CN112552436B - Metallocene catalyst, preparation method and application thereof - Google Patents
Metallocene catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heterocyclic constrained geometry metallocene catalyst based on pyrrole metallocene and a preparation method thereof. The preparation method comprises the following steps: 2-pyrrole formaldehyde and derivatives thereof are used as raw materials to synthesize fulvene with indene, ligand is prepared by lithium aluminum hydride reduction, and a high-yield catalyst is obtained by an amine elimination method and can catalyze olefin polymerization. Pyrrole N heterocycle is used as an electron donor to replace tert-butylamine, the molecular structure of the catalyst is symmetrical, and the olefin polymerization efficiency is improved. The catalyst has the advantages of simple synthetic route, easily obtained raw materials, low cost, greatly improved yield and good catalytic activity in olefin polymerization.
Description
Technical Field
The present invention relates to a constrained geometry metallocene catalyst of a pyrrole metallocene, a method for preparing the catalyst, and a method for preparing polyolefin using the same.
Background
When the bridging heteroatom of the ligand forms a semi-sandwich bifunctional compound with the metal atom, they exhibit a high ability to catalyze olefin polymerization under the action of MAO, which is known as Constrained Geometry Catalyst (CGC). The constrained geometry catalyst is characterized in that a constrained geometry substituent group is introduced on a delocalized pi electron bonding group Cp, so that the geometric configuration of a metal atom in a complex is constrained, and an included angle formed by the Cp-a metal central atom-a coordination group connected with a bridging group is smaller than that of a similar complex, so that the constrained geometry catalyst has the characteristic of more open.
In 1990 Dow chemical company synthesized the so-called "constrained configuration catalyst". It is a complex formed by substituting one cyclopentadiene (or indenyl and fluorenyl) in Si1 or C1 bridged metallocene catalyst structure by amino, and a monocyclopentadiene and a transition metal of the IV subgroup by a coordination bond, wherein the bond angle between the monocyclopentadiene, the transition metal and a heteroatom (such as nitrogen) is less than 115 degrees, and a strong Lewis acid system can activate the catalyst into a high-efficiency positive ion. On one hand, the bidentate ligand stabilizes the metal electron cloud, on the other hand, the position of the ligand is deviated due to the existence of the short bridge group, and the active center of the catalyst can be opened only to one direction from the spatial configuration, thereby achieving the purpose of limiting the geometric configuration. Dow chemical company called Constrained-Geometry Catalyst (CGC). The typical structure is shown in formula 1.
Typical structure of CGC of formula 1
The first CGC synthesized by Shapiro and Bercaw et al used t-butyl as the electron donor and shortly thereafter, the experimenter tried to modify with other groups, such as more electron-withdrawing phenyl rings and adamantane, etc., as in formulas 2 and 3.
Formula 2 first constrained geometry catalyst
Constrained-configuration catalysts substituted with benzene ring and adamantane of formula 3
In addition to alkyl and aryl groups, researchers have also introduced other groups such as sulfonamido, pyrrolyl, hydrazino and imino groups, etc., as in formula 4, sulfonamido, pyrrolyl, etc. have a stronger electron withdrawing property than alkyl and aryl groups, so that the Ti-N bond is longer and also facilitates the insertion of alpha-olefins.
Constrained configuration catalysts of other substituent groups of formula 4
Certainly, besides N group as electron donor group, there are also groups of heteroatoms such as P, S, O, etc. as electron donor, but compared with the N-containing electron donor, the CGC synthesized by using other heteroatoms as electron donor is not ideal in both activity and performance of the obtained polymer, so that currently, research on CGC using other heteroatoms as electron donor is very little, for example, only an example is reported at present about CGC containing S atom, the structure is as formula 5, and there is basically no catalytic activity.
