CN114702531A - Metallocene, catalyst containing same, synthesis and application thereof - Google Patents

Metallocene, catalyst containing same, synthesis and application thereof Download PDF

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CN114702531A
CN114702531A CN202110000205.XA CN202110000205A CN114702531A CN 114702531 A CN114702531 A CN 114702531A CN 202110000205 A CN202110000205 A CN 202110000205A CN 114702531 A CN114702531 A CN 114702531A
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catalyst
solvent
metallocene
product
alkyl
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张志智
孙潇磊
王陶
刘全杰
张喜文
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium

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Abstract

The invention discloses an olefin polymerization catalyst. The catalyst comprises polysubstituted cyclopenta five-membered heterocyclic metallocene, an organic boride, alkyl metal and a solvent; metallocene is used as main catalyst, organic boride and alkyl metal are used as cocatalyst; the mol ratio of the metallocene, the organic boride and the alkyl metal is 1: (0.8-1.4): (10-500); the weight ratio of the solvent in the catalyst is 70-90%. The catalyst of the invention adopts a novel metallocene structure, effectively regulates and controls the electron and space effects of the metallocene, and improves the yield of trimerization, tetramerization and penta-polymerization end olefin products of heavy olefin polymerization.

Description

Metallocene, catalyst containing same, synthesis and application thereof
Technical Field
The invention relates to a metallocene and application thereof. In particular to a metallocene with a novel structure and synthesis and application thereof.
Background
Polyolefins have become a class of synthetic polymer materials widely used in our daily lives, and the market demand of traditional polyolefin materials, such as polyethylene and polypropylene, is still increasing. Polyolefin materials having specific functions, such as optical properties, continue to be of interest. The efficient transition metal complex is designed to accurately control the coordination polymerization of olefin, so that a novel polyolefin material which is difficult to synthesize by a traditional catalyst is synthesized. Therefore, considerable attention has been paid to the research for designing highly efficient transition metal complexes to accurately control coordination polymerization of olefins.
Metallocene catalysts can be used to synthesize a range of high performance polyolefin products such as isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, high density polyethylene, low density polyethylene, syndiotactic polystyrene and cyclic olefin copolymers, polybutene, PAO, etc. The metallocene catalyst has obvious advantages in the aspect of controlling and synthesizing polyolefin products, further optimizes the catalyst structure, synthesizes a new metallocene catalyst, and can synthesize the polyolefin products with excellent performance.
CN1020101897 describes a kind of metallocene catalyst structure with side chain containing N and O atoms, and its application in olefin polymerization is high in activity. Also described in CN 10224540 is a large class of metallocene complexes having a substituent in the 5-position of the indenyl ring and optionally a substituted furyl or thienyl group in the 2-position of the indenyl ring, which catalysts improve the absorption efficiency of ethylene or α -olefins and make it possible to obtain rubber components, in particular ethylene/propylene copolymer components, having a high molecular weight. CN 105985372A describes a kind of metallocene catalyst containing S or O heterocyclic ring for catalyzing long-chain alpha-olefin copolymerization. CN2016112389522 describes a bridged metallocene compound containing a heterocyclic structure, which is used for copolymerization of ethylene and alpha-olefin and improves the insertion rate of the alpha-olefin.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a metallocene with a novel structure, a catalyst containing the same, and synthesis and application thereof.
According to a first aspect of the present invention, there is provided a metallocene of novel structure.
A polysubstituted cyclopenta five-membered heterocyclic metallocene has the following structural general formula:
Figure DEST_PATH_IMAGE002
wherein X is sulfur, nitrogen or oxygen, preferably sulfur or nitrogen; r1、R2、R3Is CH3、C2H5、C3H7、C6H5Etc. alkyl is preferably CH3、C2H5(ii) a M is Zr, Ti or Hf, preferably Zr; z is Cl, Br, I, CH3、C2H5、C3H7Or C4H9Etc., are preferably Cl, Br, I or C2H5(ii) a M is the valence state-2 of the M metal.
According to a second aspect of the present invention, there is provided a process for the synthesis of the above metallocene.
