CN113307896A - Binuclear rare earth catalyst and preparation method and application thereof - Google Patents
Binuclear rare earth catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113307896A CN113307896A CN202110643812.8A CN202110643812A CN113307896A CN 113307896 A CN113307896 A CN 113307896A CN 202110643812 A CN202110643812 A CN 202110643812A CN 113307896 A CN113307896 A CN 113307896A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- earth catalyst
- binuclear
- mol
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
- C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention provides a binuclear rare earth catalyst for olefin polymerization and a preparation method and application thereof, wherein the binuclear rare earth catalyst has a structure shown in a formula I; compared with a corresponding mononuclear rare earth metal catalyst or a cyclopentadienyl binuclear rare earth catalyst with a long-chain group and a rigid group bridged, the binuclear rare earth catalyst provided by the invention shows a remarkable bimetal synergistic effect in the process of catalyzing olefin polymerization.
Description
Technical Field
The invention belongs to the technical field of metallocene catalysts, and particularly relates to a binuclear rare earth catalyst and a preparation method and application thereof.
Background
Compared with a mononuclear catalyst, the binuclear catalyst has unique catalytic action, such as the advantages of generating higher molecular weight polymers, obtaining copolymers with high comonomer content, having higher tolerance to polar monomers and the like. Researchers have invested a great deal of effort in the synthesis of binuclear catalysts and have achieved certain achievements, particularly in the design and synthesis of binuclear group iv metal catalysts (chem. rev.2011,111, 2450-2485). However, there are few reports on binuclear rare earth catalysts, especially binuclear cyclopentadienyl tetraanionic rare earth catalysts (one chelating cyclopentadienyl ligand and two initiating anionic groups on each metal) with better catalytic performance.
Non-patent documents Angew. chem. int. Ed.2017,56,15964-2)Si(Me2) -and-Si (Me)2)CH2CH2Si(Me2) The long-chain group bridged cyclopentadienyl rare earth binuclear catalyst can be obtained by a common synthesis method (the rigidity of the bis-dimethylsilicon bridge is higher, so that the synthesis of the bridged cyclopentadienyl rare earth binuclear rare earth complex is ensured). In addition, according to literature data and experimental results, the long-chain group bridged binuclear rare earth complex has a long rare earth metal center distance, and the synergistic effect between two metals is very limited in the process of catalyzing olefin polymerization.
Disclosure of Invention
In view of the above, the present invention aims to provide a binuclear rare earth catalyst, a preparation method and an application thereof, wherein the catalyst exhibits a significant bimetal synergistic effect in the process of catalyzing olefin polymerization.
The invention provides a binuclear rare earth catalyst for olefin polymerization, which has a structure shown in formula I:
the Cp1 and Cp2 are independently selected from substituted or unsubstituted cyclopentadiene groups, substituted or unsubstituted indene groups and substituted or unsubstituted fluorene groups;
r is selected from a single atom bridging group or-CH2CH2-；
The X1 and X2 are independently selected from one or more of alkyl with 1-16 carbon atoms, silyl with 4-16 carbon atoms, amido with 2-16 carbon atoms, silicon amido with 4-20 carbon atoms, arylamine with 6-20 carbon atoms, allyl with 3-10 carbon atoms, benzyl with 7-20 carbon atoms, boron tetrahydride, tetramethylaluminum and hydrogen;
the Ln is selected from scandium, yttrium or lanthanide;
l is neutral Lewis base tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, pyridine or substituted pyridine;
and w is the number of the coordination Lewis base, and the value of w is 0-3.
In the present invention, said R is a short chain bridging group;
in the present invention, the Cp1 and Cp2 are independently selected from the group consisting of fluorenyl, 2, 7-di-t-butylfluorenyl, benzofluorenyl, bisbenzofluorenyl, cycloalkane-substituted fluorenyl, indenyl, 4, 7-dimethylindenyl, 2-methylindenyl, cyclopentadienyl, tetramethylcyclopentadienyl, 1-t-butyl-2-trimethylsilylcyclopentadienyl, 1, 3-bis (trimethylsilyl) cyclopentadienyl, methylcyclopentadienyl, t-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, 1, 2-dimethylcyclopentadienyl, 1, 3-dimethylcyclopentadienyl, 1, 2-diethylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, n-octylcyclopentadienyl, tetrahydroindenyl, propylcyclopentadienyl, octahydrofluorenyl, phenylcyclopentadienyl, n-octylcyclopentadienyl, tetrahydroindenyl, propylcyclopentadienyl, octahydrofluorenyl, 1, 2-diphenylcyclopentadienyl, cyclohexylcyclopentadienyl or 2, 2' -diphenylcyclopentadienyl.
