CN114853798B - Pyrrole ring tridentate metal complex and application thereof - Google Patents
Pyrrole ring tridentate metal complex and application thereof Download PDFInfo
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Abstract
The invention provides an pyrrole ring tridentate metal complex which has a structure shown in a formula I. The invention uses a novel pyrrole ring-containing tridentate fourth subgroup metal complex as a main catalyst and uses an alkyl aluminoxane or modified alkyl aluminoxane or boron auxiliary agent system as a cocatalyst, which is used for catalyzing the copolymerization reaction of ethylene and alpha-olefin. The novel pyrrole ring-containing tridentate fourth-subgroup metal complex provided by the invention has the advantages of good thermal stability, high catalytic activity and the like, and can be used as a main catalyst for catalyzing olefin polymerization reaction, and can be used for efficiently catalyzing copolymerization reaction of ethylene and 1-octene to obtain a polyolefin elastomer material with high molecular weight and high comonomer insertion rate.
Description
Technical Field
The invention belongs to the technical field of olefin polymer catalysts, and particularly relates to a pyrrole ring tridentate metal complex and application thereof, in particular to a novel pyrrole ring tridentate fourth sub-group metal complex and application thereof in catalyzing olefin polymerization, in particular to ethylene and alpha-olefin copolymerization.
Background
The polyolefin products have the advantages of rich raw materials, low price, easy production and processing, good mechanical property, excellent performance and the like, become the synthetic resin materials which are most widely applied in the production and life at present, and the development level of the polyolefin industry directly represents the development level of the national petrochemical industry.
The olefin polymerization catalyst directly determines the internal structure and morphology of polyolefin products, and is the most core technology in the development process of the polyolefin industry; the non-metallocene catalyst has single active center, relatively high activity and strong tolerance of central metal to hetero atoms, has the advantages of ZN catalyst and metallocene catalyst, can catalyze the homopolymerization and copolymerization of multiple olefin monomers, realizes precise control on the molecular weight and the internal morphology of polyolefin products, enriches the variety of polyolefin products, and has very wide application prospect.
The catalyst types are enriched, the temperature resistance and activity of the catalyst are improved, and the catalysis preparation of high molecular polymers and high monomer content high polymers become hot spots for research in the field.
Disclosure of Invention
In view of the above, the invention aims to provide a pyrrole ring tridentate metal complex and application thereof, and the pyrrole ring tridentate metal complex provided by the invention has good temperature resistance, high catalytic activity, high molecular weight of the obtained polymer and high comonomer content as a catalyst.
The invention provides an pyrrole ring tridentate metal complex, which has a structure shown in formula I:
In formula I, R 1、R2、R3、R4、R5、R6、R7 is independently selected from alkyl or substituted alkyl, aryl or substituted aryl;
X is selected from halogen, alkyl or benzyl;
M is selected from the fourth subgroup transition metals.
Preferably, the alkyl in R 1、R2、R3、R4、R5、R6、R7 is independently selected from C1-C12 alkyl.
Preferably, the R 1、R2、R3、R4、R5、R6、R7 ring is a C3-C6 alkyl ring or a substituted alkyl ring, aryl ring or a substituted aryl ring.
Preferably, R 1 is selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 9-anthracenyl.
Preferably, R 2、R3 is independently selected from H and methyl.
Preferably, R 4～R7 is independently selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl.
Preferably, R 1 and R 2 form an aryl ring, R 2 and R 3 form an aryl ring, and R 4 and R 5 form an aryl ring.
Preferably, said M is selected from titanium, zirconium or hafnium.
Preferably, X is selected from Cl, methyl and benzyl.
The invention provides a polymer which is prepared by taking the pyrrole ring tridentate metal complex as a catalyst.
The invention provides a novel pyrrole ring-containing tridentate fourth-subgroup metal complex, which has the characteristics of good temperature resistance, high catalytic activity, high polymer molecular weight and high comonomer content when used as a catalyst by reasonably modifying the structure of a compound.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a complex formula 3 prepared in example 3 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the complex formula 13 prepared in example 3 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an pyrrole ring tridentate metal complex, which has a structure shown in formula I:
In formula I, R 1、R2、R3、R4、R5、R6、R7 is independently selected from alkyl or substituted alkyl, aryl or substituted aryl;
X is selected from halogen, alkyl or benzyl;
M is selected from the fourth subgroup transition metals.