A method for synthesizing polysubstituted cyclopenta five-membered heterocyclic metallocene comprises the following steps:
(1) adding substituted acyl chloride and substituted five-membered heterocycle into a solvent, uniformly stirring, cooling to-40-0 ℃, then adding a catalyst, and stirring for reaction for 10-24 hours; separating the reaction materials to obtain a product Pa (number Pa);
(2) adding the Pa product obtained in the step (1) and hexamethylenetetramine into acetic anhydride, and stirring to react for 24-48 h at the reaction temperature of 80-100 ℃; adding alkali liquor, and stirring and reacting for 1-4 h; separating organic matters by an extraction technology; then adding the extract and a strong acid catalyst into a solvent, and stirring for reaction at room temperature to 50 ℃ for 1-4 h; separating to obtain a product Pb;
(3) adding the product Pb obtained in the step (2) into ether to prepare a solution Ep; adding lithium aluminum hydride into diethyl ether to prepare lithium aluminum hydride diethyl ether solution Es; cooling the solution Es to-20-40 ℃; dropwise adding the solution Ep into the solution Es, heating to room temperature-40 ℃, and reacting for 1-2 h; separating by adopting an extraction-reduced pressure distillation technology to obtain a product Pc;
(4) adding the product Pc obtained in the step (3) and a strong acid catalyst into a solvent, heating and refluxing for 0.5-2 h, and separating to obtain a product Pd;
(5) dissolving the product Pd prepared in the step (4) in a solvent, cooling to-40-0 ℃, dropwise adding alkyl lithium, stirring and reacting for 0.5-3 h, wherein the reaction temperature is room temperature-40 ℃; then adding chloride salt, stirring and reacting for 24-48 h at room temperature-40 ℃ to obtain a solution S;
(6) and (4) pumping the solvent in the solution S obtained in the step (5), adding methyl chloride for dissolving, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain a product CpM.
Further, the substituted acyl chloride structure in the step (1) is R-CH2-CO-Cl, R is various alkyl and aromatic hydrocarbon, etc. Specifically, the substituted acyl chloride structure may be acetyl chloride, propionyl chloride, butyryl chloride, phenylacetyl chloride, or phenylpropyl chloride, or the like. The five-membered heterocyclic ring has the structure of
Figure 953773DEST_PATH_IMAGE004
R (R1, R2) is various alkyl and aromatic hydrocarbons. The solvent is at least one of benzene, toluene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide and the like, and benzene (0.8765 g/cm) is preferred3) Or toluene.
Further, the catalyst in the step (1) is anhydrous aluminum chloride or anhydrous tin chloride, and anhydrous tin chloride is preferred. The extraction-vacuum distillation is a conventional technology in the field, and the extraction agent used in the extraction process is at least one of dichloromethane, chloroform, dichloroethane, benzene, toluene and the like, and benzene is preferred.
Further, the molar ratio of the substituted acyl chloride to the substituted five-membered heterocyclic ring to the catalyst in the step (1) is 1 (0.8-1.2) to (0.01-0.1), and the weight ratio of the substituted five-membered heterocyclic ring to the solvent is 1: (4-10). And (2) stirring and reacting for 10-24 h in the step (1). The separation in step (1) is carried out by conventional procedures in the art, such as extraction-vacuum distillation.
The alkali liquor in the step (2) is an aqueous solution of alkali, the alkali is sodium hydroxide, sodium tert-butoxide, sodium bicarbonate and the like, and sodium hydroxide is preferred. The extractant is dichloromethane, chloroform, dichloroethane, benzene, toluene and the like, and dichloromethane is preferred. The strong acid catalyst is methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid and the like, and preferably methanesulfonic acid.
In the step (2), the concentration of the alkali liquor is 1-4 mol/L. The mole ratio of Pa, hexamethylenetetramine and acetic anhydride is 1: (0.8-1.6): (1.2-2.0), wherein the molar ratio of the alkali to the acetic anhydride is 1: (5-10). The molar ratio of the Pa product to the strong acid catalyst is 1 (0.1-0.5). The weight ratio of Pa product to solvent is generally 1: (4-10). The separation of the reaction mass in step (2) is carried out by conventional procedures in the art, such as extraction-vacuum distillation techniques.
In the step (3), the concentration of the prepared solution Ep is 1-3 mol/L. The concentration of the lithium aluminum hydride ethyl ether solution is generally 0.1-0.3 mol/L. The molar ratio of the product Pb to the lithium aluminum hydride is 1: (0.2-0.4).
The strong acid catalyst in the step (4) is methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (172 g/mol), hydrochloric acid, sulfuric acid and the like, and preferably is p-toluenesulfonic acid. The solvent is chloroform, carbon tetrachloride, benzene, toluene and the like, and benzene is preferred. Further, the molar ratio of Pc to the strongly acidic catalyst is 1: (0.02-0.05), wherein the weight ratio of the Pc to the solvent is 1: (10-18). The separation in step (4) is carried out by means of operations well known in the art, such as extraction-vacuum distillation techniques.
The chloride salt in the step (5) is zirconium chloride, hafnium chloride, titanium chloride and the like. Zirconium chloride is preferred. The solvent in the step (5) is diethyl ether, tetrahydrofuran and the like. Tetrahydrofuran is preferred. Further, the mole ratio of Pd to butyl lithium and zirconium chloride is 1: (1.8-2.4): (0.4-0.6). The weight ratio of Pd to the solvent is 1: (8-20).