Constrained configuration catalysts with other hetero atoms as electron donating groups of formula 5
Because the unique stereo structure of the CGC catalyst can allow various olefin monomers to be inserted, the CGC catalyst can catalyze olefin homopolymerization and ethylene/alpha-olefin copolymerization. Since the first CGC was synthesized, a series of CGCs were synthesized in 30 years, but most CGCs have little structural difference, and the properties of polymers for catalyzing polymerization are not improved, so that the production of polyolefin products such as low density polyethylene (LLDPE) and POE (polyolefin elastomer) is limited, and the development of constrained geometry catalysts with novel structures is very significant.
Disclosure of Invention
The invention mainly aims to provide a metallocene catalyst, and a preparation method and application thereof, so that the activity of the metallocene catalyst for catalyzing olefin polymerization and the insertion rate of an alpha-olefin monomer can be flexibly regulated and controlled.
In order to achieve the above object, the present invention provides a metallocene catalyst having the following structure of formula i:
wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups; r 4 Is straight-chain or branched C 1 -C 5 An alkyl group.
The metallocene catalyst of the present invention, wherein R is 4 Is CH 3 -or CH 3 CH 2 -。
In order to achieve the above object, the present invention also provides a method for preparing a metallocene catalyst, the method comprising the steps of:
step 1, reacting 2-pyrrole carboxaldehyde or its derivative with indene to prepare nitrogen-containing fulvene shown in formula III, R 1 、R 2 And R 3 Each independently selected from H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups;
step 2, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step 3, ligand of pyrrole-containing N heterocyclic ring and Zr [ N (R) in formula IV 4 ) 2 ] 4 A complexation reaction occurs to form a metallocene catalyst, R 4 Is straight-chain or branched C 1 -C 5 An alkyl group;
the preparation method of the metallocene catalyst is that R is 4 Is CH 3 -or CH 3 CH 2 -。
The preparation method of the metallocene catalyst comprises the following steps of 1: dissolving 2-pyrrole formaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent, cooling to-10-5 ℃, dropwise adding pyrrolidine, heating to room temperature, and stirring for reaction for 0.5-20 hours to obtain nitrogen-containing fulvene shown in the formula III;
wherein, the mass ratio of 2-pyrrole formaldehyde or its derivative, indene and tetrahydropyrrole in formula II is 1: 1-5: 1 to 5.
The preparation method of the metallocene catalyst comprises the following steps of 2: dissolving the nitrogen-containing fulvene of the formula III obtained in the step 1 in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, then heating to 40-70 ℃, stirring and reacting for 5-50h to obtain a pyrrole N heterocyclic-containing ligand of the formula IV;
wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5.
The preparation method of the metallocene catalyst comprises the following steps of 3: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step 2 in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Zr [ N (R) dissolved in the organic solvent 4 ) 2 ] 4 Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;
wherein, the formula IV contains pyrrole N heterocyclic ligand and Zr [ N (R) 4 ) 2 ] 4 In a molar ratio of 1: 0.5 to 5.
The preparation method of the metallocene catalyst comprises the step 1, the step 2 and the step 3, which are all carried out under the protection of inert gas, wherein the inert gas is one or more of the group consisting of nitrogen, helium and argon.
In order to achieve the above object, the present invention further provides an olefin polymerization process carried out by the above metallocene catalyst.
The olefin polymerization method of the present invention is characterized in that the olefin is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene and divinylbenzene.
The olefin polymerization reaction method of the invention is characterized in that the metallocene catalyst is a main catalyst, the alkylaluminium or aluminoxane compound is a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.
