CN104860999A - Dinuclear metallocene compound used for olefin polymerization, and preparation method and application thereof - Google Patents

Dinuclear metallocene compound used for olefin polymerization, and preparation method and application thereof Download PDF

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Publication number
CN104860999A
CN104860999A CN201510165277.4A CN201510165277A CN104860999A CN 104860999 A CN104860999 A CN 104860999A CN 201510165277 A CN201510165277 A CN 201510165277A CN 104860999 A CN104860999 A CN 104860999A
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alpha
reaction
compound
olefin
under
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Inventor
许胜�
朱玉玲
赵妍
米普科
义建军
王斯晗
杨楠
梁春超
王建伟
吕中文
张翠
许鹄飞
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East China University of Science and Technology
China Petroleum and Natural Gas Co Ltd
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East China University of Science and Technology
China Petroleum and Natural Gas Co Ltd
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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
    • 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
    • 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

Abstract

The invention discloses a p-dibenzyl bridged dinuclear metallocene compound and a preparation method thereof, and application for the p-dibenzyl bridged dinuclear metallocene compound in catalyzing of ethylene polymerization and copolymerization of ethylene and alpha-olefin. The preparation method comprises the following steps: subjecting fulvene and benzene to lithiation reaction and then carrying out coupling by using p-cyclite so as to obtain a ligand; after lithiation, carrying out reaction with CpMCl3 so as to obtain a catalyst; using methylaluminoxane (MAO) as a cocatalyst and catalyzing ethylene polymerization so as to obtain a polymerization product which is high-molecular-weight unbranched polyethylene; and catalyzing copolymerization of ethylene and alpha-olefin so as to obtain a copolymer, wherein the alpha-olefin in the obtained copolymer has a high insertion rate. The catalyst provided by the invention has the following significant advantages: the catalyst has simple synthesis process, high alpha-olefin content in the copolymer; meanwhile, the catalyst has a structure shown as in the following general formula.