The alkyl lithium in the step (5) comprises ethyl lithium, propyl lithium, butyl lithium and the like. Butyl lithium is preferred. The concentration of the alkyllithium solution is 2 to 4 mol/L.
In the step (6), the weight ratio of S to dichloromethane is 1: (10-20). The chloromethane is one of dichloromethane, trichloromethane and carbon tetrachloride.
According to a third aspect of the present invention, there is also provided an olefin polymerization catalyst comprising the polysubstituted cyclopenta five-membered heterocyclic metallocene as described above.
The olefin polymerization catalyst comprises polysubstituted cyclopentadiene and five-membered heterocyclic metallocene, organic boride, alkyl metal and solvent; metallocene is used as main catalyst, organic boride and alkyl metal are used as cocatalyst; the mol ratio of the metallocene, the organic boride and the alkyl metal is 1: (0.8-1.4): (10-500). Preferably 1 (0.9-1.3) to 20-100% by weight of the solvent in the catalyst, in an amount of 70-90%.
Further, the organic boride is selected from BF3、B(CF3)3、[MePhNH][B(CF3)3]、[(Me)2PhNH][B(CF3)4]、[R2NH][B(CF3)3]、[R3N][B(CF3)3]、[R3NH][B(CF3)4]、[Ph3C][B(CF3)2]、[NH3][B(CH3)3]、[Ph(Me)2N][B(C6F5)3]、[Ph(Me)2NH][B(C6F5)4]Wherein R ═ C2-C10Ph is phenyl and Me is methyl. The organic boron compound is preferably [ (Me)2PhNH][B(CF3)4]、[R3NH][B(CF3)4]Or [ Ph (Me)2NH][B(C6F5)4]More preferably [ Ph (Me)2NH][B(C6F5)4]。
Further, the metal alkyl comprises at least one of alkyl magnesium, alkyl aluminum and alkyl zinc. The alkyl magnesium is at least one selected from the group consisting of diethyl magnesium, dipropyl magnesium, diisopropyl magnesium and dibutyl magnesium; the alkyl aluminum is at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, tri-tert-butyl aluminum and the like; the alkyl zinc is at least one selected from diethyl zinc, dipropyl zinc, diisopropyl zinc, dibutyl zinc, di-tert-butyl zinc and the like. Preferably, the metal alkyls are tributylaluminum and tri-tert-butylaluminum, more preferably tri-tert-butylaluminum.
Further, the solvent may be at least one of benzene, toluene, n-octane, n-decane, alkylated oils, and the like.
According to a fourth aspect of the present invention, there is also provided an olefin oligomerization reaction in which the above-described olefin polymerization catalyst is used.
Specifically, the olefin oligomerization reaction comprises the following steps: the olefin and the catalyst are introduced into an autoclave and polymerization is carried out under oligomerization conditions.
Further, the oligomerization conditions were as follows: the reaction temperature is 40-100 ℃, preferably 60-80 ℃, and the reaction time is 1-8 hours, preferably 2-4 hours.
Compared with the prior art, the catalyst and the preparation method have the following beneficial effects:
the catalyst adopts a novel metallocene structure, effectively regulates and controls the electron and space effects of the metallocene, and can obviously improve the yield of trimerization, tetramerization and penta-polymerization end olefin products of heavy olefin polymerization. In particular, the five-membered heterocyclic ring increases the aromaticity of the cyclopentadiene. Meanwhile, the existence of the heteroatom shifts the electron cloud of the aromatic ring, which is helpful for stabilizing alkyl or hydrogen atoms on the metallocene and promoting the exposure of a cation center, thereby promoting the coupling of macromolecular olefin and the cation center and realizing chain initiation and chain growth. The existence of the substituent further promotes the movement of electrons to zirconium metal, reduces the electropositivity of the zirconium metal, is beneficial to beta-H elimination reaction, realizes chain termination, prevents the occurrence of olefin high polymer, effectively adjusts the three factors, optimizes the catalytic performance of metallocene, and improves the selectivity of oligomers such as trimerization, tetramerization, pentamer and the like of heavy olefin polymerization. Meanwhile, the steric hindrance and the power supply effect prevent the bimolecular dehydrogenation reaction of the metallocene, effectively reduce the generation of the hydrogenation saturated product of the olefin reactant and improve the reaction activity of the catalyst.
Detailed Description
The technical solution of the present invention will be further described with reference to the following specific examples.
The organic solvent used for the experiment was purified on a solvent purification system of Mikana SolvPurer A3/G3, the purification of which is a procedure well known to those skilled in the art. The required water and oxygen free operation was performed in a Mikenana Super (1220/750) glove box. The product analysis was performed by Agilent 7890A gas chromatography. The element detection of the catalyst was carried out by means of an X-ray fluorescence spectrometer model ZSX100e, manufactured by Nippon chemical company.
