PREPARATION OF BIMETALLIC CATALYST BASED ON ANTHRACENE FRAMEWORKS AND USE THEREOF IN OLEFIN HIGH TEMPERATURE SOLUTION POLYMERIZATION

Abstract

A preparation method of bimetallic catalysts based on anthracene frameworks and use thereof in olefin polymerization is reported. Anthrecene frameworks were introduced, heat resistance of the catalysts is improved, and by changing central metals and configurations of the frameworks, steric and electronic effects of the metal catalysts of this model can be adjusted and controlled conveniently, and polyolefin polymer materials of different structures and different properties can be prepared, the bimetallic catalyst can be used in ethylene homopolymerization for preparation of high density polyethylene, ethylene/1-octene copolymerization for preparation of polyolefin elastomers and ethylene/norbornene copolymerization for preparation of cycloolefin copolymers. The bimetallic catalyst based on anthracene frameworks can be used in olefin high temperature solution polymerization for preparing polyolefin elastomers and cycloolefin copolymers, the polyolefin elastomers obtained have molecular weights as high as M.sub.W=890 kg.Math.mol.sup.−1, and the cycloolefin copolymers have copolymerization monomer insertion rates as high as 45 mol %.

Claims

1. A bimetallic catalyst based on anthracene frameworks as shown in formula (I): ##STR00002## wherein, M is selected from titanium, zirconium and hafnium; and X is selected from methyl, chlorine and dimethylamino.

2. A preparation method of the bimetallic catalyst based on anthracene frameworks as defined in claim 1, comprising following steps: under a nitrogen atmosphere, adding Pd(OAc).sub.2 (89 mg, 0.4 mmol), dppf (0.456 g, 0.8 mmol), 1,8-dichrloroanthracene (1.24 g, 5 mmol), 2-anisidine (1.85 g, 15 mmol) and Cs.sub.2CO.sub.3 (4.78 g, 15 mmol) into a 200 mL two-neck flask, adding methylbenzene 50 mL, refluxing and reacting for 12-24 hours; adding water and ethyl acetate for extraction, removing water in an organic phase, pressurizing and removing solvents; purifying a product by column chromatography, wherein eluting reagents are petroleum ether and ethyl acetate with a volume ratio of 1˜20:1, and an organic ligand can be obtained; dissolving the organic ligand in a nonaqueous solvent, adding (NMe.sub.2).sub.4 2-3 molar equivalents, reacting for 12-24 hours; vacuumizing and removing solvents, washing with a poor solvent and obtaining the bimetallic catalyst based on anthracene frameworks.

3. The preparation method of the bimetallic catalyst based on anthracene frameworks as defined in claim 2, wherein the nonaqueous solvent is selected from benzene, methylbenzene, dimethylbenzene and n-hexane; and the poor solvent is selected from n-hexane, pentane, n-heptane and cyclohexane.

4. A method for conducting olefin polymerization reaction, wherein a catalyst used in the polymerization reaction is the bimetallic catalyst based on anthracene frameworks as defined in claim 1.

5. The method for conducting olefin polymerization reaction as defined in claim 4, wherein the olefin is any one or combination of ethylene, propylene, phenyl ethylene, 1-butylene, 1-hexylene, 1-octylene, norbornene, cyclohexene and TCD monomer.

6. The method for conducting olefin polymerization reaction as defined in claim 4, wherein the catalyst further comprises a cocatalyst, wherein the cocatalyst is any one or combination of tri(pentafluorophenyl) borane, trityl tetrakis(pentafluorophenyl)borate, aluminoxide, alkyl aluminum and aluminium alkyl chloride.

7. The method for conducting olefin polymerization reaction as defined in claim 6, wherein the aluminoxide comprises methyl aluminium oxane, ethylaluminoxane or isobutylaluminoxane; alkyl aluminium comprises trimethyl aluminium, triethylaluminium or tri-n-hexyl aluminum; and the aluminium alkyl chloride comprises aluminium diethyl monochloride, diethylaluminum sesquichloride or ethylaluminium dichloride.

8. The method for conducting olefin polymerization reaction as defined in claim 4, wherein polymerization temperature is 0-180° C., polymerization pressure 0.1-5 Mpa, polymerization solvent is any one or combination of methylbenzene, hexane and heptane.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0015] The sole figure is a crystal structural diagram of the ligand syn-Hf.sub.2.

EMBODIMENTS

[0016] Hereinafter the present invention will be further described with some embodiments, however, the present invention is not limited to the embodiments disclosed herein. The embodiments in the present invention can help those skilled in the art understand the present invention comprehensively.

[0017] Experimental methods used in the following embodiments are common methods unless indicated otherwise.

[0018] Hereinafter the present invention will be described with some embodiments.