Description

A kind of for olefinic polymerization dinuclear metallocene compounds and preparation method thereof and application
Technical field
The present invention relates to and be a kind ofly applied to Bibridge binucleus cyclopentadienyl metal compound of catalyzed ethylene polymerization and copolymerization and preparation method thereof and application, this compounds is applied to catalyzed ethylene polymerization and ethene and alpha-olefin copolymer, has active high, feature that alpha-olefin insertion rate is high.
Background technology
The production method of current LLDPE mainly carries out copolymerization with ethene and a small amount of alpha-olefin under catalyst for copolymerization effect, in Polyethylene Chain, side chain is introduced with this, catalyzer used mainly contains restriction configuration metallocene catalyst (CGC), is DOW company the earliest [1]exploitation CpSiN type CGC, East China University of Science in recent years [2]exploitation with sp 3the CGC of carbon bridging, its feature is shown in following structural formula:
DOW CN1049849A EXXON CN1328580A China reason CN102190687A
The catalyst system that above-mentioned CGC and organoaluminum and boron compound form is used for ethene/1-octene copolymer and closes, a kind of narrow molecular weight distribution can be obtained, comonomer insertion is high and adjustable, copolymer components distribution is homogeneous, have the new copolymer of long-chain branched polyethylene chain structure, alpha-olefin insertion rate is 5 ~ 8%mol.Use dinuclear catalyst to carry out ethylene/alpha-olefin to carry out copolymerization and also have report, East China University of Science [3-5]develop bis-silicon-bridged dinuclear metallocene catalyzer, such compound structure feature is as follows:
Reason CN100556910A China of China reason CN101638422A
Above-claimed cpd obtains the content range 2 ~ 6%mol of alpha-olefin in multipolymer, not yet reaches the level of CGC, and multipolymer can't use as elastomerics.The people such as U.S. Tobin in recent years [6]prepared two CGC compound to investigate the nuclear effect between two atoms metals, this compounds can the alpha-olefin copolymer of effectively catalyzed ethylene and small-molecular-weight, when abutment synthesis binuclear compound with rigidity more [7-9]copolymerized ability greatly strengthens.Spain scholar [10]synthesize bicentric CGC compound, but the report do not applied about its olefinic polymerization.
Above-mentioned catalyst preparing route is long, and yield is low, and the promotor used is expensive, is not too applicable to industrial application.
Reference
1. G.A. Luinstra, J.H. Teuben, J. Chem. Soc.-Chem. Commun. 1990，1470。
2. meter Pu Ke, Kong Xiaojuan, Xu Sheng, Zhu Yuling, appoints winter jasmine, Journal of Molecular Catalysis, 2012,26(6): 493.
3. Sheng Xu, Junji Jia, Jiling Huang, J. Polym. Sci: Part A: Polym Chem., 2007，45：4901。
4. Puke Mi, Sheng Xu, Liangduan Qu, Zhang Deshun, Chen Qian, Wang Sihan, J. APPL. POLYM. SCI. 2011，121：21。
5. Sheng Xu, Jiling Huang, J. APPL. POLYM. SCI. 2013, 130（4）：2891。
6. Liting Li，Matthew V. Metz， Hongbo Li，Ming-Chou Chen, Tobin J. Marks，Louise Liable-Sands, Arnold L. Rheingold，J. AM. CHEM. SOC. 2002, 124, 12725。
7. Salata, M. R.; Marks, T. J. J. Am. Chem. Soc. 2008, 130, 12。
8. Salata, M. R.; Marks, T. J. Macromolecules 2009, 42, 1920。
9. Hongbo Li, Liting Li,Tobin J. Marks，Angew. Chem. Int. Ed. 2004, 43, 4937。
10. Cristina Paniagua, Marta E. G. Mosquera, Tomás Cuenca,Gerardo Jimánez，Organometallics 2011, 30, 2993。
Summary of the invention
In order to solve the problem, obtain alpha-olefin and insert the stronger metallocene catalyst of ability, one of the object of the invention is open a kind of dinuclear metallocene compounds, aromatic group is introduced in dual-core architecture, greatly facilitate copolymerized ability, can as high reactivity ethylene/alpha-olefin catalyst for copolymerization, this patent has that synthetic route is short, synthesis technique simple, product yield advantages of higher, can regulate compound for catalysis character by modifying benzene ring substituents.
For achieving the above object, the invention provides a kind of metallocene compound of double-core, its structure is such as formula shown in I:
formula 1
Wherein: R 1be selected from H, C1-C4 alkyl, methoxyl group, R 2be selected from H, C1-C4 alkyl, R 3, R 4be selected from methyl, ethyl, pentamethylene, M=Ti, Zr.
According to the specific embodiment of the present invention, preferably, the compound of the titanium of above-mentioned double-core includes, but are not limited to:
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)CMe 2(C 6H 5) TiCl 2(η 5-C 5H 5)] 2、