In the present invention, the alkyl group in R 1、R2、R3、R4、R5、R6、R7 is preferably independently selected from C1-C12 alkyl groups, more preferably independently selected from C2-C10 alkyl groups, more preferably independently selected from C3-C8 alkyl groups, and most preferably independently selected from C4-C6 alkyl groups.
In the present invention, R 1 is preferably selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 9-anthracenyl.
In the present invention, R 2、R3 is preferably independently selected from H and methyl.
In the present invention, R 4～R7 is preferably independently selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl.
In the present invention, the R 1、R2、R3、R4、R5、R6、R7 is preferably cyclic, preferably forming a C3-C6 alkyl ring or a substituted alkyl ring, an aryl ring or a substituted aryl ring; more preferably, R 1 forms an aryl ring with R 2, R 2 forms an aryl ring with R 3, and R 4 forms an aryl ring with R 5.
In the present invention, the M is preferably selected from titanium, zirconium or hafnium, more preferably Zr, hf.
In the present invention, the X is preferably selected from Cl, methyl, benzyl.
In the present invention, the pyrrole ring tridentate metal complex is preferably selected from one of the formulae 1 to 20:
The preparation method of the pyrrole ring tridentate metal complex is not particularly limited, and the pyrrole ring tridentate metal complex can be prepared by various compound synthesis methods known to those skilled in the art according to the compound structure, for example, the pyrrole ring tridentate metal complex can be prepared by the method in the embodiment of the invention.
The invention provides a polymer which is prepared by taking the pyrrole ring tridentate metal complex as a catalyst.
In the present invention, the pyrrole ring tridentate metal complex is consistent with the description of the above technical scheme, and will not be described herein.
In the present invention, the preparation method of the polymer preferably includes:
under the action of main catalyst and cocatalyst, ethylene and alpha-olefin are copolymerized to obtain polymer.
In the invention, the main catalyst is the pyrrole ring tridentate metal complex in the technical scheme.
In the present invention, the cocatalyst is one or more selected from alkylaluminoxane, modified alkylaluminoxane, haloalkylaluminum and alkylaluminum, more preferably selected from methylaluminoxane or modified methylaluminoxane. In the present invention, the cocatalyst preferably further comprises a boron-containing material, preferably selected from triphenylcarbon-tetrakis (pentafluorophenyl) borate.
In the present invention, the molar ratio of Al in the cocatalyst to the metal element in the main catalyst is preferably (5 to 5000): 1, more preferably (10 to 4000): 1, more preferably (20 to 3000): 1, more preferably (30 to 2000): 1, more preferably (40 to 1000): 1, more preferably (50 to 800): 1, more preferably (100 to 600): 1, more preferably (200 to 500): 1, most preferably (300 to 400): 1.
In the present invention, the molar ratio of boron in the cocatalyst to the metal element in the main catalyst is preferably (0.1 to 2): 1, more preferably (0.5 to 2): 1, more preferably (1 to 2): 1, most preferably 1.5: 1.
In the present invention, the alpha-olefin is preferably selected from 1-octene.
In the present invention, the α -olefin is preferably dissolved in a solvent, preferably isoparaffin (Isopar E), to form a solution; the concentration of the alpha-olefin in the solution is preferably 0.1 to 5mol/L, more preferably 0.5 to 4mol/L, still more preferably 1 to 3mol/L, and most preferably 1mol/L.
In the present invention, the ratio of the amount of the solution of the procatalyst and the α -olefin is preferably (2 to 3) μmol: (350-450) mL, more preferably (2.4-2.6) mu mol: (380-420) mL, most preferably 2.5. Mu. Mol:400mL.
In the present invention, the pressure of ethylene during the copolymerization reaction is preferably 0.1 to 10MPa, more preferably 1 to 8MPa, still more preferably 2 to 6MPa, and most preferably 2 to 4MPa.