The reagents and solvents used in the examples were derived from carbofuran and were chemically pure.
Example 1
(1) Propionyl chloride 92.5g (92.5 g/mol) and 2, 3-dimethylpyrrole 95g (95 g/mol) were added to 736g benzene (0.8765 g/cm 3), stirred well, cooled to-20 ℃ and then 13g anhydrous tin chloride (260 g/mol) was added dropwise. The reaction was stirred for 20 h. The product Pa1 (151 g/mol) was isolated using extraction-vacuum distillation techniques. The yield thereof was found to be 91%.
(2) 75.5g of the Pa1 product obtained in step (1) and 91g of hexamethylenetetramine (140 g/mol) were added to 92g of acetic anhydride (102 g/mol), and the mixture was stirred and reacted for 20 hours at a reaction temperature of 90 ℃.56 mL of 2mol/L sodium hydroxide was added, and the reaction was stirred for 3 hours. The extraction technology separates the organic matter. The extract and 14.4g of methanesulfonic acid (96 g/mol) were then added to 608g of dichloromethane and the reaction was stirred at 30 ℃ for 2 h. The product Pb1 was isolated by extraction-vacuum distillation. The yield thereof was found to be 88%.
(3) 41g of the product Pb1 (163 g/mol) obtained in step (2) was added to 125mL of diethyl ether to prepare a solution Ep 1. The concentration of Ep1 was 2 mol/L. 2.9g of lithium aluminum hydride (38 g/mol) was added to 375mL of diethyl ether to prepare a lithium aluminum hydride diethyl ether solution having a concentration of 0.2 mol/L. The solution was cooled to-30 ℃. Ep1 was added dropwise to the lithium aluminum hydride in ether solution. The temperature is increased to 30 ℃ and the reaction is carried out for 2 h. The product P1c was isolated using an extraction-vacuum distillation technique. The yield thereof was found to be 84%.
(4) 41g of the product Pc1 (165 g/mol) obtained in step (3) and 1.2g of benzenesulfonic acid (158 g/mol) were added to 615g of benzene and heated under reflux for 1.5 hours. The product Pd1 is separated by extraction-reduced pressure distillation technology. The yield thereof was found to be 89%.
(5) 18g of the product Pd1 (147 g/mol) prepared in step (4) was dissolved in 270g of tetrahydrofuran, cooled to-40 ℃, 131mL of a 2mol/L butyllithium hexane solution was added dropwise, and the reaction was stirred for 2 hours at a reaction temperature of 30 ℃. Then, 14.6g of zirconium chloride (233 g/mol) was added thereto, and the mixture was stirred and reacted at 30 ℃ for 30 hours to obtain a solution S.
(6) And (3) pumping the solvent in the solution S1 obtained in the step (4), adding 560g of dichloromethane for dissolving, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the product CpM 1. The yield thereof was found to be 94%. The overall yield of CpM1 was 56%.
The obtained product metallocene is characterized by an element analysis method and has the following structural general formula:
Figure 795827DEST_PATH_IMAGE002
wherein R1, R2 and R3 are CH3(ii) a X is nitrogen element; m is Zr; z is Cl; m is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C20ZrCl2H24, and the theoretical weight percentage composition is 6.17wt% N, 52.86wt% C, 20.04wt% Zr, 15.64wt% Cl and 5.29wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene conforms to the theoretical composition, indicating that a zirconocene was synthesized.
Example 2
(1) Propionyl chloride 92.5g/mol and 2g, 3-dimethylpyrrole 95g/mol were added to 920g benzene 0.8765g/cm3) Then, the mixture was stirred uniformly, cooled to-20 ℃ and 26g of anhydrous tin chloride (260 g/mol) was added dropwise thereto. The reaction was stirred for 20 h. The product Pa2 (151 g/mol) was isolated using extraction-vacuum distillation techniques. The yield thereof was found to be 88%.
(2) 75.5g of the Pa product obtained in step (1) and 112g of hexamethylenetetramine (140 g/mol) were added to 102g of acetic anhydride (102 g/mol), and the mixture was stirred and reacted for 20 hours at a reaction temperature of 90 ℃. 50mL of 2mol/L sodium hydroxide was added, and the reaction was stirred for 3 hours. The extraction technology separates the organic matter. The extract and 24g of methanesulfonic acid (96 g/mol) were then added to 755g of dichloromethane and the reaction was stirred at 30 ℃ for 2 h. The product Pb2 was isolated by extraction-vacuum distillation. The yield thereof was found to be 81%.