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)CMe 2(C 6H 5) ZrCl 2(η 5-C 5H 5)] 2、
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)CMe 2(4-MeC 6H 4) TiCl 2(η 5-C 5H 5)] 2、
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)CMe 2(4-MeC 6H 4) ZrCl 2(η 5-C 5H 5)] 2、
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)CMe 2(C 6H 5) TiCl 2(η 5-MeC 5H 4)] 2、
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)CMe 2(C 6H 5) ZrCl 2(η 5-MeC 5H 4)] 2、
[μ,μ-(1,4-(CH 2) 2(C 6H 4)][(η 5-C 5H 3)C(CH 2) 5(C 6H 5) TiCl 2(η 5-C 5H 5)] 2、。
Two of the object of the invention is to provide a kind of preparation method of compound of titanium of above-mentioned double-core, and it comprises the following steps:
(1) the present invention is raw material with 6,6-dimethyl fulvene, with to dibenzyl coupling obtains ligand L after reacting with benzene lithium, the structure of described ligand L as shown in Equation 2,
formula 2,
Wherein: R 1be selected from H, C1-C4 alkyl, methoxyl group, R 2be selected from H, C1-C4 alkyl, R 3, R 4be selected from methyl, ethyl, pentamethylene.
(2) ligand L and CpTiCl is made 3or CpZrCl 3dME reaction is to prepare described binuclear compound
In above-mentioned preparation method, preferably, step (1) comprising:
Under argon shield; under-30-25 ° of C condition, fulvene solution is slowly added dropwise to benzene lithium solution; fulvene and benzene lithium amount of substance ratio control are at 0.9:1 to 1.1:1; react filtration after 2-10 hour and obtain white solid; dissolve with tetrahydrofuran (THF); slowly add dibenzyl bromine solutions under-30-25 ° of C condition, reaction is spent the night.Reaction terminates, hydrolysis, separatory, and aqueous phase ether 2 × 30mL extracts, and merges organic phase, anhydrous magnesium sulfate drying, and filter, removal of solvent under reduced pressure, chromatography over CC, obtains dark red oil, is ligand L.
In above-mentioned preparation method, preferably, step (2) comprising: with normal hexane solvent, get the ligand L that step (1) obtains, under-78 DEG C of-30 DEG C of conditions, slowly instill the solution of the butyllithium of 2 times amount, 30 DEG C of reaction 6-15 hour are warming up to after dropwising, cross and filter solvent, the solid obtained adds tetrahydrofuran (THF) or toluene, slowly adds CpMCl under-78-25 ° of C condition 3, reaction is spent the night, and gets supernatant liquid and concentrates, obtain described binuclear compound after gained solid recrystallization.
Three of the object of the invention is to provide the application of above-mentioned binuclear compound catalyzed ethylene polymerization, carry out in accordance with the following methods: with toluene or heptane for solvent, add promotor MAO, add the toluene solution of above-claimed cpd, maintenance ethylene pressure is 0.1-1.5MPa, polymerization reaction time 0.5-2.0 hour at temperature of reaction 0 DEG C-50 DEG C, obtains the unbranched polyethylene of high molecular.
Four of the object of the invention is to provide the application that above-claimed cpd closes at catalyzed ethylene and alpha-olefin copolymer, carry out in accordance with the following methods: with toluene or heptane for solvent, add promotor MAO, alpha-olefin, add the toluene solution of above-claimed cpd, maintain ethylene pressure and be greater than 0.1-1.0 MPa, reaction times 0.5-2.0 hour at temperature of reaction 0 DEG C-50 DEG C, obtain polymkeric substance, wherein alpha-olefin insertion rate is more than 8.0mol%.
In sum, the synthetic route of binuclear compound provided by the invention is short, and preparation technology is simple, and product yield is high, and separation and purification is easy, has excellent copolymerized ability, and in polymkeric substance, alpha-olefin content exceedes CGC catalyzer under equal conditions.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
embodiment 1
Complex compound 1[μ, μ-(Isosorbide-5-Nitrae-(CH 2) 2(C 6h 4)] [(η 5-C 5h 3) CMe 2(C 6h 5) TiCl 2(η 5-C 5h 5))] 2synthesis
Complex compound 1synthetic route as follows:
Under argon shield; take 2.1g (0.025mol) benzene lithium in 200mL Schlenk bottle; be dissolved in 60mL tetrahydrofuran (THF); under cryosel bath; drip the 50mL tetrahydrofuran solution of 6,6-dimethyl fulvene 2.7g (0.0253mol), slowly adularescent precipitation produces; dropwise, rise to room temperature reaction 6h.Leave standstill, press filtration, solid ether 2 × 100mL washs, and drains solvent and obtains white solid powder PhC (Me) 2cpLi 3.8g, productive rate 79.2%.