In the present invention, the temperature of the copolymerization reaction is preferably 60 to 210 ℃, more preferably 80 to 200 ℃, more preferably 100 to 180 ℃, more preferably 120 to 160 ℃, and most preferably 140 ℃; the time for the copolymerization is preferably 3 to 40 minutes, more preferably 5 to 30 minutes, still more preferably 10 to 20 minutes, and most preferably 15 minutes.
The pyrrole ring tridentate metal complex structure provided by the invention is convenient to modify; the catalyst has good temperature resistance and can keep high catalytic activity under high temperature conditions; the copolymerization of ethylene and 1-octene is catalyzed, and a polymer product with high molecular weight and high comonomer insertion rate can be obtained. The experimental results show that: the molecular weight of the polymer obtained by copolymerizing ethylene and 1-octene under the catalysis of the complex provided by the invention is up to 39.2 multiplied by 10 4 g/mol, and the molar insertion rate of 1-octene is up to 16.7%.
Example 1
The structural ligand of the formula II is prepared according to the following synthetic route:
R 1、R2、R3、R4、R5、R6、R7 in the structure of formula II has no ring structure formed by direct connection, and specifically is a compound of formulas L1-L9:
The preparation process comprises the following steps:
the pyrrole starting materials for R 1 = H, methyl and isopropyl are commercially available directly;
R 1 = phenyl, anthracenyl pyrrole compound, i.e. compound of formula C, is prepared as follows:
Dropwise adding a compound (pyrrole, 40 mmol) of the formula A into 100mL of dry tetrahydrofuran suspension containing NaH (40 mmol) cooled to 0 ℃ in advance under nitrogen atmosphere, and then heating to room temperature for reaction for 5h; then zinc chloride (40 mmol) is added in batches, and the reaction is carried out for 20min after the addition; 2- (dicyclohexylphosphino) biphenyl (0.4 mmol) and tris (dibenzylideneacetone) dipalladium (namely Pd 2(dba)3; 0.2 mmol) are added into the mixture in turn and reacted for 10min; then adding R 1 -Br (bromobenzene or 9-bromoanthracene; 10 mmol) into the mixture, and heating and refluxing the mixture for reaction for 24 hours; after the reaction, cooling to room temperature, ethyl acetate (200 mL) and water (20 mL) were added thereto, insoluble matters were removed by filtration, then 100mL of water was added thereto, the organic phase was retained by separation, the aqueous phase was further extracted 3 times with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography (eluent ethyl acetate: petroleum ether=1:30) to give a compound of formula C (R 1 =phenyl, anthracenyl).
The specific preparation method of the intermediate compound of the formula D is as follows:
In a 250mL Schlenck bottle under nitrogen atmosphere, adding a compound of formula C (20 mmol), normal hexane (100 mL), methoxy (cyclooctadiene) iridium (I) dimer (i.e., [ Ir (COD) OMe ] 2; 0.3 mmol), a compound of formula G (pinacol borane; 30 mmol) and 4,4 '-di-tert-butyl-2, 2' -bipyridine (i.e.,: dibbpy;0.6 mmol) in sequence, stirring and reacting for 10min, then adding pyrrole (10 mL), and heating and refluxing for reacting for 24h; after the reaction was completed, cooled to room temperature, ethyl acetate (200 mL) and methanol (20 mL) were added thereto, stirred for 20min to quench the reaction thoroughly, then 100mL of water was added thereto, the organic phase was separated to remain the aqueous phase, the aqueous phase was further extracted with ethyl acetate for 3 times, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography (eluent: dichloromethane: petroleum ether=1:3) to give the compound of formula D.
The specific preparation method of the intermediate compound of the formula F is as follows:
under nitrogen atmosphere, the compound of formula E (50 mmol), the compound of formula D (50 mmol), deoxygenated ethylene glycol dimethyl ether (200 mL), deoxygenated deionized water (25 mL), cesium carbonate (55 mmol) and tetrakis (triphenylphosphine) palladium (5 mmol) are sequentially added into a 500mL round bottom flask, reflux reacted for 72h, cooled to room temperature, the majority of the solvent is removed by rotary evaporation, 100mL diethyl ether and 100mL water are added, the organic phase is separated and retained, the aqueous phase is continuously extracted 3 times with diethyl ether, the organic phases are combined, anhydrous magnesium sulfate is added for drying, filtration and rotary evaporation are carried out to remove the solvent, and the crude product is purified by column chromatography (eluent is ethyl acetate: petroleum ether=1:30) to obtain the compound of formula F.
