Source: https://patents.google.com/patent/US7056996?oq=6%2C408%2C309
Timestamp: 2018-03-23 19:24:20
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Matched Legal Cases: ['§ 119', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60']

US7056996B2 - Productivity catalysts and microstructure control - Google Patents
US7056996B2
US7056996B2 US10648357 US64835703A US7056996B2 US 7056996 B2 US7056996 B2 US 7056996B2 US 10648357 US10648357 US 10648357 US 64835703 A US64835703 A US 64835703A US 7056996 B2 US7056996 B2 US 7056996B2
US10648357
US20040077809A1 (en )
Amy Kathryn Farthing
B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
This is a continuation-in-part of application Ser. No. 09/985,614, filed Nov. 5, 2001; which is a continuation-in-part of application Ser. No. 09/563,812, filed May 3, 2000 now U.S. Pat. No. 6,545,108; which is a continuation-in-part of application Ser. No. 09/507,492, filed Feb. 18, 2000 now U.S. Pat. No. 6,559,091, the entire contents of which are incorporated herein by reference. The '614 application claims the benefit of the following applications under 35 USC § 119: Provisional Application No. 60/231,920, filed Sep. 11, 2000; Provisional Application No. 60/246,254, filed Nov. 6, 2000; Provisional Application No. 60/246,255, filed Nov. 6, 2000; Provisional Application No. 60/246,178, filed Nov. 6, 2000; and Provisional Application No. 60/298,893, filed Jun. 19, 2001, the entire contents of which are incorporated herein by reference.
In a second preferred embodiment of the second aspect, the olefin is ethylene, M is nickel, the temperature is at least 80° C., the pressure is less than about 800 psig, sufficient hydrogen is added to reduce the number average molecular weight of the polymer by at least 20% relative to an otherwise similar reaction conducted in the absence of hydrogen, the catalyst productivity is at least 500 kg polyethylene per g nickel, and the polymer has a DSC (Differential Scanning Calorimetry) first cycle peak melting point greater than 131° C.
In a third, more preferred embodiment of the second embodiment of the second aspect, sufficient hydrogen is added to reduce the number average molecular weight of the polymer by at least 50% relative to an otherwise similar reaction conducted in the absence of hydrogen, and the polymer has a DSC first cycle peak melting point greater than 133° C.
In a fourth aspect, this invention pertains to a process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8–10 metal complex of a bidentate, N,N-donor ligand, wherein the first of the donor nitrogens, N1, is substituted by an aromatic or heteroaromatic ring wherein the ortho substituents are aryl or heteroaryl groups, and the second of the donor nitrogens, N2, is substituted by an aromatic or heteroaromatic ring wherein one or both of the ortho substituents are other than aryl or heteroaryl; wherein the catalyst is capable of homopolymerizing ethylene to produce a polymer with a number average molecular weight of at least 20,000 g/mole and at least 20 branch points per 1000 carbons with a catalyst productivity of at least 500 kg polyethylene per g of Group 8–10 metal at a temperature of at least 60° C. at a partial pressure of ethylene of at least 350 psia at a partial pressure of hydrogen of at least 2 psia. Preferred substituents other than aryl or heteroaryl include Br, Cl, CF3 and fluoroalkyl.
In a fourth, more preferred embodiment of this fourth aspect, the metal is nickel, N1 is substituted by a 2,6-diaryl substituted aryl group, N2 is substituted by an aromatic ring wherein one or both of the ortho substituents are other than aryl or heteroaryl, and the catalyst productivity is at least 500 kg polyethylene per g nickel at a temperature of at least 70° C.
By “olefin rotation”, we mean rotation by at least 180° about a vector extending from said Group 8–10 metal to the olefin centroid. The rate of olefin rotation may be calculated using Density Field Theory/Molecular Mechanics programs (c.f. Ziegler et al. in J. Am. Chem. Soc. 1997, 119, 1094 and 6177).
By “elevated temperatures”, we mean a temperature of at least 60° C., preferably at least 70° C., even more preferably at least 80° C.