Under argon shield, take 1.6g (8.4mmol) PhC (Me) 2cpLi is dissolved in 30mL tetrahydrofuran (THF), under cryosel bath, drops to 1.11g(4.2mmol) in cyclite 30mL tetrahydrofuran solution, dropwise, slowly rise to room temperature, reaction is spent the night.Reaction terminates, hydrolysis, separatory, and aqueous phase ether 2 × 30mL extracts, and merges organic phase, anhydrous magnesium sulfate drying, and filter, removal of solvent under reduced pressure, chromatography over CC, obtains dark red oil 2g, be ligand L, productive rate 50.6%. 1H NMR (400MHz, CDCl 3): δ = 7.29-7.03 (m, 14H), 5.74-6.35 (m, 3H), 3.57-3.72 (t, 4H), 2.84-2.93 (d, 3H), 2.62-2.73 (d, 2H), 1.50-1.56 (s, 6H), 1.23-1.28 (s, 6H). EIMS: m/z 470 (79) [M +], 455 (10) [M +－CH 3], 287 (56) [M +－2C 7H 8], 119 (100) [M +－C 6H 5C(Me) 2C 5H 4CH 2C 6H 4CH 2C 5H 4]
Take 1.13g(2.13mmol) lpart is dissolved in 60mL normal hexane, drips 2.0mol/L under-78 ° of C, the hexane solution of 2.13mL n-Butyl Lithium, and slowly adularescent muddiness occurs, dropwise and slowly heat up, room temperature reaction spends the night.Next day, reactant is white precipitate, and filter, solid normal hexane 2 × 50mL washs, and obtains the two lithium salts 1.1g of white, productive rate 95%.
Take part ltwo lithium salts 1.1g(2.28mmol), add 50mL toluene suspend, add 1.1g(4.6mmol under-78 ° of C) CpTiCl 3solid, room temperature reaction spends the night.Next day, reaction solution is scarlet turbid solution, leaves standstill, and filters the transparent red liquid in upper strata, concentrated, drips a small amount of normal hexane recrystallization.Occur red solid two days later, filter, solid is drained and is obtained red solid, and weigh 1.06g(1.14mmol), productive rate 50%.
1H NMR (400MHz, δ，CDCl 3): 1.69 (s, 12H), 3.98 (m, J= 4.4Hz, 4H), 6.16 (m, J= 3.2Hz, 2H), 6.25 (s, 5H), 6.42 (m, J= 1.2Hz, 2H), 6.52 (s, 5H), 6.58 (d, J= 5.2Hz, 2H), 7.08(m, 4H), 7.15-7.27 (m, J= 6.8Hz, 10H). 13C NMR (100.62MHz, δ, CDCl 3): 24.21, 25.48, 30.52, 33.54, 44.37, 118.55, 121.54, 125.45, 125.87, 126.63, 128.12, 137.71, 147.28, 149.75, 159.69. ESI-MS: m/z 834.1 (15) [M +], 651.2 (43) [M +-CpTiCl 2], 468.3 (100) [M +-2CpTiCl 2].
embodiment 2
Complex compound 1catalyzed ethylene polymerization
The 250mL polymeric kettle ethylene gas being equipped with magnetic stir bar replaces 3 times, add toluene successively, MAO (6.5mL, 1.5mol/L, Al/Ti=1000), finally add catalyzer (toluene solutions of 10 μm of ol), cumulative volume is 100mL, control temperature is 25 DEG C, and ethylene pressure is 0.2MPa, reaction 30min.Reaction end adds hydrochloric acid-ethanol (1:29) and stops, and filters, and by washing with alcohol twice, 50 ° of C vacuum-dryings to constant weight, calculating polymerization catalyst activity is 3.4 × 10 5g/mol Cath, 13C NMR characterizes, and polymkeric substance does not have side chain, Mn=59241, Mw=135339, MWD=2.28.
embodiment 3
Complex compound 1catalyzed ethylene and 1-hervene copolymer close
Poly-unit is with embodiment 2, add toluene successively, MAO (6.5mL, 1.5mol/L, Al/Ti=1000), the 1-hexene of 5mL, finally add catalyzer (toluene solutions of 10 μm of ol), cumulative volume is 100mL, and control temperature is 35 DEG C, ethylene pressure is 0.3MPa, reaction 30min.Reaction end adds hydrochloric acid-ethanol (1:29) and stops, and hold over night, filters, and polymkeric substance is by washing with alcohol to neutral, and dried in vacuo overnight under 30 DEG C of conditions, weigh quality, calculated activity is 1.5 × 10 5g/mol Cath, 13c NMR analytical results shows, 1-ahexene content 11.85mol% in polymkeric substance, Mn=30665g/mol, Mw=68488g/mol, molecular weight distribution MWD=2.23.
embodiment 4
Complex compound 2[μ, μ-(Isosorbide-5-Nitrae-(CH 2) 2(C 6h 4)] [(η 5-C 5h 3) CMe 2(C 6h 5) ZrCl 2(η 5-C 5h 5))] 2synthesis
The 2-in-1 one-tenth method of complex compound is synthesized with complex compound 1 in embodiment 1, with CpZrCl 3dME replaces CpTiCl 3.Light yellow solid 1.50g, yield 37%, 1h NMR (400MHz, CDCl 3): 1.73 (s, 12H), 3.90 (m, j=4.4Hz, 4H), 6.18 (m, j=3.2Hz, 2H), 6.27 (s, 5H), 6.40 (m, j=1.2Hz, 2H), 6.55 (s, 5H), 6.61 (d, j=5.2Hz, 2H), 7.12 (m, 4H), 7.16-7.29 (m, j=6.8Hz, 10H).
embodiment 5
Complex compound 2catalyzed ethylene polymerization
Poly-unit and treatment process are with embodiment 2.Calculated activity is 3.4 × 10 6g/mol Cath, 13c NMR analytical results shows, polymkeric substance is unbranched polyethylene, M η=1.9 × 10 5g/mol.
embodiment 6
Complex compound 2catalyzed ethylene and 1-hervene copolymer close
Polymerizing reactor and treating processes are with embodiment 3.Calculated activity is 6.2 × 10 6g/mol Cath, 13c NMR analytical results shows, 1-ahexene content 9.54mol% in polymkeric substance, M η=0.87 × 10 5g/mol.