The specific preparation method of the intermediate compound of the formula J is as follows:
Under nitrogen atmosphere, the compound (50 mmol) of formula H is dissolved in 100mL of dry tetrahydrofuran, cooled to-78 ℃, 55mmol of n-butyllithium is dripped into the solution, the solution is kept at a low temperature for reaction for 0.5H, then triisopropyl borate (60 mmol) is dripped into the solution, the solution is removed from the solution, the temperature is raised to room temperature for continuous reaction for 1H, 100mL water and 100mL of diethyl ether are added, the organic phase is remained after separation, the aqueous phase is continuously extracted with diethyl ether for 3 times, the organic phases are combined, anhydrous magnesium sulfate is added for drying, filtration and rotary evaporation are carried out, and the solvent is removed, thus obtaining the compound of formula J.
The preparation method of the structural ligand of the formula II comprises the following steps:
Under nitrogen atmosphere, the compound of formula F (50 mmol), the compound of formula J (55 mmol), deoxygenated ethylene glycol dimethyl ether (200 mL), deoxygenated deionized water (25 mL), cesium carbonate (55 mmol) and tetrakis (triphenylphosphine) palladium (5 mmol) are sequentially added into a 500mL round bottom flask, heated and refluxed for reaction for 72h, cooled to room temperature, distilled to remove most of the solvent, 100mL diethyl ether and 100mL water are added, the separated organic phase is retained, the aqueous phase is extracted with diethyl ether for 3 times, the organic phases are combined, anhydrous magnesium sulfate is added for drying, filtration and distilled to remove the solvent, and the crude product is purified by column chromatography (eluent is ethyl acetate: petroleum ether=1:30) to obtain the ligand of formula II.
Example 2
The ligand of the formula II has a ring structure formed by interconnecting R 1、R2、R3、R4、R5、R6、R7, and the specific structure is shown as the formulas L10-L17:
The compound of formula F is prepared according to the following synthetic route:
the specific method comprises the following steps:
R 1 = pyrrole starting material H, methyl, isopropyl and tert-butyl; indole (compound of formula L7) obtained by connecting R 1 and R 2 to form a ring, isoindole (compound of formula L8) obtained by connecting R 2 and R 3 to form a ring can be purchased directly;
The specific preparation method of the pyrrole compound with R 1 = phenyl and anthracene group, namely the compound with the formula C is as follows:
Dropwise adding a compound (pyrrole, 40 mmol) of the formula A into 100mL of dry tetrahydrofuran suspension containing NaH (40 mmol) cooled to 0 ℃ in advance under nitrogen atmosphere, and then heating to room temperature for reaction for 5h; then zinc chloride (40 mmol) is added in batches, and the reaction is carried out for 20min after the addition; 2- (dicyclohexylphosphino) biphenyl (0.4 mmol) and tris (dibenzylideneacetone) dipalladium (namely Pd 2(dba)3; 0.2 mmol) are added into the mixture in turn and reacted for 10min; then adding R 1 -Br (bromobenzene or 9-bromoanthracene; 10 mmol) into the mixture, and heating and refluxing the mixture for reaction for 24 hours; after the reaction, cooling to room temperature, ethyl acetate (200 mL) and water (20 mL) were added thereto, insoluble matters were removed by filtration, then 100mL of water was added thereto, the organic phase was retained by separation, the aqueous phase was further extracted 3 times with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography (eluent ethyl acetate: petroleum ether=1:30) to give a compound of formula C (R 1 =phenyl, anthracenyl).