The invention discloses a pyrrole indene-based group IVB complex catalyst. The catalyst is prepared by replacing a catalyst which adopts tert-butyl as an electron donor in the prior art with a pyrrolyl heterocycle and utilizing an amine elimination method with fewer steps, and the electronic environment and the space environment of a metal center are controlled by adjusting the difference of the positions of substituents on the pyrrolyl, so that the activity of a catalytically prepared polymer and the insertion rate of an alpha-olefin monomer are regulated and controlled; compared with tert-butylamine, the pyrrole group has stronger electron withdrawing property, so that the Zr-N bond is longer, the insertion of alpha-olefin is facilitated, higher monomer insertion rate can be obtained, and the polymer with excellent performance is prepared; the catalyst obtained by the invention has the advantages of short synthetic route, simple synthetic process and low industrial cost.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The invention provides a pyrrole metallocene heterocycle constrained geometry metallocene catalyst, which has the following structure:
wherein R is 1 、R 2 、R 3 、R 4 The structure is respectively as follows:
R 1 is H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups;
R 2 is H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups;
R 3 is H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 In hydrocarbon radicalsOne kind of the material is selected;
R 4 is straight-chain or branched C 2 -C 5 An alkyl group. As a preferred embodiment, R 4 Is CH 3 -or CH 3 CH 2 -。
The preparation method of the pyrrole metallocene heterocycle constrained geometry metallocene catalyst provided by the invention comprises the following steps:
step 1, reacting 2-pyrrole carboxaldehyde or its derivative with indene to prepare nitrogen-containing fulvene shown in formula III, R 1 、R 2 And R 3 Each independently selected from H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups;
step 2, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step 3, ligand of pyrrole-containing N heterocyclic ring and Zr [ N (R) in formula IV 4 ) 2 ] 4 A complexation reaction occurs to produce a metallocene catalyst, R 4 Is straight-chain or branched C 1 -C 5 An alkyl group;
in detail, the preparation method of the pyrrole metallocene heterocycle constrained geometry metallocene catalyst comprises the following steps:
step 1, dissolving 2-pyrrole-carbaldehyde shown in a formula II or a derivative thereof and indene in an organic solvent in a Schlenk bottle, cooling to-10-5 ℃, for example, placing in an ice water bath, and then slowly dropwise adding pyrrolidine, wherein the ratio of the amount of the 2-pyrrole-carbaldehyde or the derivative thereof to the amount of the indene to the amount of the pyrrolidine is 1: 1-5: 1-5; after the dropwise addition, the temperature is raised to the room temperature, and the mixture is stirred for 0.5 to 20 hours to react; and after the reaction is finished, carrying out liquid separation extraction and washing by using an organic solvent, taking an organic phase, drying the organic phase, and carrying out rotary evaporation to obtain the nitrogen-containing fulvene in the formula III. Wherein the organic solvent can be one or more of methanol, ethanol, formaldehyde, acetaldehyde, diethyl ether, toluene and ethylbenzene.
Step 2, dissolving the nitrogen-containing fulvene of the formula III prepared in the step 1 in an organic solvent such as tetrahydrofuran in a Schlenk bottle, cooling to-10-5 ℃, for example, placing in an ice water bath, then dropwise adding lithium aluminum hydride dissolved in the solvent (such as tetrahydrofuran), withdrawing the ice water bath, slowly heating to 40-70 ℃, reacting for 5-50h, adding the organic solvent, separating, extracting, washing, drying the organic phase, and then performing rotary evaporation to obtain a ligand containing pyrrole N heterocycle of the formula IV; wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5. Wherein the organic solvent is one or more of ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.
Step 3, Zr (N (R) in Schlenk flask 4 ) 2 ) 4 Dissolving in an organic solvent, cooling to-10-5 ℃, for example, placing in an ice-water bath, dissolving the pyrrole N heterocycle-containing ligand of formula IV prepared in step 2 in the organic solvent, slowly adding into a Schlenk bottle, removing the ice-water bath, heating to 50-100 ℃, and reacting for 1-30 h.
Or, dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step 2 in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Zr [ N (R) dissolved in the organic solvent 4 ) 2 ] 4 After the dripping is finished, the temperature is raised to 50-100 ℃, and the stirring reaction is carried out for 1-30 h.