(3) 41g of the product Pb2 (163 g/mol) from step (2) was added to 83mL of diethyl ether to prepare a solution Ep 2. The concentration of Ep2 was 3 mol/L. 3.8g of lithium aluminum hydride (38 g/mol) was added to 1000mL of diethyl ether to prepare a lithium aluminum hydride diethyl ether solution having a concentration of 0.1 mol/L. The solution was cooled to-30 ℃. Ep2 was added dropwise to the lithium aluminum hydride in ether solution. The temperature is increased to 30 ℃ and the reaction is carried out for 2 h. The product Pc2 was isolated by extraction-vacuum distillation. The yield thereof was found to be 79%.
(4) 41g of the product Pc2 (165 g/mol) from step (3) and 2g of benzenesulfonic acid (158 g/mol) were added to 738g of benzene and heated under reflux for 1.5 h. The product Pd2 was isolated by extraction-vacuum distillation. The yield thereof was found to be 91%.
(5) 18g of the product Pd2 (147 g/mol) prepared in step (4) was dissolved in 360g of tetrahydrofuran, cooled to-40 ℃, 150mL of a 2mol/L butyllithium hexane solution was added dropwise, and the reaction was stirred for 2 hours at a reaction temperature of 30 ℃. Then, 17.5g of zirconium chloride (233 g/mol) was added thereto, and the mixture was stirred and reacted at 30 ℃ for 30 hours to obtain a solution S.
(6) And (3) pumping the solvent in the solution S2 obtained in the step (4), adding 700g of dichloromethane for dissolving, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the product CpM 2. The yield thereof was found to be 93%. The overall yield of CpM2 was 47%.
The obtained product metallocene is characterized by an element analysis method and has the following structural general formula:
Figure 191036DEST_PATH_IMAGE002
wherein R1, R2, R3 are CH3(ii) a X is nitrogen element; m is Zr; z is Cl; m is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C20ZrCl2H24, and the theoretical weight percentage composition is 6.17wt% N, 52.86wt% C, 20.04wt% Zr, 15.64wt% Cl and 5.29wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene conforms to the theoretical composition, indicating that a zirconocene was synthesized.
Example 3
(1) Propionyl chloride 92.5g (92.5 g/mol) and 2, 3-dimethylpyrrole 76g (95 g/mol) were added to 368g benzene (0.8765 g/cm 3), stirred well, cooled to-20 ℃ and then 2.6g anhydrous stannic chloride (260 g/mol) was added dropwise. The reaction was stirred for 20 h. The product Pa3 (151 g/mol) was isolated using extraction-vacuum distillation techniques. The yield thereof was found to be 79%.
(2) 75.5g of the product Pa3 obtained in step (1) and 56g of hexamethylenetetramine (140 g/mol) were added to 61g of acetic anhydride (102 g/mol), and the mixture was stirred and reacted for 20 hours at a reaction temperature of 90 ℃. 60mL of 2mol/L sodium hydroxide was added, and the reaction was stirred for 3 hours. The extraction technology separates the organic matter. The extract and 4.8g of methanesulfonic acid (96 g/mol) were then added to 302g of dichloromethane and the reaction was stirred at 30 ℃ for 2 h. The product Pb3 was isolated by extraction-vacuum distillation. The yield thereof was found to be 78%.
(3) 41g of the product Pb3 from step 2 (163 g/mol) were added to 250mL of diethyl ether to prepare a solution Ep 3. The concentration of Ep3 was 1 mol/L. 1.9g of lithium aluminum hydride (38 g/mol) was added to 167mL of diethyl ether to prepare a lithium aluminum hydride diethyl ether solution having a concentration of 0.3 mol/L. The solution was cooled to-30 ℃. Ep was added dropwise to the lithium aluminum hydride in ether solution. The temperature is increased to 30 ℃ and the reaction is carried out for 2 h. The product Pc3 was isolated by extraction-distillation under reduced pressure. The yield thereof was found to be 74%.
(4) 41g of the product Pc3 (165 g/mol) obtained in step (3) and 0.8g of benzenesulfonic acid (158 g/mol) were added to 410g of benzene, and the mixture was refluxed for 1.5 hours. The product Pd3 was isolated by extraction-vacuum distillation. The yield thereof was found to be 81%.
(5) 18g of the product Pd3 (147 g/mol) prepared in step (4) was dissolved in 144g of tetrahydrofuran, cooled to-40 ℃, 112mL of a 2mol/L butyllithium hexane solution was added dropwise, and the reaction was stirred for 2 hours at a reaction temperature of 30 ℃. Then, 11.6g of zirconium chloride (233 g/mol) was added thereto, and the mixture was stirred and reacted at 30 ℃ for 30 hours to obtain a solution S.
(6) And (3) pumping the solvent in the solution S3 obtained in the step (4), adding 320g of dichloromethane for dissolving, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the product CpM 3. The yield thereof was found to be 84%. The overall yield of CpM3 was 31%.