The specific preparation method of the intermediate compound of the formula D is as follows:
in a 250mL Schlenck bottle under nitrogen atmosphere, adding a compound of formula C (20 mmol), normal hexane (100 mL), methoxy (cyclooctadiene) iridium (I) dimer (i.e., [ Ir (COD) OMe ] 2; 0.3 mmol), a compound of formula G (pinacol borane; 30 mmol) and 4,4 '-di-tert-butyl-2, 2' -bipyridine (i.e.,: dibbpy;0.6 mmol) in sequence, stirring and reacting for 10min, then adding pyrrole (10 mL), and heating and refluxing for reacting for 24h; after the reaction was completed, cooled to room temperature, ethyl acetate (200 mL) and methanol (20 mL) were added thereto, stirred for 20min to quench the reaction thoroughly, then 100mL of water was added thereto, the organic phase was separated to remain the aqueous phase, the aqueous phase was further extracted with ethyl acetate for 3 times, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography (eluent: dichloromethane: petroleum ether=1:3) to give the compound of formula D.
The specific preparation method of the intermediate compound of the formula F is as follows:
under nitrogen atmosphere, the compound of formula E (50 mmol), the compound of formula D (50 mmol), deoxygenated ethylene glycol dimethyl ether (200 mL), deoxygenated deionized water (25 mL), cesium carbonate (55 mmol) and tetrakis (triphenylphosphine) palladium (5 mmol) are sequentially added into a 500mL round bottom flask, reflux reacted for 72h, cooled to room temperature, the majority of the solvent is removed by rotary evaporation, 100mL diethyl ether and 100mL water are added, the organic phase is separated and retained, the aqueous phase is continuously extracted 3 times with diethyl ether, the organic phases are combined, anhydrous magnesium sulfate is added for drying, filtration and rotary evaporation are carried out to remove the solvent, and the crude product is purified by column chromatography (eluent is ethyl acetate: petroleum ether=1:30) to obtain the compound of formula F.
The preparation method of the structural ligand of the formula II comprises the following steps:
Under nitrogen atmosphere, sequentially adding a compound of a formula F (50 mmol), 1-naphthalene boric acid (55 mmol), deoxidized ethylene glycol dimethyl ether (200 mL), deoxidized deionized water (25 mL), cesium carbonate (55 mmol) and tetrakis (triphenylphosphine) palladium (5 mmol) into a 500mL round-bottomed flask, heating and refluxing for reaction for 72h, cooling to room temperature, removing most of the solvent by rotary evaporation, adding 100mL of diethyl ether and 100mL of water, separating liquid to keep an organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the organic phases, adding anhydrous magnesium sulfate for drying, filtering, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether=1:30) to obtain the ligand of the structure of the formula II.
Example 3
General preparation method of metal complex (preparation method of metal methylation compound, formula C1-C9, C11-C18 and C20):
Dissolving 2mmol of ligand (one of formulas L1-L17) in 30mL of toluene under nitrogen atmosphere, cooling to 0 ℃, dropwise adding 2mmol of n-butyllithium solution into the solution, removing low temperature, continuing to react for 3h at room temperature, slowly transferring the solution into a toluene (10 mL) suspension of MX 4 (2 mmol, M=Hf or Zr, X=Cl) which is cooled to 0 ℃ in advance by a syringe, keeping the temperature of 0 ℃ for reacting for 1.5h, adding CH 3 MgBr (6 mmol) into the solution, and heating to 100 ℃ for continuing to react for 2h; cooling to room temperature, filtering to remove insoluble substances, removing volatile components in the filtrate under vacuum, and recrystallizing the crude product (toluene/n-hexane=1:20) to obtain metal complex formulas C1-C9, C11-C18 and C20.
Example 4
General preparation method of metal complex (preparation method of metal benzyl compound, formula C10 and C19):
Dissolving 2mmol of ligand (one of formulas L1-L17) in 30mL of toluene under nitrogen atmosphere, cooling to 0 ℃, dropwise adding 2mmol of n-butyllithium solution into the solution, removing low temperature, continuing to react for 3h at room temperature, slowly transferring the solution into a toluene (10 mL) suspension of MX 4 (2 mmol, M=Hf or Zr, X=Cl) which is cooled to 0 ℃ in advance by a syringe, keeping the temperature of 0 ℃ for reacting for 1.5h, adding PhCH 2 MgBr (6 mmol) into the solution, and heating to 100 ℃ for continuing to react for 2h; cooling to room temperature, filtering to remove insoluble substances, removing volatile components in the filtrate under vacuum, and recrystallizing the crude product (toluene/n-hexane=1:20) to obtain metal complex formula C10 and C19.