Wherein, the formula IV contains pyrrole N heterocyclic ligand and Zr [ N (R) 4 ) 2 ] 4 In a molar ratio of 1: 0.5 to 5.
And after the reaction is finished, pumping the solvent, and finally recrystallizing in an organic solvent at a low temperature to obtain the product. Wherein the organic solvent is one or more of methane, ethane, ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.
The whole reaction process of the preparation method of the pyrrole metallocene heterocycle constrained geometry metallocene catalyst is always carried out under the protection of inert gas, and the inert gas can be one of hydrogen, nitrogen, helium and argon.
The pyrrole metallocene heterocycle constrained geometry metallocene catalyst provided by the invention can be used as a catalyst in olefin polymerization reaction. As a preferred technical solution, the pyrrole metallocene heterocycle constrained geometry metallocene catalyst is used as a main catalyst, the alkyl aluminum or the aluminoxane compound is used as a cocatalyst, and the ratio of the mass of the main catalyst to the mass of the cocatalyst is 1: 500-2000. Among them, the alkylaluminum or the aluminoxane compound is preferably methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum or a mixture thereof.
The olefin monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene and divinylbenzene.
In detail, the olefin polymerization reaction may be carried out according to the following method:
the ethylene homopolymerization or the copolymerization of ethylene and alpha-olefin is carried out in a set of high-pressure reaction device, the capacity of the high-pressure kettle is 250mL, and the temperature and the rotating speed can be monitored and adjusted in real time. Before the reaction, preheating the reaction kettle in vacuum, opening argon to flush the reaction kettle for three times after the set temperature is reached, keeping the temperature constant, weighing the catalyst in a glove box, dissolving the catalyst in a toluene solvent, sequentially adding a half of the solvent, 1-hexene or 1-octene comonomer, MAO (methyl ammonium oxide) serving as a cocatalyst and a main catalyst into a feeding hopper, flushing the residual half of the solvent, flushing the residual catalyst in the feeding hopper into a feeder, closing a valve of the feeder, taking out the glove box, and flushing the solution in the feeder into the reaction kettle by using argon. Opening a valve, increasing the pressure of an ethylene steel cylinder to a set value, opening stirring, starting timing, controlling the temperature to be about the set value as far as possible in the reaction process, closing an ethylene inlet valve after the reaction is finished, opening condensed water for cooling, opening a reaction kettle, taking out a lining, pouring a product into a beaker, and adding a hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol ═ 1:15) to terminate the reaction. The polymer is washed repeatedly by hydrochloric acid-ethanol solution to dissolve aluminum salt remained in the reaction, then washed three times (30mL multiplied by 3) by deionized water, finally placed in a vacuum drying oven, dried at 60 ℃ to constant weight, and the catalytic activity of the catalyst is calculated.
The upper partWhen the pyrrole metallocene catalyst with heterocyclic constrained geometry is used for catalyzing ethylene homopolymerization, MAO is used as a cocatalyst, and the catalytic activity is as high as 4.5 multiplied by 10 6 g/(mol. Zr. h); when catalyzing ethylene/1-hexene copolymerization, MAO is used as a cocatalyst, and the catalytic activity reaches 2.3 multiplied by 10 6 g/(mol. Zr. h), 1-hexene insertion rate 9.14%; when catalyzing the copolymerization of ethylene/1-octene, MAO is used as a cocatalyst, and the catalytic activity reaches 1.3 multiplied by 10 6 g/(mol. Zr. h), 1-octene insertion rate 8.14%; in contrast to conventional tert-butylamine-based carbon bridge constrained geometry catalysts, e.g. [ t-BuN (Me) ] 2 C(η 5 -C 5 H 4 )]ZrCl 2 Under the same condition, the insertion rate of the ethylene/1-hexene copolymer obtained by catalysis is only 8.34 percent, the insertion rate of the ethylene/1-octene copolymer is only 5.46 percent, and the catalytic activity is in the same order of magnitude, so the catalyst obtained by the invention has higher industrial application value.