The obtained product metallocene is characterized by an element analysis method and has the following structural general formula:
Figure 5409DEST_PATH_IMAGE002
wherein R1, R2 and R3 are CH3(ii) a X is nitrogen element; m is Zr; z is Cl; m is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C20ZrCl2H24, and the theoretical weight percentage composition is 6.17wt% N, 52.86wt% C, 20.04wt% Zr, 15.64wt% Cl and 5.29wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene conforms to the theoretical composition, indicating that a zirconocene was synthesized.
Example 4
The CpM4 of the invention was prepared as in example 1, except that acetyl chloride was used in place of propionyl chloride and 2-methylpyrrole was used in place of 2, 3-dimethylpyrrole. The overall yield of CpM4 was 53%.
The obtained product metallocene is characterized by an element analysis method and has the following structural general formula:
Figure 391653DEST_PATH_IMAGE002
wherein R1, R3 are H; r2 is CH3(ii) a X is nitrogen element; m is Zr; z is Cl; m is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C16ZrCl2H16, and the theoretical weight percentage composition is 7.03 weight percent of N, 48.24 weight percent of C, 22.86 weight percent of Zr, 17.84 weight percent of Cl and 4.02 weight percent of H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene conforms to the theoretical composition, indicating that a zirconocene was synthesized.
Example 5
CpM5 according to the invention was prepared as in example 1, except that 2, 3-dimethylpyrrole was replaced by 2, 3-dimethylthiophene. The overall yield of CpM5 was 56%.
The obtained product metallocene is characterized by an element analysis method and has the following structural general formula:
Figure DEST_PATH_IMAGE005
wherein, R1, R2, R3 are CH 3; x is sulfur element; m is Zr; z is Cl; m is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is S2C20ZrCl2H24, and the theoretical weight percentage composition is 13.06wt% S, 48.98wt% C, 18.57wt% Zr, 14.49wt% Cl and 4.90wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene conforms to the theoretical composition, indicating that a zirconocene was synthesized.
Example 6
The CpM6 of the invention was prepared as in example 1, except that butyryl chloride was used in place of propionyl chloride and 2, 3-dimethylthiophene was used in place of 2, 3-dimethylpyrrole. The overall yield of CpM6 was 48%.
The obtained product metallocene is characterized by an element analysis method and has the following structural general formula:
Figure 658686DEST_PATH_IMAGE002
wherein R1 is CH3HC2R2, R3 are CH3(ii) a X is sulfur element; m is Zr; z is Cl; m is 2.
The element composition of the polysubstituted cyclopentadienylpentaheterocycle metallocene is S2C22ZrCl2H28, and the theoretical weight percentage composition is 12.36wt% of S, 50.97wt% of C, 17.56wt% of Zr, 13.71wt% of Cl and 5.40wt% of H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene conforms to the theoretical composition, indicating that a zirconocene was synthesized.
TABLE 1 metallocene elemental analysis
Figure DEST_PATH_IMAGE007
Example 7
4.68g of the metallocene CpM1 prepared in example 1 (468 g/mol), 10.9g [ Ph (Me)2NH][B(C6F5)4](1089 g/mol) and 39.6g of tributylaluminum (198 g/mol) were added to 497g of alkylate oil and stirred well to obtain catalyst composition C1.
The molar ratio of the metal alkyl is 1:1:20, and the weight ratio of the solvent in the catalyst is 90%.
Example 8
4.68g of the metallocene CpM1 prepared in example 1 (468 g/mol), 14.1g [ Ph (Me)2NH][B(C6F5)4](1089 g/mol) and 99g of tributylaluminum (198 g/mol) were added to 274g of the alkylate and stirred well to obtain catalyst composition C2.
The molar ratio of the metal alkyl is 1:1.3:50, and the weight ratio of the solvent in the catalyst is 70%.
Example 9
4.68g of the metallocene CpM1 prepared in example 1 (468 g/mol), 9.8g [ Ph (Me)2NH][B(C6F5)4](1089 g/mol) and 198g of tributylaluminum (198 g/mol) were added to 850g of alkylate and stirred well to obtain catalyst composition C3.
The molar ratio of the metal alkyl is 1: 0.9: 100, and the weight ratio of the solvent in the catalyst is 80%.
Example 10
Catalyst C4 according to the invention was prepared as in example 7, except that the CpM4 prepared in example 4 was used.
Example 11
Catalyst C5 according to the invention was prepared as in example 7, except that the CpM5 prepared in example 5 was used.
Example 12
Catalyst C6 according to the invention was prepared as in example 7, except that the CpM6 prepared in example 6 was used.