Fig. 1 is a nmr hydrogen spectrum of the complex of formula 3 prepared in example 3, and fig. 2 is a nmr hydrogen spectrum of the complex of formula 13 prepared in example 3, and as can be seen from fig. 1 and 2, the target structural product was synthesized.
The yields, yields and elemental analysis results of the metal complexes of formulae 1 to 20 prepared according to example 3 and example 4 were as follows:
metal complex of formula 1 (Cat 1), yield: 0.6865g, yield: 73.2%, elemental analysis: actual measurement (calculation) C:51.24 (51.23) H:4.72 (4.73) N:5.98 (5.97);
Metal complex of formula 2 (Cat 2), yield: 0.8621g, yield: 82.1%, elemental analysis: actual measurement (calculation) C:54.90 (54.91) H:5.76 (5.76) N:5.34 (5.34);
Metal complex of formula 3 (Cat 3), yield: 0.6937g, yield: 69.8%, elemental analysis: actual measurement (calculation) C:53.18 (53.17) H:5.27 (5.27) N:5.64 (5.64);
Metal complex of formula 4 (Cat 4), yield: 0.8995g, yield: 77.4%, elemental analysis: actual measurement (calculation) C:57.95 (57.87) H:6.60 (6.59) N:4.82 (4.82);
metal complex of formula 5 (Cat 5), yield: 0.6880g, yield: 80.6%, elemental analysis: actual measurement (calculation) C:47.85 (47.84) H:3.78 (3.78) N:6.55 (6.56);
Metal complex of formula 6 (Cat 6), yield: 0.5634g, yield: 63.9%, elemental analysis: actual measurement (calculation) C:49.11 (49.04) H:4.13 (4.12) N:6.36 (6.35);
Metal complex of formula 7 (Cat 7), yield: 0.7418g, yield: 79.1%, elemental analysis: actual measurement (calculation) C:51.24 (51.23) H:4.73 (4.73) N:5.97 (5.97);
Metal complex of formula 8 (Cat 8), yield: 0.6880g, yield: 68.4%, elemental analysis: actual measurement (calculation) C:54.96 (54.93) H:4.00 (4.01) N:5.58 (5.57);
Metal complex of formula 9 (Cat 9), yield: 0.9709g, yield: 80.5%, elemental analysis: actual measurement (calculation) C:61.77 (61.74) H:4.02 (4.01) N:4.65 (4.65);
metal complex of formula 10 (Cat 10), yield: 1.0397g, yield: 83.7%, elemental analysis: actual measurement (calculation) C:61.89 (61.88) H:4.87 (4.87) N:4.51 (4.51);
metal complex of formula 11 (Cat 11), yield: 0.7067g, yield: 74.1%, elemental analysis: actual measurement (calculation) C:52.92 (52.89) H:3.79 (3.80) N:5.88 (5.87);
metal complex of formula 12 (Cat 12), yield: 0.7187g, yield: 73.2%, elemental analysis: actual measurement (calculation) C:53.86 (53.83) H:4.10 (4.11) N:5.71 (5.71);
metal complex of formula 13 (Cat 13), yield: 0.7234g, yield: 69.7%, elemental analysis: actual measurement (calculation) C:55.59 (55.55) H:4.66 (4.66) N:5.40 (5.40);
Structural metal complex of formula 14 (Cat 14), yield: 0.8656g, yield: 81.2%, elemental analysis: actual measurement (calculation) C:56.35 (56.34) H:4.92 (4.92) N:5.26 (5.26);
Structural metal complex of formula 15 (Cat 15), yield: 0.7996g, yield: 72.3%, elemental analysis: actual measurement (calculation) C:58.69 (58.65) H:4.00 (4.01) N:5.07 (5.07);
Metal complex of formula 16 (Cat 16), yield: 1.0136g, yield: 77.6%, elemental analysis: actual measurement (calculation) C:64.32 (64.37) H:4.02 (4.01) N:4.28 (4.29);
metal complex of formula 17 (Cat 17), yield: 0.7524g, yield: 71.4%, elemental analysis: actual measurement (calculation) C:56.90 (56.98) H:3.83 (3.83) N:5.32 (5.32);
Metal complex of formula 18 (Cat 18), yield: 0.8494g, yield: 80.6%, elemental analysis: actual measurement (calculation) C:57.03 (56.98) H:3.84 (3.83) N:5.33 (5.32);
metal complex of formula 19 (Cat 19), yield: 1.0319g, yield: 75.3%, elemental analysis: actual measurement (calculation) C:64.90 (64.86) H:5.02 (5.00) N:4.10 (4.09);
Metal complex of formula 20 (Cat 20), yield: 0.8088g, yield: 77.5%, elemental analysis: actual measurement (calculation) C:71.42 (71.35) H:5.82 (5.80) N:5.38 (5.37);