In the present invention, both X1 and X2 are monoanionic initiating groups; in a specific embodiment, both X1 and X2 are independentSelected from CH on the ground2SiMe3。
In the present invention, the monoatomic bridging group is selected from CH2 2-、CMe2 2-、SiMe2 2-、SiHMe2-、SiPhMe2-、PMe2-、BMe2-And SnMe2 2-One or more of (a).
In the present invention, Ln is selected from one or more of scandium, yttrium, lutetium, erbium, holmium, dysprosium, thulium, ytterbium, gadolinium, neodymium, and lanthanum.
In the invention, the binuclear rare earth catalyst is specifically selected from any one of complexes 1 to 12:
the invention provides a preparation method of the binuclear rare earth catalyst in the technical scheme, which comprises the following steps:
dissolving a ligand with Cp1-R-Cp2 in an organic solvent under anhydrous and oxygen-free conditions to obtain a ligand solution;
reacting the ligand solution with an alkali metal reagent with twice molar weight to obtain an alkali metal salt of the ligand;
mixing an alkali metal salt of the ligand with twice the molar amount of YLNX1X2L(w)Reacting to obtain a binuclear rare earth catalyst with a structure shown in formula I;
the YLnX1X2L(w)Wherein Y is selected from halogen, BH4 -、[(C6H5)4B]-Or [ (C)6F5)4B]-。
The ligands of Cp1-R-Cp2 are preferably prepared by methods described or reported in the prior art.
The invention provides a binuclear rare earth catalyst composition for catalyzing olefin polymerization, which comprises the following components in a mass ratio of 1: (0-4): (0-1000) a binuclear rare earth catalyst, an organic boron salt and a main group metal alkyl reagent;
the binuclear rare earth catalyst is the binuclear rare earth catalyst in the technical scheme or the binuclear rare earth catalyst prepared by the preparation method in the technical scheme.
In the present invention, the organoboron salt is selected from the group consisting of [ B (C) and [ C ]6F5)4]-Organic boron salt containing negative ion [1,4- (C)6F5)3BC6F4B(C6F5)3]2-Organic boron salt of negative ion, B (C)6F5)3And 1,4- (C)6F5)2BC6F4B(C6F5)2One or more of;
the main group metal alkyl reagent is selected from one or more of the group consisting of alumoxane, aluminum alkyl, zinc alkyl, and magnesium alkyl reagents. In the present invention, the aluminum alkyl is preferably selected from one or more of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisobutylaluminum, triisopropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum hydride and diisobutylaluminum hydride; the aluminoxane is selected from one or more of Methylaluminoxane (MAO), dried aluminoxane (DMAO), and modified aluminoxane (MMAO). The zinc alkyl is preferably diethyl zinc; the alkyl magnesium is preferably selected from one or more of diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium and dibutyl magnesium.
The invention provides a method for catalyzing olefin polymerization, which comprises the following steps:
under the anhydrous and anaerobic conditions, olefin monomers are subjected to homopolymerization or copolymerization reaction under the catalysis of the binuclear rare earth catalyst composition in the technical scheme.
In the invention, the molar ratio of the olefin monomer to the binuclear rare earth catalyst of the formula I in the binuclear rare earth catalyst composition is (50-1000000): 1, preferably (1000-500000): 1, more preferably (5000-100000): 1, and most preferably (10000-100000): 1.
In the invention, the temperature of the homopolymerization or copolymerization reaction is preferably 0-160 ℃, more preferably 20-140 ℃, most preferably 40-120 ℃, and most preferably 50-120 ℃; the time is preferably 1min to 100h, more preferably 1min to 72h, most preferably 1min to 48h, most preferably 2min to 12 h.