TABLE 2 molar composition of the components of the catalyst
Figure DEST_PATH_IMAGE009
Examples 13 to 16
The oligomerization of 1-decene was carried out in an autoclave equipped with electromagnetic stirring. Before the reaction, the autoclave was cleaned, heated in an oil bath at 140 ℃ and evacuated to a negative pressure for 0.5 h. The autoclave was charged with high-purity nitrogen gas and evacuated again, and this was repeated three times. The reaction kettle was cooled to the reaction temperature. Heating in oil bath, and stirring. Respectively connecting a liquid 1-decene steel cylinder and a catalyst feeding tank with a metering pump, and introducing the 1-decene and the catalyst into the high-pressure kettle through the metering pump. The reaction temperature was 70 ℃ and the reaction time was 2 hours.
Specific process conditions and reaction results are shown in table 3.
TABLE 3 Process conditions and results
Figure DEST_PATH_IMAGE011
Comparative example 1
The existing metallocene catalyst adopts n-butyl cyclopentadiene zirconium chloride metallocene and methyl aluminoxane to catalyze butene oligomerization, 4.06g of n-butyl cyclopentadiene zirconium chloride metallocene, 58g of methyl aluminoxane and 14L 1-decene are respectively added into an autoclave, stirred and heated. The reaction conditions were a pressure of 3MPa, a temperature of 70 ℃ and a time of 2 hours. Conversion of 1-decene 59mol%, C30+C40+C50The total selectivity was 42 wt%.
Compared with the existing catalyst, the activity and the total selectivity of C30+ C40+ C50 of the catalyst are obviously superior to those of the existing catalyst.

Claims (24)

1. A polysubstituted cyclopenta five-membered heterocyclic metallocene, characterized by the general structural formula as shown in the following formula:
Figure DEST_PATH_IMAGE001
wherein X is sulfur, nitrogen or oxygen, preferably nitrogen; r1、R2、R3Is CH3、C2H5、C3H7And C6H5At least, preferably H, CH, is contained in the alkyl group3、C2H5At least one of (a); m is Zr, Ti or Hf, preferably Zr; z is Cl, Br, I, CH3、C2H5、C3H7Or C4H9Preferably Cl, Br, I or C2H5(ii) a M is the valence state-2 of the M metal.
2. A process for synthesizing a metallocene as claimed in claim, comprising:
(1) adding substituted acyl chloride and substituted five-membered heterocycle into a solvent, uniformly stirring, cooling to-40-0 ℃, then adding a catalyst, and stirring for reaction for 10-24 hours; separating the reaction material to obtain a product Pa;
(2) adding the Pa product obtained in the step (1) and hexamethylenetetramine into acetic anhydride, and stirring to react for 24-48 h at the reaction temperature of 80-100 ℃; adding alkali liquor, and stirring and reacting for 1-4 h; separating organic matters by an extraction technology; then adding the extract and a strong acid catalyst into a solvent, and stirring for reaction at room temperature to 50 ℃ for 1-4 h; separating to obtain a product Pb;
(3) adding the product Pb obtained in the step (2) into ether to prepare a solution Ep; adding lithium aluminum hydride into diethyl ether to prepare lithium aluminum hydride diethyl ether solution Es; cooling the solution Es to-20-40 ℃; dropwise adding the solution Ep into the solution Es, heating to room temperature-40 ℃, and reacting for 1-2 h; separating to obtain a product Pc;
(4) adding the product Pc obtained in the step (3) and a strong acid catalyst into a solvent, heating and refluxing for 0.5-2 h, and separating to obtain a product Pd;
(5) dissolving the product Pd prepared in the step (4) in a solvent, cooling to-40-0 ℃, dropwise adding alkyl lithium, stirring and reacting for 0.5-3 h, wherein the reaction temperature is room temperature-40 ℃; then adding chloride salt, stirring and reacting for 24-48 h at room temperature-40 ℃ to obtain a solution S;
(6) and (4) pumping the solvent in the solution S obtained in the step (5), adding methyl chloride for dissolving, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain a product CpM.
3. The method as claimed in claim 2, wherein the substituted acyl chloride of step (1) has a structure of R-CH2-CO-Cl, R being various alkyl and aromatic hydrocarbons, preferably substituted acyl chlorides having the structure acetyl chloride, propionyl chloride, butyryl chloride, phenylacetyl chloride or phenylpropyl chloride; the structure of the five-membered heterocyclic ring is that R (R1, R2) is various alkyl and arene.
4. The method of claim 2, wherein the solvent is benzene, toluene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, or the like.
5. The synthesis method according to claim 2, wherein the catalyst in step (1) is anhydrous aluminum chloride or anhydrous tin chloride.
6. The synthesis method according to claim 2, wherein the molar ratio of the substituted acyl chloride, the substituted five-membered heterocyclic ring and the catalyst in the step (1) is 1 (0.8-1.2) to (0.01-0.1), and the weight ratio of the substituted five-membered heterocyclic ring to the solvent is 1: (4-10).
7. The synthesis method according to claim 2, wherein the stirring reaction in the step (1) is carried out for 10-24 hours.