A variety of protocols may be used to generate active polymerization catalysts comprising transition metal complexes of various nitrogen, phosphorous, oxygen and sulfur donor ligands. Examples include (i) the reaction of a Group 4 metallocene dichloride with MAO, (ii) the reaction of a Group 4 metallocene dimethyl complex with N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, (iii) the reaction of a Group 8 or 9 metal dihalide complex of a tridentate N-donor ligand with an alkylaluminum reagent, (iv) the reaction of a Group 8 or 9 metal dialkyl complex of a tridentate N-donor ligand with MAO or HB(3,5-bis(trifluoromethyl)phenyl)4, (v) the reaction of (Me2N)4Zr with 2 equivalents of an N-pyrrol-1-ylsalicylimine, followed by treatment of the product of that reaction with Me3SiCl and then a triisobutylaluminum-modified methylaluminoxane, and (vi) the reaction of a nickel or palladium dihalide complex of a bidentate N-donor ligand with an alkylaluminum reagent. Additional methods described herein include the reaction of (tridentate N-donor ligand)M(acac)B(C6F5)4 salts with an alkylaluminum reagent, where M is Fe(II) or Co(II), and the reaction of (bidentate N-donor ligand)Ni(acac)X salts with an alkylaluminum reagent, where X is a weakly coordinating anion, such as B(C6F5)4 −, BF4 −, PF6 −, SbF6 −, (F3CSO2)2N−, (F3CSO2)3C−, and OS(O)2CF3 −. Cationic [(ligand)M(π-allyl)]+ complexes with weakly coordinating counteranions, where M is a Group 10 transition metal, are often also suitable catalyst precursors, requiring only exposure to olefin monomer and in some cases elevated temperatures (40–100° C.) or added Lewis acid, or both, to form an active polymerization catalyst.
Temperature and olefin pressure have significant effects on catalyst activity, and on polymer structure, composition, and molecular weight. Suitable polymerization temperatures are preferably from about 20° C. to about 160° C., more preferably 60° C. to about 100° C. Suitable polymerization pressurse range from about 1 bar to about 200 bar, preferably 5 bar to 50 bar, more preferably 10 bar to 50 bar.
EXAMPLES Example 1 Ethylene Polymerization at Elevated Temperature and Pressure. General Procedure Used to Obtain the Polymerization Data Given in Table I
The data given in Table I was generated using a procedure substantially similar to the following procedure. A 1 L Parr® autoclave, Model 4520, was dried by heating under vacuum to 180° C. at 0.6 torr for 16 h, then cooled and refilled with dry nitrogen. The autoclave was charged with dry, deoxygenated hexane (450 mL) and 1.0 mL of a 10 wt % solution of MAO in toluene (Aldrich®), then purged by pressurizing it to 200 psig with ethylene and venting (3 cycles). Hydrogen was added to the reactor either by direct pressurization to the indicated partial pressure (for hydrogen partial pressures >4 psia), or by pressurizing a 40 mL gas sample loop to 40 or 65 psia with hydrogen, and using ethylene gas to sweep the hydrogen into the reactor (for hydrogen partial pressures ≦4 psia). The autoclave was then heated to the temperature indicated in Table I and pressurized to within about 100 psig of the indicated pressure (see Table I) with ethylene gas while being vigorously stirred. Ethylene pressure was then used to inject 2.0 mL of dry, deoxygenated toluene from a sample loop (to clean the loop), followed by 2.0 mL (corresponding to 0.5 micromole of catalyst) of a toluene stock solution of [(ligand)Ni(acac)][B(C6F5)4], (see Table I for ligand) followed by another 2.0 mL of dry, deoxygenated toluene (to flush the loop), thereby raising the total reactor pressure to 5–10% over the target pressure, after which the reactor was isolated from the ethylene supply and the pressure was allowed to fall to approximately 5–10% below the target pressure, after which more ethylene was added to raise the pressure back to 5–10% over the target pressure and the cycle was repeated as required. In some cases, multiple catalyst injections were made, with the final injection being made at the indicated last injection time. After the indicated total reaction time, 2.0 mL MeOH was injected via the sample loop, and the reactor was promptly cooled, depressurized and opened. The polyethylene product was recovered by filtration, washed with MeOH and then a dilute solution of Irganox™ 1010 (Ciba-Geigy) in acetone, and dried in vacuo at 160° C., 1 mm Hg.
Pressure injection Kg PE/ mol Ni 1000 Mn
Entry Ligand T (° C.) (psig) H2 (psi) t (min) (min) Yield (g) g Ni (×10−3) carbons (×10−3) PDI1 Tm (° C.)2
12 wa4 81 385 0 60 33 20.5 355 732 18.9 69.7 2.49 114.5
13 wa4 81 382 0 45 0 12.0 414 854 14.9 90.7 2.42 116.7
14 wa4 70 411 3 432 84 23.8 819 1690 115.5 2.29 129.0
15 wa4 70 403 3 264 58 24.9 857 1770
16 hcr10 71 392 0 53 12 36.0 308 636 48.8 292.1 1.98 68.6
17 hcrl2 70 401 2 89 0 64.6 373 769 42 83.4 3.19 76.8,
18 wa6 79 420 0 123 48 15.6 270 557 41.5 340.3 2.01 86.5
19 hcr11 70 418 3 160 90 27.8 482 994 94.9
20 ill16 70 200 5 335 112 21.9 184 387 41 13.7 1.93
21 hcr117 80 182 6 107 70 8.6 74 153 52 15.9 2.01 60.8,
22 shcr10 80 460 7 404 167 31.6 309 649 13.4 34.3 2.50 122.3
23 shcr118 60 193 7 229 126 46.3 399 836 35 35.0 2.69 80.5,
4AlMe3 (2 mmol) used in place of MAO; 2,6-di-tert-butyl-4-methylphenol (9.1 mmol) injected and allowed to react with the AlMe3 at 80° C. for 30 min prior to addition of the Ni catalyst.
Example 2 Preparation of da2, a Ti Complex thereof, and Ethylene Polymerization
Example 3 Ethylene polymerization using [(w3)Ni(acac)]B(C6F5)4 using MAO to Activate
The procedure of Example 1 was followed using 15.72 psi hydrogen, an average reaction temperature of 90° C., an average pressure of 400 psig, two catalyst injections, with the last injection at 0.32 min, and a total reaction time of 120 min to obtain 18.0 g polyethylene, corresponding to 6.1 million mol C2H4/mol Ni. The reactor pressure was followed as a function of time, and showed an increasing rate of ethylene consumption for the first 20–30 min, after which the rate stabilized and then slowly decreased until the end of the experiment.
Example 4 Ethylene Polymerization using [(w3)Ni(acac)]B(C6F5)4 using AlMe3 to Activate
The procedure of Example 3 was followed using 14.7 psi hydrogen and 0.36 mmol AlMe3 in hexane instead of MAO, an average temperature of 81° C., an average pressure of 399 psig, two injections of catalyst, with the last injection at 0.35 min and a total reaction time of 57 min to obtain 49.9 g polyethylene, corresponding to 1.7 million turnovers. A graph of reactor pressure as a function of time showed a more rapid increase in activity than was observed in Example 3, with full activity apparently being reached within about 5 min.
Example 5 Synthesis of wa6-i1
Benzaldehyde (3.0 g, 28.3 mmol) and 4′-bromoacetophenone (15.0 g, 75.4 mmol) were nearly dissolved in 95% ethanol (60 mL). Solid sodium hydroxide (1 pellet, ca. 100 mg) was added. The mixture was heated at reflux for ca. 30 s, then allowed to cool. Upon cooling, an orange oil settled. The mixture was again heated at reflux for ca. 1 min. Upon cooling, near-colorless crystals separated from the orange supernatant. Ethanol (150 mL) was added, and the large chunky crystals were crushed with a glass rod, then collected by vacuum filtration and washed with ethanol (3×20 mL). The desired diketone wa6-i1 was used without further purification. Crude yield: 10.3 g, 74%.
Example 6 Synthesis of wa6-i2
Triphenylmethanol (6.6 g, 25.4 mmol) was suspended in acetic anhydride (70 mL) and warmed until in solution. Tetrafluoroboric acid (48% in water, 4.15 mL, 31.8 mmol) was slowly added dropwise while cooling the exothermic reaction in a room temperature water bath. Diketone wa6-i1 (10.3 g, 21.2 mmol) was added in portions over a few minutes. Yellow needles of the desired pyrylium salt wa6-i2 began to separate from solution within minutes. The mixture was stirred at room temperature for 16 h, then vacuum filtered and washed with acetic anhydride (3×25 mL) and dried in vacuo at 100° C. to obtain 9.9 g wa6-i2. An additional 540 mg was obtained by treating the filtrate/washings with diethyl ether. Combined yield: 89%.
Example 7 Synthesis of wa6-i3
Example 8 Synthesis of wa6-i4
To a suspension of wa6-i3 (11.81 g, 20.2 mmol) and Pd(PPh3)4 (2.67 g, 2.4 mmol) in toluene (201 ml) was added 4-tert-butylphenylboronic acid (10.77 g, 60.5 mmol) as a solution in EtOH (40 ml). 2 M aqueous Na2CO3 (80 ml) was added and the resulting suspension was heated at 85° C. for 41.5 h, then cooled to 23° C. and extracted with Et2O. The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was dissolved in toluene and filtered through a plug of silica gel and celite then concentrated in vacuo. The residue was suspended in a small amount of CH2Cl2 and filtered, washing with heptane. A second amount of precipitate was collected from the filtrate, again washing with heptane. The filtrate was filtered a third time to afford a gray solid, which was adsorbed onto silica gel and eluted through a short plug of silica and celite with CH2Cl2. The filtrate was combined with the solids obtained previously to afford wa6-i4 (6.14g, 44%), which was used without further purification.
Example 9 Synthesis of wa6-i5
A suspension of wa6-i4 (9.14 g, 13.2 mmol) and 5% Pd/C (1.84 g) in a mixture of toluene (149 ml) and MeOH (25 ml) was stirred under a balloon of H2 at 55° C. for 17 h. The reaction was cooled to rt, and filtered through a plug of celite, rinsing with toluene. The filtrate was concentrated in vacuo to afford wa6-i5 (8.72 g, 100%), which was used without further purification.
Example 10 Synthesis of wa6-i6
To an ice cold suspension of wa6-i5 (8.72 g, 13.2 mmol) in acetic acid (102 ml) and CH2Cl2 (20 ml) was added NaOAc (2.18 g) in portions. Following the completion of the addition, bromine (1.37 ml) was added via syringe. The ice bath was removed, and the reaction stirred at 23° C. under Ar for 1.5 h then poured over ice, resulting in the formation of a yellow solid (7.96 g), which was collected by vacuum filtration. The filtrate was extracted with CH2Cl2. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo. The residue was combined with the solid collected previously to afford wa6-i6 (10.13 g, 94%), which was used without further purification.
Example 11 Synthesis of wa6-i7
To a suspension of wa6-i6 (4.5 g, 5.5 mmol) and Pd(Ph3P)4 (0.722 g, 0.65 mmol) in toluene (54.6 ml) was added 4-tert-butylphenylboronic acid (2.91 g, 16.4 mmol) and EtOH (10.9 ml). The resulting suspension was treated with 2 M aqueous Na2CO3 (21.7 ml) then heated to 85° C. for 22.5 h. The reaction was cooled to rt, and extracted with toluene. The organic layer was washed with water, dried over Na2SO4, filtered and concentrated in vacuo. The residue was divided into two portions and purified by flash chromatography (SiO2, 5–50% CH2Cl2/heptane) on two columns to afford wa6-i7 (1.9 g and 2.16 g, total 4.06 g, 80%).
Example 12 Synthesis of wa6-i8
To a suspension of wa6-i7 (250 mg, 0.27 mmol) in CH2Cl2 (1.5 ml) was added ethyl chlorooxoacetate (0.032 ml, 0.28 mmol). The resulting solution was stirred at 23° C. for 1 h, then diluted with CH2Cl2 and washed with saturated aqueous NaHCO3 and water. The organic layer was concentrated in vacuo to afford wa6-i8 (277 mg), which was used without further purification.
Example 13 Synthesis of wa-i9
A suspension of wa6-i8 (246 mg, 0.24 mmol) in iPrOH (1.7 ml) was treated with 2 M NaOH (1.08 ml). The resulting suspension was heated to 60° C. for 1 h, then cooled to 23° C. and acidified with 2 M HCl (pH=2). The solid that formed was filtered, washed with H2O and dried in vacuo to afford wa6-i9 (220 mg, 92%), which was used without further purification.
Example 14 Synthesis of wa6-i10
Amide/acid wa6-i9 (215 mg, 0.215 mmol) was added portionwise to a suspension of NaH (60% in oil, 10 mg, 0.254 mmol) in toluene (2 ml). The resulting suspension was stirred at 23° C. for 15 min then treated with oxalyl chloride (338 μl, 3.88 mmol) and stirred at 23° C. for an additional 15 min. The mixture was concentrated in vacuo, and the residue was treated with wa6-i6 (184 mg, 0.225 mmol) followed by CH2Cl2 (2 ml). The resulting suspension was stirred at 23° C. for 3 days then concentrated in vacuo to afford crude wa6-i10 (415 mg), which was used without further purification.
Example 15 Synthesis of wa6-i11
A suspension of wa6-i10 (385 mg (assume 100% yield from example 10), 0.214 mmol) in o-xylene (1.5 ml) was treated with P4S10 (48 mg, 0.108 mmol). The resulting suspension was heated to 140° C. under Ar for 1.5 h, then cooled to rt. The residue was diluted with toluene and washed with water. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo to afford wa6-i11 (413 mg), contaminated with residual xylene. The crude product was not purified further.
Example 16 Synthesis of wa6
To a suspension of wa6-i11 (392 mg (assume 100% yield from example 11), 0.214 mmol,) in 1,2-dibromoethane (2.17 ml) was added 2 M NaOH (2.55 ml) and tetrabutylammonium bromide (12.8 mg, 0.04 mmol). The resulting biphasic mixture was stirred rapidly under Ar at 23° C. for 17 h, then diluted with CH2Cl2 and washed with H2O. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (SiO2, 20–70% CH2Cl2/heptane) to afford wa6 (280 mg, 70% from wa6–19).
Example 17 Synthesis of wa5-i1
A solution of wa6-i7 (329 mg, 0.355 mmol) in CH2Cl2 (2 ml) was treated with oxalyl chloride (20 μl, 0.22 mmol). The resulting solution was stirred at 23° C. under Ar for 1 h, then poured into MeOH. The precipitate was filtered and dried in vacuo. NMR indicated the crude product contained a significant amount of wa6-i7, so the mixture was redissolved in CH2Cl2 (2 ml) and treated with oxalyl chloride (10 μl, 0.11 mmol). The resulting mixture was stirred at 23° C. under Ar for 25.5 h, then poured into MeOH. The precipitate was filtered and dried in vacuo to afford wa5-i1 (319 mg), which was used without further purification.
Example 18 Synthesis of wa5-i2
P4S10 (37.5 mg, 0.084 mmol) was added to a suspension of wa5-i1 (319 mg, 0.167 mmol) in o-xylene (1.4 ml). The resulting suspension was heated to 140° C. under Ar for 5.5 h, then cooled to 23° C. overnight. TLC indicated the reaction was not complete, so the mixture was heated to 140° C. for an additional 6 h. The reaction was cooled to 23° C. and allowed to stand under Ar overnight. The suspension was diluted with toluene and washed with H2O. The organic layer was dired over Na2SO4, filtered and concentrated in vacuo to afford wa5-i2 (242 mg), which was used without further purification.
Example 19 Synthesis of wa5
Example 20 Ethylene Polymerization with the Nickel Catalyst Derived from Ni(acac)7, Ph3C(C6F5)4 and Ligand v22
A 1 L Parr® autoclave, Model 4520, was dried by heating under vacuum to 180 C at 0.6 torr for 1 h, then cooled and refilled with dry nitrogen. The autoclave was charged with dry, deoxygenated hexane (450 mL) and 2.0 mL of a 0.25 M solution of triisobutylaluminum in hexanes. The reactor was sealed and heated to 80° C. under nitrogen, then sufficient hydrogen was added to raise the pressure by 8.9 psi, after which ethylene was introduced to raise the total pressure to 250 psig. A sample loop injector was first purged with 2.0 mL dry, deoxygenated dichloromethane (injected into the reactor), and then used to inject 3×2.0 mL of a stock solution (corresponding to a total of 3.0 μmol of pro-catalyst) prepared from 17.34 mL of CH2Cl2 and 2.66 mL of a second stock solution prepared from 45.3 mg ligand v22, 15.0 mg Ni(acac)2, 54 mg Ph3C(C6F5)4 and 19.546 g (14.75 mL) CH2Cl2, followed by 2.0 mL of CH2Cl2, using ethylene gas to force the liquids into the autoclave and raise the pressure to ca. 440 psig, after which time the reactor was isolated and the pressure was allowed to fall to about 380 psig. More ethylene was then reintroduced to raise the pressure back to ca. 430 psig, after which the pressure was allowed to fall to ca. 400 psig, to give an average pressure of 402 psig, and an average temperature was 80.4° C. After 47 min, the reaction was quenched by injection of MeOH, then the reactor was cooled, depressurized and opened. The polyethylene was recovered by concentrating the mixture to dryness under vacuum to obtain 13.01 g amorphous polyethylene, corresponding to 1.55×105 mol ethylene/mol Ni.
Example 21 Ethylene Polymerization with the Nickel Catalyst Derived from Ni(acac)2, Ph3C(C6F5)4 and Ligand v22
The procedure of Example 20 was followed, except the average temperature was 60.1 C, the average pressure was 605 psig, the partial pressure of hydrogen was 4.49 psi, and the total reaction time was 59.7 min. This afforded 38.6 g amorphous polyethylene, corresponding to 4.6×105 mol ethylene/mol nickel.
Example 22 Ethylene Polymerization with the Nickel Catalyst Derived from Ni(acac)2, Ph3C(C6F5)4 and Ligand v5
The procedure of Example 20 was followed using 2 μmol of the nickel catalyst derived from Ni(acac)2, Ph3C(C6F5)4 and ligand v5, and an average temperature of 60.8 C, an average pressure of 397 psig, a partial pressure of hydrogen of 5.12 psi, and a total reaction time of 21.7 min. This afforded 38. g partially crystalline polyethylene, corresponding to 6.8×105 mol ethylene/mol nickel.
Example 23 Ethylene Polymerization with the Nickel Catalyst Derived from Ni(acac)2, Ph3C(C6F5)4 and 2,3-bis(2,6-diisopropylphenylimino)butane
The procedure of Example 20 was followed using 4.2 μmol of the nickel catalyst derived from Ni(acac)2, Ph3C(C6F5)4 and 2,3-bis(2,6-diisopropylphenylimino)-butane, and an average temperature of 60.5 C, an average pressure of 398 psig, a partial pressure of hydrogen of 4.64 psi, and a total reaction time of 60 min. This afforded 18.7 g polyethylene, corresponding to 1.6×105 mol ethylene/mol nickel.
Example 24 Ethylene Polymerization with the Nickel Catalyst Derived from Ni(acac)2, Ph3C(C6F5)4 and Ligand v4
The procedure of Example 20 was followed using 2 μmol of the nickel catalyst derived from Ni(acac)2, Ph3C(C6F5)4 and ligand v4, an initial temperature of 60° C. (the reaction exothermed to 81° C.), an average temperature of 63.7 C, an average pressure of 590 psig, a partial pressure of hydrogen of 4.03 psi, and a total reaction time of 34.5 min. This afforded 33.7 g partially crystalline polyethylene, corresponding to 6.0×105 mol ethylene/mol nickel.
Example 25 Ethylene Polymerization with the Nickel Catalyst Derived from Ni(acac)2, Ph3C(C6F5)4 and Ligand v5
The procedure of Example 22 was repeated using 3 μmol nickel catalyst, 13.32 psi hydrogen, an average temperature of 80.4 C, and an average pressure of 406 psig to obtain 19.9 g polyethylene, corresponding to 2.4×105 mol ethylene/mol Ni.
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US20040077809A1 (en) 2004-04-22 application