In specific embodiments of the invention, the temperature of the polymerization is room temperature, 80 ℃, 40 ℃, 140 ℃, or 25 ℃; the time is 1h, 20min, 2min, 40min, 1min, 30min, 5min, 60min or 15 min. The olefin is selected from the ternary copolymerization of ethylene, propylene and isoprene; or ethylene and dicyclopentadiene; or copolymerizing ethylene and norborneol; or styrene syndiotactic homopolymerization; or ethylene copolymerized with isoprene; or ethylene homopolymerization; or ethylene copolymerized with hexene-1; or octene-1 copolymerized with ethylene; or p-methoxystyrene and ethylene are copolymerized; or styrene and ethylene.
The olefin monomer is preferably selected from one or more of ethylene, alpha-olefin, styrene monomer, conjugated diene monomer, cyclic olefin monomer and non-conjugated diene monomer; more preferably one or more selected from the group consisting of ethylene, propylene, butene-1, hexene-1, octene-1, dicyclopentadiene, norbornene, styrene, p-methylstyrene, p-methoxystyrene, m-methoxystyrene, o-methoxystyrene, 1, 3-butadiene, isoprene, 1, 3-pentadiene, 2, 3-dimethyl-1, 3-butadiene, β -myrcene and ocimene. The polymerization of the olefin monomer may be homopolymerization of each of the above monomers or copolymerization of two or more of the above monomers. In the present invention, the gas pressure of the olefin at the time of the homopolymerization or copolymerization is not less than 0MPa, preferably 0.1 to 10.0MPa, more preferably 0.1 to 5.0MPa, and most preferably 0.2 to 1.0 MPa.
The above polymerization may be bulk polymerization or polymerization in an organic solvent; the organic solvent used for the olefin polymerization according to the present invention is not particularly limited, and is preferably one or a mixture of saturated alkanes, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and cycloalkanes. One or more of n-hexane, decalin, cyclohexane, petroleum ether, benzene, toluene and xylene are preferably used.
The invention provides a binuclear rare earth catalyst for olefin polymerization, which has a structure shown in a formula I; compared with a corresponding mononuclear rare earth metal catalyst or a cyclopentadienyl binuclear rare earth catalyst with a long-chain group and a rigid group bridged, the binuclear rare earth catalyst provided by the invention shows a remarkable bimetal synergistic effect in the process of catalyzing olefin polymerization.
Drawings
FIG. 1 shows the preparation of complex 1 according to catalyst example 11HNMR spectrogram (C)6D6)；
FIG. 2 shows the preparation of complex 2 according to catalyst example 21HNMR spectrogram (C)6D6)；
FIG. 3 shows the preparation of complex 3 in catalyst example 31HNMR spectrogram (C)6D6)；
In FIG. 4, (a) shows the NMR spectrum of the copolymer obtained in polymerization example 5 and (b) shows the NMR spectrum of the copolymer obtained in comparative example 1.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the binuclear rare earth catalyst and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Catalyst example 1
To a Schlenk flask containing a solution of 2mmol of ligand 1 in tetrahydrofuran (10mL) was slowly dropped a solution of 4mmol of butyllithium in n-hexane at-30 ℃ under anhydrous and oxygen-free conditions. In addition, 4 mmoleSc (CH) was charged at room temperature2SiMe3)3(THF)2To a Schlenk flask containing a tetrahydrofuran (4mL) solution, 4mmol of [ Et ] was slowly dropped3NH][BPh4]In tetrahydrofuran (5 mL). Subsequently, the two reaction systems were allowed to react at room temperature for 2 hours. Then the lithium of ligand 1The salt solution is poured into the alkyl scandium reaction system (Sc (CH)2SiMe3)2(BPh4)(THF)n) The reaction was further stirred at room temperature for 30 minutes. Finally, all solvents were removed under reduced pressure in vacuo, extracted with 20mL of toluene, filtered and the filtrate collected. After the filtrate was concentrated, it was left to stand in a refrigerator at-30 ℃ for crystallization, and the yield of the complex 1 was 70%.
Catalyst example 2
The procedure is as in example 1, using ligand 2 and the corresponding rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 2 in 72% yield.
Catalyst example 3
The procedure is as in example 1, using ligand 3 and the corresponding rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 3 in 76% yield.
Catalyst example 4
The procedure of example 1 is followed, using ligand 4 and rare earth cationic reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 4 in 69% yield.