Claims (5)

1. a dinuclear metallocene compounds, is characterized in that: structure as shown in Equation 1:
formula 1
Wherein: R 1be selected from H, C1-C4 alkyl, methoxyl group, R 2be selected from H, C1-C4 alkyl, R 3, R 4be selected from methyl, ethyl, pentamethylene, M=Ti, Zr.
2. a preparation method for compound according to claim 1, is characterized in that: following steps:
Fulvene and benzene lithium are reacted, then obtain ligand L with to the coupling of dibenzyl bromine, the structure of L as shown in Equation 2:
formula 2,
Wherein: R 1be selected from H, C1-C4 alkyl, methoxyl group, R 2be selected from H, C1-C4 alkyl, R 3, R 4be selected from methyl, ethyl, pentamethylene;
(2) after ligand L lithiumation with CpMCl 3be obtained by reacting described binuclear compound;
In above-mentioned preparation method; preferably; step (1) comprising: under argon shield; under-30-25 ° of C condition, fulvene solution is slowly added dropwise to benzene lithium solution; fulvene and benzene lithium amount of substance ratio control, at 0.9:1 to 1.1:1, are reacted filtration after 2-10 hour and are obtained white solid, dissolve with tetrahydrofuran (THF); slowly add dibenzyl bromine solutions under-30-25 ° of C condition, reaction is spent the night.
3. reaction terminates, hydrolysis, separatory, and aqueous phase ether 2 × 30mL extracts, and merges organic phase, anhydrous magnesium sulfate drying, and filter, removal of solvent under reduced pressure, chromatography over CC, obtains dark red oil, is ligand L;
In above-mentioned preparation method, preferably, step (2) comprising: take normal hexane as solvent, get the ligand L that step (1) obtains, under-78 DEG C of-30 DEG C of conditions, slowly instill the solution of the butyllithium of 2 times amount, 30 DEG C of reaction 6-15 hour are warming up to after dropwising, cross and filter solvent, the solid obtained adds tetrahydrofuran (THF) or toluene, slowly adds the CpMCl of 2 times under-78-25 ° of C condition 3, reaction is spent the night, and gets supernatant liquid and concentrates, obtain described binuclear compound after gained solid recrystallization.
4. compound for catalysis vinyl polymerization according to claim 1, obtains the unbranched polyethylene of high molecular.
5. compound for catalysis ethene according to claim 1 and alpha-olefin copolymer close, and it is characterized in that: in the product obtained, alpha-olefin insertion rate is more than 8.0mol%.
CN201510165277.4A 2015-04-09 2015-04-09 Dinuclear metallocene compound used for olefin polymerization, and preparation method and application thereof Pending CN104860999A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111741961A (en) * 2018-02-19 2020-10-02 埃克森美孚化学专利公司 Catalysts, catalyst systems, and methods of using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111741961A (en) * 2018-02-19 2020-10-02 埃克森美孚化学专利公司 Catalysts, catalyst systems, and methods of using the same
CN111741961B (en) * 2018-02-19 2024-01-12 埃克森美孚化学专利公司 Catalyst, catalyst system and method of using the same

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