example 5 catalysis of ethylene copolymerization with 1-octene
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with mechanical stirring is heated to 150 ℃, vacuum pumping is carried out for 1h, a system is adjusted to a temperature condition required by polymerization, ethylene gas with the pressure of 0.1MPa is filled, a mixed isoparaffin (Isopar E) solution (the total volume of the final solution is 400 mL) containing a certain amount of Modified Methylaluminoxane (MMAO) and a certain concentration of alpha-olefin (1-octene) is added into the polymerization kettle, the temperature is kept constant for a period of time until the temperature is constant, ethylene gas with the pressure of 3.5MPa is filled, the reaction kettle is waited for 10min, so that the ethylene reaches dissolution balance, then a main catalyst (when boron cocatalyst is added, the main catalyst is required to be mixed with the main catalyst in advance for shaking, and the reaction kettle is kept for 5 min) and stirred for a period of time. And (3) discharging residual ethylene gas after the polymerization reaction is finished, cooling to 40 ℃, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirring for 5min, filtering, and drying a polymer product in a vacuum oven.
The polymer prepared in example 5 was weighed, the molecular weight and the molecular weight distribution were measured, the monomer insertion rate was measured by a high Wen Tanpu, and the polymerization conditions were: the dosage of the main catalyst C1-C20 is 2.5 mu mol, the cocatalyst is MMAO-7, the Al/M= 400,1-octene concentration is 1mol/L, the polymerization pressure is 3.5MPa, and the polymerization temperature is as follows: the polymerization time is 10min at 140 ℃; a Molecular weight, molecular weight distribution, as measured by GPC; b Measured by 13 CNMR; c The cocatalysts were Ph 3C[B(PhF5)4 and Al (iBu) 3, M/B/al=1:1.2:80.
The detection results are as follows:
From the above examples, the invention provides a novel pyrrole ring-containing tridentate fourth subgroup metal complex which has good temperature tolerance, can maintain high catalytic activity at 140 ℃, is used as a main catalyst for catalyzing the copolymerization of ethylene 1-octene, and has high activity, and the molecular weight and comonomer insertion rate of the polymer are also high. The experimental results show that: the molecular weight of the polymer obtained by catalyzing the copolymerization of ethylene and 1-octene by the complex provided by the invention is up to 39.2 multiplied by 10 4 g/mol, and the molar insertion rate of 1-octene is up to 16.7%.
While the application has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the application. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the application as defined by the following claims, so as to adapt the objective, spirit and scope of the application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (3)
1. A pyrrole ring tridentate metal complex having the structure of formula I:
A formula I;
In the formula I, R 1 is selected from H, C alkyl or aryl of 1 to 4, R 2、R3 is independently selected from H and methyl, and R 4~R7 is independently selected from H, C alkyl of 1 to 4;
Or R 1 and R 2 form a C6 aryl ring, R 2 and R 3 form a C6 aryl ring, and R 4 and R 5 form a C6 aryl ring;
X is selected from Cl, methyl and benzyl;
m is selected from titanium, zirconium or hafnium.
2. The pyrrole ring tridentate metal complex according to claim 1, wherein R 1 is selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 9-anthracenyl.
3. The pyrrole ring tridentate metal complex according to claim 1, wherein R 4~R7 is independently selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl.
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