Catalyst example 5
According toExample 1 method, ligand 5 and rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 5 in 79% yield.
Catalyst example 6
The procedure of example 1 is followed, using ligand 6 and rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 6 in 81% yield.
Catalyst example 7
The procedure of example 1 is followed, using ligand 7 and rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 7 in 75% yield.
Catalyst example 8
The procedure of example 1 was followed using ligand 8 and a rare earth cation reagent to provide complex 8 in 74% yield.
Catalyst example 9
The procedure of example 1 is followed, using ligand 9 and rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReaction gave complex 9 in 77% yield.
Catalyst example 10
The procedure of example 1 was followed using ligand 10 to react with a rare earth cation reagent to provide complex 10 in 82% yield.
Catalyst example 11
The procedure of example 1 is followed, using ligand 11 and rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReacting to obtain a complex 11 with the yield of 81%;
catalyst example 12
The procedure of example 1 is followed, using ligand 12 and rare earth cation reagent Sc (CH)2SiMe3)2(BPh4)(THF)nReacting to obtain a complex 12 with the yield of 78%;
polymerization example 1 syndiotactic homopolymerization of styrene
10 mu mol of complex 3 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, followed by addition of 200. mu. mol AliBu3And preparing a catalyst composition solution. Then the toluene solution of the catalyst composition is injected into a reaction bottle containing 200mmol of styrene monomer and 200mL of toluene solvent, after the reaction is carried out for 1 hour at room temperature, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction, and the syndiotactic polystyrene is preparedThe monomer conversion of the stereopolystyrene was 100%. Its regular tacticity rrrr>99 percent. Molecular weight Mn＝67.4×104g/mol, molecular weight distribution Mw/Mn＝2.12。Tm＝271℃。
Polymerization example 2: syndiotactic selective copolymerization of styrene and ethylene
10 mu mol of complex 5 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, followed by addition of 200. mu. mol AliBu3And preparing a catalyst composition solution. Then the toluene solution of the catalyst composition is injected into a reaction bottle containing 200mmol of styrene monomer, 200mL of toluene solvent and ethylene atmosphere, the reaction is carried out for 20 minutes under 4bar ethylene pressure and room temperature, and then ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction. 14.9g of a syndiotactic ethylene-styrene copolymer was obtained. Its molecular weight Mn＝60.3×104g/mol, molecular weight distribution Mw/Mn＝1.92。Tm231 ℃. The content of styrene structural units was 65 mol%.
Polymerization example 3: copolymerization of p-methoxystyrene with ethylene
10 mu mol of complex 5 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, followed by the addition of 50. mu. mol AliBu3And preparing a catalyst composition solution. Then the catalyst composition toluene solution is injected into a reaction bottle containing 5mmol of p-methoxy styrene monomer, 17.5mL of toluene solvent and ethylene atmosphere, the reaction is carried out for 2 minutes under 4bar ethylene pressure and 80 ℃, and then ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction. 0.2g of an ethylene-p-methoxystyrene copolymer was obtained. Its molecular weight Mn＝49.0×104g/mol, molecular weight distribution Mw/Mn＝1.74。Tm127.5 ℃. The content of p-methoxystyrene structural units was 2.7 mol%.
Polymerization example 4: copolymerization of octene-1 with ethylene
Under the conditions of no water and no oxygen, 10 mumol of complex 7 with 20. mu. mol [ Ph ]3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the catalyst composition toluene solution is injected into a reaction bottle containing 40mmol octene-1 monomer and 42.5mL toluene solvent, ethylene atmosphere, the reaction is carried out for 40 minutes under 1bar ethylene pressure and 40 ℃, and then ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction. 2.2g of an ethylene-octene copolymer was obtained. Its molecular weight Mn＝1.49×104g/mol, molecular weight distribution Mw/Mn2.4. The content of octene-1 structural unit was 16.5 mol%.
Polymerization example 5: copolymerization of hexene-1 with ethylene
10 mu mol of complex 3 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the catalyst composition toluene solution was injected into a reaction flask containing 80mmol hexene-1 monomer and 42.5mL toluene solvent in ethylene atmosphere, the reaction was carried out under 1bar ethylene pressure at 40 ℃ for 40 minutes, and then acidified ethanol with hydrochloric acid was added to terminate the polymerization reaction. 2.3g of an ethylene-hexene copolymer was obtained. Its molecular weight Mn＝1.52×104g/mol, molecular weight distribution Mw/Mn2.10. The hexene-1 structural unit content was 28.9 mol%.
