×10 5 ????88.4 ????11.6
????22 ????0.5 ????1000 ????4.94×10 5 ????88.1 ????11.9
????22 ????0.5 ????1500 ????3.62×10 5 ????87.4 ????12.6
????22 ????0.5 ????2000 ????2.39×10 5 ????89.7 ????10.3
????0 ????0.5 ????1000 ????1.67×10 5 ????96.9 ????3.1
????40 ????0.5 ????1000 ????3.37×10 5 ????83.4 ????16.6
????60 ????0.5 ????1000 ????2.13×10 5 ????75.9 ????24.1
????80 ????0.5 ????1000 ????0.74×10 5 ????82.0 ????18.0
????30 ????0.1 ????1000 ????15.2×10 5 ????91.5 ????8.5
????30 ????0.25 ????1000 ????9.48×10 5 ????85.5 ????14.5
????30 ????0.5 ????1000 ????4.94×10 5 ????88.1 ????11.9
????30 ????1.0 ????1000 ????3.13×10 5 ????81.4 ????18.6
????30 ????1.5 ????1000 ????2.09×10 5 ????82.3 ????17.7
????30 ????2.0 ????1000 ????2.11×10 5 ????79.7 ????20.3
??C ????23 ????0.5 ????100 ????0.72×10 5 ????85.2 ????14.8
????23 ????0.5 ????300 ????2.23×10 5 ????91.5 ????8.5
????23 ????0.5 ????500 ????1.54×10 5 ????85.2 ????14.8
????23 ????0.5 ????1000 ????1.87×10 5 ????89.7 ????10.3
????23 ????0.5 ????1500 ????1.57×10 5 ????89.6 ????10.4
????23 ????0.5 ????2000 ????1.97×10 5 ????89.7 ????10.3
????0 ????0.5 ????1000 ????0.54×10 5 ????94.1 ????5.9
????40 ????0.5 ????1000 ????1.79×10 5 ????81.4 ????18.6
????60 ????0.5 ????1000 ????1.35×10 5 ????81.5 ????18.5
Continuous table 2
The catalyzer numbering Reaction conditions The oligomerisation activity restrains oligopolymer/mole Ni hour Oligomerization product, quality %
Temperature, ℃ Time, hour Al/Ni, mol ratio
????C4 ????C6
????C ????80 ????0.5 ????1000 ????0.73×10 5 ????80.8 ????19.2
????D ????24 ????0.5 ????100 ????0.66×10 5 ????74.0 ????26.0
????24 ????0.5 ????300 ????1.36×10 5 ????88.6 ????11.4
????24 ????0.5 ????500 ????2.09×10 5 ????90.4 ????9.6
????24 ????0.5 ????1000 ????1.67×10 5 ????89.9 ????10.1
????24 ????0.5 ????1500 ????1.24×10 5 ????99.7 ????0.3
????24 ????0.5 ????2000 ????1.45×10 5 ????88.3 ????11.7
????0 ????0.5 ????1000 ????0.59×10 5 ????92.6 ????7.4
????40 ????0.5 ????1000 ????1.81×10 5 ????84.7 ????15.3
????60 ????0.5 ????1000 ????1.29×10 5 ????79.4 ????20.6
????80 ????0.5 ????1000 ????1.20×10 5 ????78.8 ????21.2
????E ????24 ????0.5 ????100 ????2.31×10 5 ????89.2 ????10.8
????24 ????0.5 ????300 ????2.42×10 5 ????86.8 ????13.2
????24 ????0.5 ????500 ????2.50×10 5 ????90.0 ????10.0
????24 ????0.5 ????1000 ????3.57×10 5 ????87.9 ????12.1
????24 ????0.5 ????1500 ????2.72×10 5 ????87.1 ????12.9
????24 ????0.5 ????2000 ????1.95×10 5 ????88.7 ????11.3
????0 ????0.5 ????1000 ????0.67×10 5 ????96.5 ????3.5
????40 ????0.5 ????1000 ????2.36×10 5 ????83.8 ????16.2
????60 ????0.5 ????1000 ????1.50×10 5 ????80.3 ????19.7
????80 ????0.5 ????1000 ????0.97×10 5 ????79.5 ????20.5
????F ????25 ????0.5 ????100 ????1.49×10 5 ????86.4 ????13.6
????25 ????0.5 ????300 ????1.78×10 5 ????90.1 ????9.9
????25 ????0.5 ????500 ????1.58×10 5 ????87.8 ????12.2
????25 ????0.5 ????1000 ????1.80×10 5 ????87.7 ????12.3
????25 ????0.5 ????1500 ????1.63×10 5 ????86.8 ????13.2
????25 ????0.5 ????2000 ????1.88×10 5 ????86.0 ????14.0
????0 ????0.5 ????1000 ????0.55×10 5 ????93.7 ????6.3
????40 ????0.5 ????1000 ????1.83×10 5 ????80.6 ????19.7
????60 ????0.5 ????1000 ????1.14×10 5 ????79.6 ????20.4
????80 ????0.5 ????1000 ????0.65×10 5 ????78.7 ????21.3
????G ????28 ????0.5 ????1000 ????2.23×10 5 ????85.1 ????14.9
????H ????28 ????0.5 ????1000 ????2.08×10 5 ????85.9 ????14.1