In conclusion, the invention adopts an amine elimination method to synthesize the IV B group constrained geometry catalyst containing pyrrole N heterocycle, simplifies the synthesis steps, the reaction yield reaches more than 90% when synthesizing fulvene and ligand, and the yield is greatly improved at the step of synthesizing the catalyst, so in general, the yield of the catalyst synthesized by the method is improved, researches show that compared with alkyl-N electron donor, the pyrrole group has stronger electron-withdrawing property, so that Zr-N bond is longer, so that the included angle between indenyl, metal central atom and the pyrrole group is smaller than that of the CGC of common alkyl N electron donor, the attack of alpha-olefin is more facilitated, the copolymerization activity of the catalyst of the type is better, and the space structure and electronic environment of an active center are influenced by changing the position of a substituent on the pyrrole group, so that the catalytic behavior of the catalyst is different, effectively improves the catalytic activity and the insertion rate of alpha-olefin in the copolymer.
Moreover, the catalyst provided by the invention has the advantages of simple synthetic route, high catalyst yield and few steps, has good activity when being used for catalyzing the copolymerization of ethylene and alpha-olefin, has high insertion rate of alpha-olefin monomers, can achieve 9.14 percent of 1-hexene insertion rate and 8.14 percent of 1-octene insertion rate, and has good application value.
The technical solution of the present invention will be further illustrated by the following specific examples.
Example 1
Complex 1[ (. eta.) ] 5 -C 9 H 6 )CH 2 (α-C 4 H 3 N)]Zr(NMe 2 ) 2 Synthesis of (2)
(1) Fulvene (C) 9 H 6 )CH(α-C 4 H 3 NH) preparation
2-Pyrrolecarboxaldehyde (4g, 42mmol) and freshly distilled indene (12.3g, 106mmol) were dissolved in 40mL of methanol in a 200mL Schlenk flask, and pyrrolidine (6g, 84mmol) was slowly added dropwise under an ice-water bath, during which the solution gradually changed from pale yellow to bright yellow, indicating that the reaction had started, and naturally warmed to room temperature after the addition was complete, and stirred for 90 min. Quenching with 50mL of distilled water in ice-water bath, adding glacial acetic acid (5g, 84mmol) to adjust pH to 7, adding 20mL of diethyl ether, separating with separating funnel, collecting upper organic phase, extracting aqueous phase with diethyl ether three times (30 mL. times.3), combining organic phases, washing twice with saturated saline solution, placing the obtained organic phase into an erlenmeyer flask, and adding anhydrous MgSO 4 And (5) drying for 6 h. Rotary evaporation gave an earth yellow solid which was separated by column chromatography (eluent: ethyl acetate/petroleum ether: 1/10) to give 6.97g (40mmol) of the pure product in 86% yield.
By passing 1 H NMR， 13 C NMR confirmed the chemical structure. ( 1 H NMR(CDCl 3 ,25℃):8.32(br s,1H,NH),6.77(s,1H,CH),7.48(m,1H,C 4 H 3 NH),7.23(m,1H,C 4 H 3 NH),7.06(m,1H,C 4 H 3 NH),7.11(m,2H,C 6 -H),6.87(m,2H,C 6 -H),6.56–6.22(m,2H,Cp-H)； 13 C NMR(100MHz,CDCl 3 ):δ140.21,136.70,132.61,131.68,129.10,125.47,124.04,123.77,121.21,120.03,117.58,117.12,113.68,110.28.)