Polymerization example 6: homopolymerization of ethylene
10 mu mol of complex 3 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. The toluene solution of the catalyst composition was then poured into a reaction flask containing 200mL of toluene solvent, the reaction was carried out under 4bar ethylene pressure at 140 ℃ for 1 minute, and then acidified ethanol with hydrochloric acid was added to terminate the polymerization. 1.8g of polyethylene was obtained. Its molecular weight Mw＝122.0×104g/mol, molecular weight distribution Mw/Mn＝2.63。
Polymerization example 7: homopolymerization of ethylene
10 mu mol of complex 5 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the catalyst composition toluene solution was poured into a reaction flask containing 1.5L of n-hexane solvent, the reaction was carried out under an ethylene pressure of 13bar at 40 ℃ for 30 minutes, and then ethanol acidified with hydrochloric acid was added to terminate the polymerization reaction. 79g of polyethylene was obtained. Its molecular weight Mw＝146×104g/mol, molecular weight distribution Mw/Mn＝2.04。
Polymerization example 8: homopolymerization of ethylene
10 mu mol of complex 3 is reacted with 60 mu mol DMAO in 2.5mL toluene at room temperature for 20min under anhydrous and oxygen-free conditions, and then 100 mu mol Al is addediBu3And preparing a catalyst composition solution. The toluene solution of the catalyst composition was then poured into a reaction flask containing 1.5L of toluene solvent, the reaction was carried out under an ethylene pressure of 13bar at 25 ℃ for 30 minutes, and then acidified ethanol with hydrochloric acid was added to terminate the polymerization reaction. 22g of polyethylene was obtained. Its molecular weight Mw＝156×104g/mol, molecular weight distribution Mw/Mn＝2.03。
Polymerization example 9: copolymerization of ethylene and isoprene
10 mu mol of complex 10 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the toluene solution of the catalyst composition was poured into a reaction flask containing 50mmol of isoprene and 50mL of toluene solvent, and after the reaction was carried out under an ethylene pressure of 1bar and at 25 ℃ for 5 minutes, ethanol acidified with hydrochloric acid was added to terminate the polymerization reaction. 0.8g of polyethylene was obtained. Its molecular weight Mn＝15.4×104g/mol, molecular weight distribution Mw/Mn1.62. With an isoprene content of 43 mol% and no polyethylene segments observed on the DSC curveMelting peak.
Polymerization example 10: syndiotactic homopolymerization of styrene
10 mu mol of complex 12 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 120min, followed by addition of 200. mu. mol AliBu3And preparing a catalyst composition solution. Then the toluene solution of the catalyst composition is injected into a reaction bottle containing 200mmol of styrene monomer and 200mL of toluene solvent, after the reaction is carried out for 1 hour at room temperature, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction, and the syndiotactic polystyrene is prepared, wherein the monomer conversion rate is 100%. Its regular tacticity rrrr>99 percent; molecular weight Mn＝57.4×104g/mol; molecular weight distribution Mw/Mn＝2.05；Tm＝270℃。
Polymerization example 11: copolymerization of ethylene with norbornene
10 mu mol of complex 10 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, and then 400. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the catalyst composition toluene solution was injected into a reaction flask containing 100mmol of norbornene and 100mL of toluene solvent, the reaction was carried out under 2bar ethylene pressure at 40 ℃ for 5 minutes, and then ethanol acidified with hydrochloric acid was added to terminate the polymerization reaction, to obtain 5.6g of ethylene-norbornene copolymer. The norbornene content was 43.5 mol%; molecular weight Mn＝15.4×104g/mol, molecular weight distribution Mw/Mn＝1.96；Tg＝101℃。
Polymerization example 12: copolymerization of ethylene with dicyclopentadiene
10 mu mol of complex 10 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, and then 400. mu. mol of Al was addediBu3And preparing a catalyst composition solution. The toluene solution of the catalyst composition was then injected into a reactor containing 60mmol of dicyclopentadiene and 30mL of toluene solventAfter the reaction was carried out in a flask under an ethylene pressure of 1bar at 40 ℃ for 5 minutes, the polymerization was terminated by adding ethanol acidified with hydrochloric acid. 2.9g of an ethylene-dicyclopentadiene copolymer was obtained. The dicyclopentadiene content was 34.2 mol%, molecular weight Mn＝14.5×104g/mol, molecular weight distribution Mw/Mn＝2.05；Tg＝124℃。
Polymerization example 13: ethylene, propylene and isoprene terpolymer
10 mu mol of complex 10 and 20 mu mol of [ Ph ] are mixed under anhydrous and oxygen-free conditions3C][B(C6F5)4]The reaction was carried out in 5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the toluene solution of the catalyst composition was poured into a reaction flask containing 40mmol of isoprene and 200mL of toluene solvent, and after the reaction was carried out at 25 ℃ under 4bar ethylene pressure for 15 minutes, ethanol acidified with hydrochloric acid was added to terminate the polymerization reaction. 4.8g of a copolymer was obtained. Its molecular weight Mn＝12.4×104g/mol, molecular weight distribution Mw/Mn＝1.47，TgAt-51 deg.C, the isoprene content was 26 mol%, the ethylene content was 48 mol%, and the propylene content was 26 mol%.