[0019] Embodiment 1 preparation of composition syn-Hf.sub.2 Under nitrogen atmosphere, adding Pd(OAc).sub.2 (89 mg, 0.4 mmol), dppf (0.456 g, 0.8 mmol), 1,8-dichrloroanthracene (1.24 g, 5 mmol), 2-anisidine (1.85 g, 15 mmol) and Cs.sub.2CO.sub.3 (4.87 g, 15 mmol) into a 200 mL two-neck flask, adding methylbenzene 50 mL, and refluxing for 12 -24 hours. Adding water and ethyl acetate for extraction, removing water in an organic phase, pressurizing to remove the solvent; purifying a product by column chromatography, wherein eluting reagents are petroleum ether and ethyl acetate with a volume ratio of 1˜20:1, and organic ligand 1.42 g is obtained; taking the organic ligand (0.42 g, 1 mmol) and dissolving in a nonaqueous solution, adding Hf(NMe.sub.2).sub.4 2.2 mmol, reacting for 24 hours; depressurizing to remove the solvent, washing with n-hexane and obtaining bimetallic catalyst based on anthracene frameworks syn-Hf.sub.2 (0.93 g, 0.9 mmol, 90% yield). .sup.1H NMR(400 MHz, C.sub.6D.sub.6) δ 9.02 (s, 1 H), 8.45 (s, 1 H), 7,74 (d, J=8.5 Hz, 2 H), 7.50-7.28 (m, 2 H), 7.05 (d, J=6.7 Hz, 2 H), 6.73 (t, J=7.4 Hz, 2 H), 6.63-6.48 (m, 4 H), 6.24 (d, J=8.0 Hz, 2 H), 3.62 (s, 6 H), 3.12-2.03 (br, 36 H). .sup.13C NMR (100 MHz, C.sub.6D.sub.6) δ 148.04, 147.71, 147.53, 133.69, 131.57, 128.19, 126.13, 125.24, 124.45, 122.84, 118.84, 115.28, 115.23, 108.62, 56.37, 41.61 (br), Anal. Calcd for C.sub.40H.sub.58N.sub.8O.sub.2Hf.sub.2:C, 46.21; H, 5.62; N, 10.78. Found: C, 45.98; H, 5.45; N, 10.66.

Embodiment 2 Preparation of Composition syn-Zr.SUB.2

[0020] Using the same method as the method used in embodiment 1, replacing Hf(NMe.sub.2).sub.4 with Zr(NMe.sub.2).sub.4, and the bimetallic catalyst based on anthracene frameworks syn-Zr.sub.2 (0.73 g, 0.84 mmol, yield 84%) is obtained. .sup.1H NMR (400 MHz, C.sub.6D.sub.6) δ 9.05 (S, 1 H), 8.45 (S, 1 H), 7.74 (d, J=8.5 Hz, 2 H), 7.47-7.30 (m, 2 H), 7.08 (d, J=6.8 Hz, 2 H), 6.74 (t, J=7.4 Hz, 2 H), 6.58 (t, J=12.1 Hz, 4 H), 6.26 (d, J=8.0 Hz, 2 H)., 3.58 (s, 6 H), 2.93-2.27 (br, 36 H). .sup.13C NMR(C.sub.6D.sub.6) δ 148.08, 147.77, 147.56, 133.80, 131.49, 127.94, 126.21, 124.97, 124.25, 122.27, 118.90, 114.95, 114.57, 108.54, 56.00, 41.91. Anal. Calcd for C.sub.40H.sub.58N.sub.8O.sub.2Zr.sub.2:C, 55.52; H, 6.76; N, 12.95. Found: C, 55.33; H, 6.65; N, 12.78.

Embodiment 3 Preparation of Composition syn-Ti.SUB.2

[0021] Using the same method as the method used in embodiment 1, replacing Hf(NMe.sub.2).sub.4 with Ti(NMe.sub.2).sub.4, the bimetallic catalyst based on anthracene frameworks (0.68 g, 0.87 mmol, 87% yield) can be obtained. .sup.1H NMR (400 MHz, C.sub.6D.sub.6) 6 8.51 (s, 1 H), 8.35 (s, 1 H), 7.61 (d, J=8.6 Hz, 2 H), 7.34-7.30 (m, 2 H), 6.75 (d, J=9.1 Hz, 4 H), 6.58 (t, J=7.6 Hz, 2 H), 6.49 (t, J=7.6 Hz, 2 H), 5.76 (d, J=9.3 Hz, 2 H), 3.81 (s, 6 H), 3.01 (s, 12 H), 2.52 (s, 12 H), 1.88 (s, 12 H). NMR (100 MHz, C.sub.6D.sub.6) δ 150.13, 148.11, 147.15, 133.56, 130.62, 127.61, 126.11, 124.51, 123.63, 121.32, 120.04, 115.44, 113.29, 108.07, 55.51, 47.76, 44.60, 44.18. Anal. Calcd for C.sub.60H.sub.58N.sub.8O.sub.2Ti.sub.2: C, 61.70; H, 7.51; N, 14.39. Found: C, 61.53; H, 7.34; N, 14.03.

Embodiment 4 syn-Hf.SUB.2 .Catalyzing Ethylene Polymerization

[0022] Drying a 250 mL polymerization flask equipped with a magnetic stirrer for 6 hours at 120° C., vacuumizing when it is still hot, evacuating and refilling N.sub.2 gas for three times. Adding syn-Hf.sub.2 2.08 mg (2 μmol), adding MAO, so that Al/Ti=2000. Vacuumizing again and evacuating and refilling N.sub.2 gas for three times. Injecting methyl benzene 50 mL with a syringe, at 100° C., maintaining an ethylene pressure of 5 atm, and mixing violently for 2 min. Neutralizing the reaction solution with ethanol solution acidified with hydrochloric acid 5%, obtaining polymer precipitates, washing with ethanol and water for several times, vacuum drying until constant weight, and weighing. Polymerization activity: 4.2×10.sup.6 gmol.sup.−1(Ti).Math.h.sup.−1. Polymer M.sub.W=770 kg.Math.mol.sup.−1, M.sub.W/M.sub.n=2.2.

Embodiment 5 syn-Zr.SUB.2 .Catalyzing Ethylene Polymerization

[0023] Drying a 250 mL polymerization flask equipped with a magnetic stirrer for 6 hours at 120° C., vacuumizing when it is still hot, evacuating and refilling N.sub.2 gas for three times. Adding syn-Zr.sub.2 1.73 mg (2 μmol), adding MAO, so that Al/Ti=2000. Vacuumizing again and evacuating and refilling N.sub.2 gas for three times. Injecting methyl benzene 50 mL with a syringe, at 100° C., maintaining an ethylene pressure of 5 atm, and mixing violently for 2 min. Neutralizing the reaction solution with ethanol solution acidified with hydrochloric acid 5%, obtaining polymer precipitates, washing with ethanol and water for several times, vacuum drying until constant weight, and weighing. Polymerization activity: 3.1×10.sup.6 gmol.sup.−1(Ti)h.sup.−1. Polymer M.sub.W=550 kgmol.sup.−1, M.sub.W/M.sub.n=2.8.

Embodiment 6 syn-Ti.SUB.2 .Catalyzing Ethylene Polymerization

[0024] Drying a 250 mL polymerization flask equipped with a magnetic stirrer for 6 hours at 120° C., vacuumizing when it is still hot, evacuating and refilling N.sub.2 gas for three times. Adding syn-Zr.sub.2 1.56 mg (2 μmol), adding MAO, so that Al/Ti=2000. Vacuumizing again and evacuating and refilling N.sub.2 gas for three times. Injecting methyl benzene 50 mL with a syringe, at 100° C., maintaining an ethylene pressure of 5 atm, and mixing violently for 2 min. Neutralizing the reaction solution with ethanol solution acidified with hydrochloric acid 5%, obtaining polymer precipitates, washing with ethanol and water for several times, vacuum drying until constant weight, and weighing. Polymerization activity: 0.5×10.sup.6 gmol.sup.−1(Ti)h.sup.−1. Polymer M.sub.W=150 kgmol.sup.−1, M.sub.W/M.sub.n=2.1.

Embodiment 7 syn-Hf.SUB.2 .Catalyzing Ethylene and 1-octene polymerization

[0025] Drying a high pressure polymerization kettle at 120° C. for 6 hours continuously, vacuumizing while the kettle is still hot and evacuating and refilling N.sub.2 gas for three times. Adding methyl benzene 150 g, 1-octene 110 g and MAO 4 mmol. Heating until 140° C., pressurizing ethylene to 4.0 MPa. Adding methyl benzene solution 2.08 mg (2 μmop syn-Hf.sub.2 into a feeding hopper, adding the same into the polymerization kettle via high pressure nitrogen, copolymerizing for 10 minutes. Terminating the reaction with ethanol 5 mL, after cooling, depressurizing, introducing the reaction liquid into the ethanol and obtaining polymer precipitates, washing several times with ethanol and water, vacuum drying until constant weight, and weighing. Polymerization activity: 2.1×10.sup.7 gmol.sup.−1(Ti)h.sup.−1. Polymer M.sub.w =890 kg.Math.mol.sup.−1, M.sub.W/M.sub.n=2.2, and an insertion rate of 1-octene 12.5 mol %.

Embodiment 8

[0026] Drying a 250 mL polymerization flask equipped with a magnetic stirrer for 6 hours at 120° C., vacuumizing when it is still hot, evacuating and refilling N.sub.2 gas for three times. Adding syn-Hf.sub.2 2.08 mg (2 μmol), and adding MAO, so that Al/Ti=2000. Vacuumizing again and evacuating and refilling N.sub.2 gas for three times. Injecting methyl benzene 50 mL with a syringe, at 100° C., adding norbornene 200 mmol, maintaining an ethylene pressure of 5 atm, and mixing violently for 2 min. Neutralizing the reaction solution with ethanol solution acidified with hydrochloric acid 5%, obtaining polymer precipitates, washing with ethanol and water for several times, vacuum drying until constant weight, and weighing.

[0027] Polymerization activity: 6.5×10.sup.6 gmol.sup.−1(Ti)h.sup.−1. Polymer M.sub.W=40 kg.Math.mol.sup.−1, M.sub.W/M.sub.n=3.4, and a norbornene insertion rate is 45 mol %.