(2) Ligand (C) 9 H 7 )CH 2 (α-C 4 H 3 NH) preparation
7.33g of fulvene (C) in a 200mL Schlenk flask 9 H 6 )CH(α-C 4 H 3 NH) (40mmol) was dissolved in 100mL of THF, and 38mL of LiAlH was added under an ice-water bath 4 Per Slow addition of THF (1M)Adding into a reaction flask, observing generation of many bubbles to indicate reaction progress, controlling dropwise adding speed to about half an hour, removing ice water bath, slowly heating to 50 deg.C, reacting for 15 hr, quenching with 50mL water in ice water bath, filtering with Buchner funnel to remove a large amount of aluminum salt, adding 20mL diethyl ether, separating with separating funnel, collecting upper organic phase, extracting aqueous phase with diethyl ether three times (30mL × 3), combining organic phases, washing with saturated saline solution twice, placing the obtained organic phase into a conical flask, and adding anhydrous MgSO (MgSO) to obtain the final product 4 Drying for 6 h. Rotary evaporation gave a white solid which was separated by column chromatography (eluent: ethyl acetate/petroleum ether: 1/20) to give the pure product 5.91g (30mmol), 79%.
By passing 1 H NMR， 13 C NMR confirmed the chemical structure. ( 1 H NMR(400MHz,CDCl 3 ,25℃):δ7.82(br s,NH),6.57(d,1H,C 4 H 3 NH),6.12(m,1H,C 4 H 3 NH),6.04(s,1H,C 4 H 3 NH),3.95(s,2H,-CH 2 -),3.32(s,CH 2 ,C 9 H 7 ),6.20(s,1H,C 9 H 7 ),7.42(d,1H,C 9 H 7 ),7.17-7.26(m,3H,C 9 H 7 )； 13 C NMR(100MHz,CDCl 3 ):δ143.72,143.41,140.92,128.96,127.85,125.14,123.74,122.72,118.26,115.62,107.27,105.24,36.63,25.65.)
(3) Complex 1[ (. eta.) ] 5 -C 9 H 6 )CH 2 (α-C 4 H 3 N)]Zr(NMe 2 ) 2 Synthesis of (2)
A100 mL Schlenk flask was taken, the flask was evacuated and purged with argon three times with a heat gun, and 30mL of freshly distilled toluene and 1.95g of ligand (C) were added 9 H 7 )CH 2 (α-C 4 H 3 NH) (10.0mmol) and 2.67g of Zr (NMe) were added in an ice-water bath 2 ) 4 (10mmol), removing the ice water bath, heating to 70 ℃ for reaction for 4h, introducing a small amount of protective gas in the whole reaction process to ensure that the gas by-product is continuously taken away, draining the solvent after the reaction is finished to obtain yellow slightly viscous solid, and recrystallizing at low temperature in a mixed solvent of n-hexane/toluene (1: 1) to obtain 2.48g of yellow solid with the yield of 75%.
By passing 1 H NMR， 13 C NMR, elemental analysis confirmed its chemical structure. ( 1 H NMR(400MHz,CDCl 3 ,25℃):7.45(m,2H,Benzo),6.70(m,2H,Benzo),6.70(m,1H,C 4 H 3 N),5.99(m,1H,C 4 H 3 N),5.91(m,1H,C 4 H 3 N),6.49(m,2H,C 5 H 2 ),4.30-4.26(m,1H,CH 2 ),3.98-3.94(m,1H,CH 2 ),3.12(s,6H,(NMe 2 ) 2 ,2.56(s,6H,(NMe 2 ) 2 )； 13 C NMR(100MHz,CDCl 3 ):δ153.22,126.07,124.58,124.09,124.04,123.57,123.29,121.77,121.49,118.07,105.95,101.24,98.56,49.05,45.17,25.98；Anal.Found:C,65.65；H,6.99；N,12.77.)