Comparative example 1
Under the anhydrous and oxygen-free conditions, 20 mu mol of mononuclear rare earth catalyst complex 13 and 20 mu mol of [ Ph ]3C][B(C6F5)4]The reaction was carried out in 2.5mL of toluene at room temperature for 20min, and then 100. mu. mol of Al was addediBu3And preparing a catalyst composition solution. Then the catalyst composition toluene solution was injected into a reaction flask containing 80mmol hexene-1 monomer and 42.5mL toluene solvent in ethylene atmosphere, the reaction was carried out under 1bar ethylene pressure at 40 ℃ for 40 minutes, and then acidified ethanol with hydrochloric acid was added to terminate the polymerization reaction. 1.3g of an ethylene-hexene copolymer was obtained. Its molecular weight Mn＝0.81×104g/mol, molecular weight distribution Mw/Mn2.00 percent; the content of hexene-1 structural units was 16.2 mol%.
As can be seen from the above examples, the present invention provides a binuclear rare earth catalyst for olefin polymerization, which has a structure of formula I; compared with a corresponding mononuclear rare earth metal catalyst or a cyclopentadienyl binuclear rare earth catalyst with a long-chain group and a rigid group bridged, the binuclear rare earth catalyst provided by the invention shows a remarkable bimetal synergistic effect in the process of catalyzing olefin polymerization.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A binuclear rare earth catalyst for olefin polymerization has a structure of formula I:
the Cp1 and Cp2 are independently selected from substituted or unsubstituted cyclopentadiene groups, substituted or unsubstituted indene groups and substituted or unsubstituted fluorene groups;
r is selected from a single atom bridging group or-CH2CH2-；
The X1 and X2 are independently selected from one or more of alkyl with 1-16 carbon atoms, silyl with 4-16 carbon atoms, amido with 2-16 carbon atoms, silicon amido with 4-20 carbon atoms, arylamine with 6-20 carbon atoms, allyl with 3-10 carbon atoms, benzyl with 7-20 carbon atoms, boron tetrahydride, tetramethylaluminum and hydrogen;
the Ln is selected from scandium, yttrium or lanthanide;
l is neutral Lewis base tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, pyridine or substituted pyridine;
and the value of w is 0-3.
2. The dinuclear rare earth catalyst of claim 1, wherein Cp1 and Cp2 are independently selected from the group consisting of fluorenyl, 2, 7-di-t-butylfluorenyl, benzofluorenyl, bisbenzofluorenyl, cycloalkane-substituted fluorenyl, indenyl, 4, 7-dimethylindenyl, 2-methylindenyl, cyclopentadienyl, tetramethylcyclopentadienyl, 1-t-butyl-2-trimethylsilylcyclopentadienyl, 1, 3-bis (trimethylsilyl) cyclopentadienyl, methylcyclopentadienyl, t-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, 1, 2-dimethylcyclopentadienyl, 1, 3-dimethylcyclopentadienyl, 1, 2-diethylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, n-octylcyclopentadienyl, tetrahydroindenyl, indenyl, tetramethylcyclopentadienyl, 1-t-butylcyclopentadienyl, 2-dimethylcyclopentadienyl, and mixtures thereof, Propylcyclopentadienyl, octahydrofluorenyl, phenylcyclopentadienyl, 1, 2-diphenylcyclopentadienyl, cyclohexylcyclopentadienyl or 2, 2' -diphenylcyclopentadienyl.