8. The synthesis method according to claim 2, wherein the alkaline solution in step (2) is an aqueous solution of a base, the base is at least one of sodium hydroxide, sodium tert-butoxide and sodium bicarbonate, and the strongly acidic catalyst is one of methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and sulfuric acid.
9. The synthesis method according to claim 2, wherein the concentration of the alkali liquor in the step (2) is 1-4 mol/L.
10. The synthesis method according to claim 2, wherein the molar ratio of Pa, hexamethylenetetramine and acetic anhydride in step (2) is 1: (0.8-1.6): (1.2-2.0), wherein the molar ratio of the alkali to the acetic anhydride is 1: (5-10), the molar ratio of the Pa product to the strong acid catalyst is 1 (0.1-0.5), and the weight ratio of the Pa product to the solvent is 1: (4-10).
11. The synthesis method of claim 2, wherein the concentration of the solution Ep prepared in the step (3) is 1-3 mol/L, the concentration of the lithium aluminum hydride ethyl ether solution is 0.1-0.3 mol/L, and the molar ratio of the product Pb to the lithium aluminum hydride is 1: (0.2-0.4).
12. The synthesis method according to claim 2, wherein the strongly acidic catalyst in step (4) is methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, etc., and the solvent is at least one of chloroform, carbon tetrachloride, benzene, toluene.
13. The synthesis method according to claim 2, wherein the molar ratio of Pc to the strongly acidic catalyst in step (4) is 1: (0.02-0.05), wherein the weight ratio of the Pc to the solvent is 1: (10-18).
14. The synthesis method of claim 2, wherein the solvent in step (5) is one of diethyl ether and tetrahydrofuran, and the molar ratio of Pd to butyllithium and zirconium chloride is 1: (1.8-2.4): (0.4-0.6), wherein the weight ratio of Pd to the solvent is 1: (8-20), wherein the concentration of the butyl lithium hexane solution is 2-4 mol/L.
15. The synthesis method according to claim 2, wherein in the step (6), the weight ratio of S to dichloromethane is 1: (10-20), wherein the chloromethane is one of dichloromethane, trichloromethane and carbon tetrachloride.
16. An olefin polymerization catalyst comprising the metallocene according to claim 1.
17. The olefin polymerization catalyst of claim 16 wherein said olefin polymerization catalyst comprises a metallocene, an organic boride, a metal alkyl, and a solvent; metallocene is used as main catalyst, organic boride and alkyl metal are used as cocatalyst; the mol ratio of the metallocene, the organic boride and the alkyl metal is 1: (0.8-1.4): (10-500), wherein the weight ratio of the solvent in the catalyst is 70-90%.
18. The process of claim 16 wherein the organic boron compound is selected from the group consisting of BF3、B(CF3)3、[MePhNH][B(CF3)3]、[(Me)2PhNH][B(CF3)4]、[R2NH][B(CF3)3]、[R3N][B(CF3)3]、[R3NH][B(CF3)4]、[Ph3C][B(CF3)2]、[NH3][B(CH3)3]、[Ph(Me)2N][B(C6F5)3]、[Ph(Me)2NH][B(C6F5)4]Wherein R ═ C2-C10Ph is phenyl and Me is methyl.
19. The olefin polymerization catalyst according to claim 18Characterised in that the organic boron compound is preferably [ (Me)2PhNH][B(CF3)4]、[R3NH][B(CF3)4]Or [ Ph (Me)2NH][B(C6F5)4]。
20. The olefin polymerization catalyst of claim 17 wherein the metal alkyl comprises at least one of magnesium alkyl, aluminum alkyl, and zinc alkyl, the magnesium alkyl is selected from at least one member of the group consisting of diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, and dibutylmagnesium, the aluminum alkyl is selected from at least one member of the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and tri-tert-butylaluminum, and the zinc alkyl is selected from at least one member of the group consisting of diethylzinc, dipropylzinc, diisopropylzinc, dibutylzinc, and di-tert-butylzinc.
21. The olefin polymerization catalyst of claim 20 wherein the metal alkyls are tributyl aluminum and tri-tert-butyl aluminum.
22. The olefin polymerization catalyst according to claim 17, wherein the solvent is at least one selected from the group consisting of benzene, toluene, n-octane, n-decane, alkylated oils, and the like.
23. An olefin oligomerization reaction wherein an olefin polymerization catalyst as claimed in any one of claims 16 to 22 is used.
24. The olefin oligomerization reaction of claim 23, wherein the olefin oligomerization reaction comprises: introducing olefin and a catalyst into a high-pressure kettle, and carrying out polymerization reaction under an oligomerization reaction condition; the oligomerization reaction conditions are as follows: the reaction temperature is 40-100 ℃, and the reaction time is 1-8 hours.
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