Example 2
Complex 1 catalyzed homogeneous polymerization of ethylene
Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the catalyst addition was 10. mu. mol, toluene 100mL, MAO 6.7mL (i.e., aluminum to zirconium ratio of 1000); after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer was washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100 mL. times.3) with deionized water, and finally dried in a vacuum oven at 60 ℃ to constant weight to give 11.5g of a solid, the catalyst activity was calculated to be 2.3X 10 6 g/(mol·Zr·h)
Example 3
Complex 1 catalyzed copolymerization of ethylene and 1-hexene
Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-zirconium ratio is 1000), and the adding amount of the 1-hexene is 20 mL; after feeding from the feeder, ethylene was setAnd (3) after the reaction is carried out for 30min under the pressure of 0.6MPa, closing an ethylene inlet valve, opening condensed water for cooling, opening the reaction kettle, taking out the product from the inner liner, pouring the product into a beaker, and adding a hydrochloric acid-ethanol solution (Vhydrochloric acid: Vethanol ═ 1:15) to terminate the reaction. The polymer is washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100mL multiplied by 3) with deionized water, finally put into a vacuum drying oven and dried at 60 ℃ to constant weight to obtain 9.5g of solid, and the calculated catalyst activity is 2.3 multiplied by 10 6 g/(mol. Zr. h), depending on the polymer 13 The C-NMR spectrum showed an insertion of 1-hexene into the copolymer of 8.72%.
Example 4
Complex 1 catalyzed copolymerization of ethylene and 1-octene
Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-zirconium ratio is 1000), and the adding amount of the 1-octene is 23 mL; after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer is washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100mL multiplied by 3) with deionized water, finally put into a vacuum drying oven and dried at 60 ℃ to constant weight to obtain 6.0g of solid, and the calculated catalyst activity is 1.3 multiplied by 10 6 g/(mol. Zr. h), depending on the polymer 13 The C-NMR spectrum showed that the insertion rate of 1-octene into the copolymer was 8.14%.
Example 5
Complex 2[ (. eta.) ] 5 -C 9 H 6 )CH 2 (α-C 4 H 3 N)]Zr(NEt 2 ) 2 Synthesis of (2)
A100 mL Schlenk flask was taken, the flask was evacuated and purged with argon three times with a heat gun, and 40mL of freshly distilled toluene and 1.95g of ligand (C) were added 9 H 7 )CH 2 (2-C 4 H 3 NH) (10.0mmol) in an ice-water bath2.80g of Zr (NEt) are added 2 ) 4 (10mmol), removing the ice water bath, heating to 80 ℃ for reaction for 4h, introducing a small amount of protective gas in the whole reaction process to ensure that the gas by-product is continuously taken away, draining the solvent after the reaction is finished to obtain mauve slightly-viscous solid, and recrystallizing in a mixed solvent of n-hexane/toluene (1: 1) at a low temperature to obtain 2.58g of dark red solid with the yield of 60%.
By passing 1 H NMR， 13 C NMR, elemental analysis confirmed its chemical structure. ( 1 H NMR(400MHz,CDCl 3 ,25℃):7.34(m,1H,C 4 H 3 N),6.04(m,1H,C 4 H 3 N),5.96(m,1H,C 4 H 3 N),7.15(m,4H,Benzo),6.50(m,1H,C 5 H 2 ),6.13(m,1H,C 5 H 2 ),4.23(s,2H,CH 2 ),3.52(m,4H,(NEt 2 ) 2 -CH 2 ),3.38(m,4H,(NEt 2 ) 2 -CH 2 ),1.09(m,12H,(NEt 2 ) 2 -CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ143.73,143.42,140.92,128.98,127.85,125.14,123.74,122.73,118.28,115.63,107.27,105.24,42.44,36.64,25.68；Anal.Found:C,61.68；H,7.24；N,9.81.)
Example 6
Complex 2 catalyzed homogeneous ethylene polymerization
Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the catalyst addition was 10. mu. mol, toluene 100mL, MAO 6.7mL (i.e., aluminum to zirconium ratio of 1000); after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer was washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100 mL. times.3) with deionized water, and finally dried in a vacuum oven at 60 ℃ to constant weight to give 22.5g of a solid with a calculated catalyst activity of 4.5X 10 6 g/(mol·Zr·h)。
Example 7
Complex 2 catalyzed copolymerization of ethylene and 1-hexene
Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-zirconium ratio is 1000), and the adding amount of the 1-hexene is 20 mL; after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer was washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100 mL. times.3) with deionized water, and finally dried in a vacuum oven at 60 ℃ to constant weight to give 11.5g of a solid, the catalyst activity was calculated to be 2.1X 10 6 g/(mol. Zr. h), depending on the polymer 13 C-NMR spectrum calculated 1-hexene insertion into the copolymer was 9.14%.