3. The dinuclear rare earth catalyst of claim 1 wherein said monoatomic bridging group is selected from CH2 2-、CMe2 2-、SiMe2 2-、SiHMe2-、SiPhMe2-、PMe2-、BMe2-Or SnMe2 2-。
4. The dinuclear rare earth catalyst of claim 1 wherein the Ln is selected from one or more of scandium, yttrium, lutetium, erbium, holmium, dysprosium, thulium, ytterbium, gadolinium, neodymium, and lanthanum.
5. The binuclear rare earth catalyst according to claim 1, wherein said binuclear rare earth catalyst is specifically selected from any one of complexes 1 to 12:
6. a method for preparing the binuclear rare earth catalyst according to any one of claims 1 to 5, comprising the following steps:
dissolving a ligand with Cp1-R-Cp2 in an organic solvent under anhydrous and oxygen-free conditions to obtain a ligand solution;
reacting the ligand solution with an alkali metal reagent with twice molar weight to obtain an alkali metal salt of the ligand;
mixing an alkali metal salt of the ligand with twice the molar amount of YLNX1X2L(w)Reacting to obtain a binuclear rare earth catalyst with a structure shown in formula I;
the YLnX1X2L(w)Wherein Y is selected from halogen, BH4 –、[(C6H5)4B]–Or [ (C)6F5)4B]–。
7. A dinuclear rare earth catalyst composition for catalyzing olefin polymerization comprises the following substances in a mass ratio of 1: (0-4): (0-1000) a binuclear rare earth catalyst, an organic boron salt and a main group metal alkyl reagent;
the binuclear rare earth catalyst is the binuclear rare earth catalyst according to any one of claims 1 to 5 or the binuclear rare earth catalyst prepared by the preparation method according to claim 6.
8. The dinuclear rare earth catalyst composition according to claim 7, wherein said organoboron salt is selected from the group consisting of [ B (C) and [ B (C) ]6F5)4]–Organic boron salt containing negative ion [1,4- (C)6F5)3BC6F4B(C6F5)3]2–Organic boron salt of negative ion, B (C)6F5)3And 1,4- (C)6F5)2BC6F4B(C6F5)2One or more of;
the main group metal alkyl reagent is selected from one or more of the group consisting of alumoxane, aluminum alkyl, zinc alkyl, and magnesium alkyl reagents.
9. A process for catalyzing the polymerization of olefins comprising the steps of:
homopolymerization or copolymerization of olefin monomers under the catalysis of the binuclear rare earth catalyst composition according to any one of claims 7 to 8 under anhydrous and oxygen-free conditions.
10. The method according to claim 9, wherein the temperature of the homopolymerization or copolymerization reaction is 0-160 ℃ and the time is 1 min-100 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110643812.8A CN113307896B (en) | 2021-06-09 | 2021-06-09 | Binuclear rare earth catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110643812.8A CN113307896B (en) | 2021-06-09 | 2021-06-09 | Binuclear rare earth catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113307896A true CN113307896A (en) | 2021-08-27 |
| CN113307896B CN113307896B (en) | 2022-11-01 |
Family
ID=77378333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110643812.8A Active CN113307896B (en) | 2021-06-09 | 2021-06-09 | Binuclear rare earth catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113307896B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113968926A (en) * | 2021-10-29 | 2022-01-25 | 大连理工大学 | Ethylene/alpha-olefin/functionalized styrene derivative terpolymer and preparation method thereof |
| CN114874258A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院长春应用化学研究所 | Binuclear cyclopentadienyl four-group metal catalyst for polymerization of styrene and its derivative, its preparation method, composition and application |
| CN114891137A (en) * | 2022-06-06 | 2022-08-12 | 中国科学院长春应用化学研究所 | Binuclear four-group metal catalyst for olefin polymerization, and preparation method, composition and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098608A (en) * | 2013-04-03 | 2014-10-15 | 中国石油化工股份有限公司 | Scandium metallocene catalyst precursor, preparation method and application thereof, and preparation method for copolymer |
-
2021