Claims (12)

1, a kind of ethylene oligomerization catalyst has the structure expression of formula (I):
Figure A2004100379320002C1
In the formula (I), R is selected from C 6～C 14Alkaryl, R 1, R 2Be selected from hydrogen, C respectively 1～C 6Alkyl or nitro, Ph is a phenyl.
2, according to the described catalyzer of claim 1, it is characterized in that the aryl in the described alkaryl is selected from phenyl or naphthyl, alkyl is selected from C 1～C 4Alkyl, R 1, R 2Be selected from hydrogen, C respectively 1～C 4Alkyl or nitro.
3,, it is characterized in that described alkaryl is selected from phenyl or naphthyl, R according to the described catalyzer of claim 1 1, R 2Be selected from hydrogen, methyl, ethyl or nitro respectively.
4, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) the Benzoyl chloride derivative shown in the formula (II) is dissolved in tetrahydrofuran (THF) and makes solution, 2-aminopyrazole derivatives shown in the formula (III) is dissolved in pyridine makes solution, then described tetrahydrofuran solution is added in the pyridine solution, formula (II) and formula (III) compound are fully reacted down at 20～100 ℃ by 1～1.1: 1 mol ratio, washing then, removing desolvates promptly gets N-pyridyl benzamides ligand compound, in described formula (II), the formula (III), and R 1, R 2Be selected from hydrogen, C respectively 1～C 4Alkyl or nitro,
Figure A2004100379320002C2
(2) with N-pyridyl benzamides ligand compound in the presence of organic medium with sodium hydride by 1: 1.0～1.5 molar ratio reaction, add toluene again and close nickel with the trans-chlorination (alkaryl) (triphenyl phosphorus) of mol ratio such as described ligand compound and continue reaction, filter then, after filtrate concentrated, add C 5～C 8Alkane, with gained solids C 5～C 8Alkane washing after drying.
5, in accordance with the method for claim 4, it is characterized in that described trans-aryl that chlorination (alkaryl) (triphenyl phosphorus) is closed in the nickel is selected from phenyl or naphthyl, alkyl is selected from C 1～C 4Alkyl.
6, in accordance with the method for claim 4, it is characterized in that the tetrahydrofuran solution concentration of (1) step Chinese style (II) compound is 0.1～1.0 mol, the pyridine solution concentration of formula (III) compound is 0.2～0.5 mol.
7, in accordance with the method for claim 4, it is characterized in that described organic medium of (2) step is a tetrahydrofuran (THF), temperature of reaction is 10～25 ℃.
8, in accordance with the method for claim 4, the reaction times that it is characterized in that N-pyridyl benzamides ligand compound and sodium hydride in (2) step is 0.5～3 hour, afterwards 10～25 ℃ with etc. the organic nickel compound continuation of mol ratio reacted 12～36 hours.
9, in accordance with the method for claim 4, it is characterized in that (2) go on foot described C 5～C 8Alkane is selected from pentane, hexane, heptane or octane, adds C in concentrated filtrate 5～C 8The amount of alkane is 3～6 times of filtrate volume.
10, a kind of ethylene oligomerization method comprises that with the described catalyzer of claim 1 be Primary Catalysts, is promotor with alkylaluminoxane or aluminum alkyls, makes ethene carry out oligomerisation reaction.
11, according to the described catalyzer of claim 10, it is characterized in that described alkylaluminoxane is selected from methylaluminoxane, aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diethyl aluminum chloride or ethylaluminum dichloride, and the mol ratio of described promotor and Primary Catalysts is 100-3000.
12, according to the described catalyzer of claim 10, it is characterized in that in described system, adding triphenyl phosphorus, the triphenyl phosphorus of adding and the mol ratio of Primary Catalysts are 1～20.
CN 200410037932 2004-05-14 2004-05-14 Ethylene oligomerization catalyst, preparation method and application Pending CN1695807A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101618343B (en) * 2008-06-30 2011-05-18 中国石油化工股份有限公司 Load-type olefin oligomerization catalyst and preparation method thereof
CN114054096A (en) * 2020-07-30 2022-02-18 中国石油化工股份有限公司 Solid base catalyst for preparing 4-methyl-1-pentene by propylene oligomerization and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101618343B (en) * 2008-06-30 2011-05-18 中国石油化工股份有限公司 Load-type olefin oligomerization catalyst and preparation method thereof
CN114054096A (en) * 2020-07-30 2022-02-18 中国石油化工股份有限公司 Solid base catalyst for preparing 4-methyl-1-pentene by propylene oligomerization and preparation method and application thereof
CN114054096B (en) * 2020-07-30 2023-10-24 中国石油化工股份有限公司 Solid base catalyst for preparing 4-methyl-1-pentene by propylene oligomerization, preparation method and application thereof

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