Example 8
Complex 2 catalyzed copolymerization of ethylene and 1-octene
Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-zirconium ratio is 1000), and the adding amount of the 1-octene is 23 mL; after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer is washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100mL multiplied by 3) with deionized water, finally put into a vacuum drying oven and dried at 60 ℃ to constant weight to obtain 6.5g of solid, and the calculated catalyst activity is 1.2 multiplied by 10 6 g/(mol. Zr. h), depending on the polymer 13 The C-NMR spectrum showed that the insertion rate of 1-octene into the copolymer was 8.05%.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A metallocene catalyst, wherein the metallocene catalyst has the following structure:
wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 Saturated or double-bond containing linear or branched C 2 -C 5 One of the hydrocarbon groups; r 4 Is straight-chain or branched C 1 -C 5 An alkyl group.
2. The metallocene catalyst of claim 1, wherein R is 4 Is CH 3 -or CH 3 CH 2 -。
3. A method for preparing a metallocene catalyst, comprising the steps of:
step 1, reacting 2-pyrrole carboxaldehyde or its derivative with indene to prepare nitrogen-containing fulvene shown in formula III, R 1 、R 2 And R 3 Each independently selected from H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups;
step 2, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step 3, ligand of pyrrole-containing N heterocyclic ring and Zr [ N (R) in formula IV 4 ) 2 ] 4 A complexation reaction occurs to produce a metallocene catalyst, R 4 Is straight-chain or branched C 1 -C 5 An alkyl group;
4. the method for preparing a metallocene catalyst according to claim 3, wherein R is 4 Is CH 3 -or CH 3 CH 2 -。
5. The method for preparing a metallocene catalyst according to claim 3, wherein the step 1 is: dissolving 2-pyrrole formaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent, cooling to-10-5 ℃, dropwise adding pyrrolidine, heating to room temperature, and stirring for reaction for 0.5-20 hours to obtain nitrogen-containing fulvene shown in the formula III;
wherein, the mass ratio of the 2-pyrrole formaldehyde or the derivatives thereof, indene and tetrahydropyrrole in the formula II is 1: 1-5: 1 to 5.
6. The method for preparing a metallocene catalyst according to claim 3, wherein the step 2 is: dissolving the nitrogen-containing fulvene of the formula III obtained in the step 1 in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, then heating to 40-70 ℃, stirring and reacting for 5-50h to obtain a pyrrole N heterocyclic-containing ligand of the formula IV;
wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5.
7. The method for preparing a metallocene catalyst according to claim 3, wherein the step 3 is: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step 2 in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Zr [ N (R) dissolved in the organic solvent 4 ) 2 ] 4 Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;
wherein, the formula IV contains pyrrole N heterocyclic ligand and Zr [ N (R) 4 ) 2 ] 4 In a molar ratio of 1: 0.5 to 5.
8. The method for preparing a metallocene catalyst according to claim 3, wherein the steps 1, 2 and 3 are performed under the protection of inert gas, and the inert gas is one or more selected from the group consisting of nitrogen, helium and argon.
9. A process for the polymerization of olefins carried out under the action of a metallocene catalyst as claimed in claim 1 or 2.
10. The olefin polymerization process of claim 9, wherein the alkene is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene, and divinylbenzene.
11. The olefin polymerization reaction method according to claim 9, wherein the metallocene catalyst of claim 1 or 2 is a main catalyst, the alkylaluminum or aluminoxane compound is a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.
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