- 2021-06-09 CN CN202110643812.8A patent/CN113307896B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098608A (en) * | 2013-04-03 | 2014-10-15 | 中国石油化工股份有限公司 | Scandium metallocene catalyst precursor, preparation method and application thereof, and preparation method for copolymer |
Non-Patent Citations (2)
| Title |
|---|
| 孙俊全等: "桥联稀土异双核Mt-Sm(Mt=Zr,Ti)茂金属配合物催化乙烯聚合研究", 《浙江大学学报(工学版)》 * |
| 张志红等: "新型硅桥联Ti-Sm,Zr-Sm异核茂催化乙烯聚合", 《浙江大学学报(工学版)》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113968926A (en) * | 2021-10-29 | 2022-01-25 | 大连理工大学 | Ethylene/alpha-olefin/functionalized styrene derivative terpolymer and preparation method thereof |
| CN114874258A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院长春应用化学研究所 | Binuclear cyclopentadienyl four-group metal catalyst for polymerization of styrene and its derivative, its preparation method, composition and application |
| CN114891137A (en) * | 2022-06-06 | 2022-08-12 | 中国科学院长春应用化学研究所 | Binuclear four-group metal catalyst for olefin polymerization, and preparation method, composition and application thereof |
| CN114891137B (en) * | 2022-06-06 | 2024-04-09 | 中国科学院长春应用化学研究所 | Binuclear group IV metal catalyst for olefin polymerization, and preparation method, composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113307896B (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113307896B (en) | Binuclear rare earth catalyst and preparation method and application thereof | |
| KR100449196B1 (en) | Carrier for olefin polymerization catalyst, olefin polymerization catalyst and process for producing olefin polymer | |
| CN103025770B (en) | Catalyst component for the polymerization of olefins having a guanidinate ligand | |
| Atiqullah et al. | Synthesis of functional polyolefins using metallocenes: a comprehensive review | |
| EP0955305B1 (en) | Metallocene compound, and process for preparing polyolefin by using it | |
| CN108530572B (en) | Preparation method of ethylene-styrene derivative copolymer | |
| JP2000513761A (en) | Method for producing functional polyolefin | |
| CN111116801B (en) | Preparation method of olefin-unsaturated carboxylic acid copolymer | |
| CN107312115B (en) | Bis-indole rare earth metal catalyst, preparation method and application | |
| WO1999014247A1 (en) | Catalysts for the polymerization of olefins, process for the production of olefin polymers, and processes for the production of styrene polymers | |
| EP1114069A1 (en) | A method for preparing a supported catalyst system and its use in a polymerization process | |
| JP3473955B2 (en) | Catalyst for producing vinyl polymer and method for producing vinyl aromatic polymer | |
| KR101421309B1 (en) | Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins | |
| CN114891137B (en) | Binuclear group IV metal catalyst for olefin polymerization, and preparation method, composition and application thereof | |
| CN107141391B (en) | Ethylene-polar styrene quasi-random copolymer and preparation method thereof | |
| JP3572339B2 (en) | Catalyst for producing olefin polymer, method for producing the same, and method for producing olefin polymer using the same | |
| CN112552429B (en) | Supported metallocene catalyst and preparation method and application thereof | |
| CN113683716B (en) | Ethylene polymerization catalyst, preparation method thereof and preparation method of ethylene-isobutylene copolymer | |
| CN114933665B (en) | Heterometal binuclear catalyst and preparation method, composition and application thereof | |
| CN114874258A (en) | Binuclear cyclopentadienyl four-group metal catalyst for polymerization of styrene and its derivative, its preparation method, composition and application | |
| JP6539337B2 (en) | Functionalized high syndiotactic polystyrene and method for producing the same | |
| CN112851841B (en) | Preparation method of polyalkyl vinyl ether | |
| JP2000264913A (en) | Catalyst for olefin polymerization and production of olefin polymer | |
| JP2006056849A (en) | Metallocene compound, alpha olefin polymerization catalyst component using the same, alpha olefin polymerization catalyst, and method for producing alpha olefin polymer | |
| CN118324823A (en) | Heterofluorene rare earth compound, preparation method thereof and application thereof in olefin polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |