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
  • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • 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
  • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
  • C07F13/005—Compounds without a metal-carbon linkage
• • 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

Definitions

• Chromium(III) silicate catalysts suitable for PE synthesis Chromium(III) silicate catalysts suitable for PE synthesis
• the present invention concerns polyethylene (PE) synthesis, in particular PE synthesis based on a Phillips type catalyst.
• PE polyethylene
• PE Polyethylene
• Polyethylene is a commodity material that is ubiquitous in modern society. PE is encountered in countless applications ranging from the mundane to the essential: plastic bags, water bottles, food packaging, automotive parts, wires, pipes, and medical packs are only a few examples of how PE permeates everyday life. PE is produced on very large scales using processes tailored to the particular need of the final polymeric material. Over 80 million tons of PE are produced annually, a figure likely to rise.
• chromium trioxide supported on silica polymerizes ethylene.
• Using the Cr/Si0 2 composition, commonly referred to as Phillips catalyst 40-50 % of high density PE is produced globally.
• the Phillip's catalyst polymerizes ethylene without an activator, a unique feature among olefin polymerization catalysts.
• the catalyst precursor is prepared by impregnation of Cr0 3 on silica, which is then calcined at high temperatures. The calcination step is necessary to attach the Cr(VI) center to the silica via chromate esters.
• the chromates can be present as monomers, dimers, or polymeric species.
• the precatalyst is usually depicted as a monomeric chromium site. Ethylene polymerization occurs when the surface bound Cr(VI) species are activated in-situ with ethylene to form a "reduced" chromium species that is the proposed active site. Because the Cr(VI) species must be reduced prior to polymerization initiation there is a pronounced induction period for these materials. Alternatively the Cr(VI) containing silica material can be pre -reduced in the presence of carbon monoxide at 300 °C to produce a catalyst that polymerizes ethylene with a less pronounced induction period.
• Phillips catalyst by synthesizing homogeneous equivalents that could mimic the surface Cr environment. By definition this is a difficult task because the chromium coordination environment should only contain (X 3 SiO) 2 Cr moieties, which is difficult to obtain and to stabilize in solution due to the propensity of low-coordinate Cr-complexes to form strong metal-metal multiple bonds. Despite the lack of discrete (R 3 SiO) 2 Cr complexes, detailed studies have been conducted with homogeneous Cr(II) and Cr(III) complexes.
• SOMC Organometallic Chemistry
• the intent of the present invention was to provide well defined Phillip's like chromium on silica catalysts, preferably such catalysts that are easily obtainable and/or that can be prepared with different activities due to more or less concentrated active chromium centers and thus may influence the polymerization rate and/or polymerization grade.
• chromium molecular precursor chromium compound also termed chromium molecular precursor or chromium molecular precursor compound
• chromium on silica catalyst a molecular precursor chromium compound suitable for use in producing a silica supported chromium catalyst, further on termed chromium on silica catalyst and such use.
• Other objects of the present invention are to provide a method for producing a chromium on silica catalyst precursor and a method for producing a chromium on silica catalyst starting from a chromium on silica catalyst precursor and a method for producing a molecular precursor chromium compound.
• Another object is a method for producing polyethylene (PE) using such chromium on silica catalyst.
• Still another object is the use of a chromium on silica catalyst for producing polyethylene (PE).
• the molecular precursor chromium compound suitable for use in producing a chromium on silica catalyst is manifested by the features that it is a chromium(II), a chromium (III) or a chromium(IV) compound with all ligands selected from silanolates or alcoholates or amides that can be decomposed upon thermal treatment.
• the advantage of the catalysts of the present invention is that they are produced from well defined and predictably decomposable precursors resulting in the formation of well- defined Cr(II), Cr(III) and Cr(IV) monomeric or dimeric sites on silica surfaces. While Cr(II) species were found to display polymerization activity lower than their Cr(III) analogues, the Cr(III) containing materials were found to exhibit activities higher than Phillip's catalyst, while maintaining similar polymer molecular weight properties.
• the molecular precursors of the present invention in general are monomers or dimers.
• ligand as used in the scope of the present invention is any group present in or originating from the molecular precursor chromium compound.
• the ligand environment around the chromium center is critical for the success of discrete metal silicate formation.
• the soluble precursors comprise at least one group suitable for covalently attaching the Cr(III) catalyst to the silica surface and the other ligands being easily removable like decomposable to result in a carbon free, in particular a Cr(III)-catalyst with exclusively -O-Si- coordination.
• Such easily removable ligands are e.g.
• coordinated solvents such as ethers like thf, or amines, or nitrogen containing heterocycles and/or anionic groups of type -0-CR 3 R 4 -CH-R1R 2 and/or -0-Si-(0- CR 3 R 4 -CH-R 1 R 2 ) 3
• Rl , R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of the beta- hydrogen from -CR3R4-CH-R1R2, and/or easily removable covalently bound amides of the type -N-(Si-R 5 R 6 R 7 ) 2 and/or -N-(C-R 5 R 6 R 7 ) 2 wherein R 5 , R 6 and R 7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups or iso-propyl groups, tert-butyl groups or aromatic groups, in particular an amide like
• Preferred groups Rl to R4 independently from each other are selected from the group consisting of hydrogen, methyl groups, ethyl groups, n-propyl groups, iso- propyl groups, tert-butyl groups or aromatic groups, more preferred Rl to R 4 are
• Rl and R 2 independently from each other selected from the group consisting of hydrogen, methyl or phenyl.
• Rl and R 2 hydrogen is presently most preferred and for R 3 and R 4 methyl groups.
• Such compounds are e.g. monomers or dimers wherein all ligands are -0-CR 3 R 4 - CH-R!R 2 or -0-Si-(0-CR 3 R 4 -CHR 1 R 2 ) 3 (see e.g. Figure 1) or combinations thereof-.
• a preferred group is of the type -0-Si-(0-CR 3 R 4 -CH-RlR 2 ) 3 , in particular tri-tert- butoxysilanolate (-OSi(O l Bu) 3 ) because chromium complexes containing this ligand are known to decompose at relatively low temperatures (e.g. 200 °C) to yield silicate materials.
• chromium complexes containing this ligand are known to decompose at relatively low temperatures (e.g. 200 °C) to yield silicate materials.
• molecular precursor chromium compounds suitable for use in producing chromium on silica catalyst precursors and chromium on silica catalysts are
• These molecular precursors can be grafted to silica surfaces to give chromium on silica catalyst precursor.
• at least one ligand usually one or possibly two ligands is/are replaced by a surface O-Si-0 group ( ⁇ SiO) by grafting. Via decomposition it is possible to remove all remaining ligands.
• ligand(s) is(are) replaced or all ligands are removed or replaced.
• Preferred chromium on silica catalyst precursors that still comprise ligands are [( ⁇ SiO)Cr 2 (OSi(O t Bu) 3 ) 3 ] or C 4 8Hio8Cr 2 Oi7Si4 grafted on silica (6) or
• a preferred chromium on silica catalyst is a Cr(III) compound attached to the silica surface via Si-0 bonds, wherein all ligands have been either removed or replaced by a surface O-Si-0 group ( ⁇ SiO), in particular [( ⁇ SiO) 6 Cr 2 ] or [( ⁇ SiO) 3 Cr].
• ⁇ SiO surface O-Si-0 group
• a molecular precursor chromium compound may be obtained by a method comprising treating a Cr(II) and/or a Cr(III) and/or a Cr(IV) starting compound with starting-ligands that are so weakly bound that they can easily be removed/replaced by stronger binding ligands.
• Such starting compound is treated with one or more ligand precursor(s), like protonated ligand(s) or metal salts of the ligand(s), in particular the sodium or potassium salts, wherein the ligand(s) are as defined above under conditions that allow coordination of the one or more ligands, in particular by reacting a slurry of the Cr(II) or Cr(III) or Cr(IV) starting compound in a non coordinating solvent at temperatures of -40 to 150°C, preferentially at temperatures comprised between 15 and 40 °C.
• Suitable starting compounds comprise
• hexamethyldisilazide or chloride optionally together with solvent ligands (e.g. thf), in particular Cr(HMDS) 2 *2thf or Cr(HMDS) 3 76> or CrCl 3 *3thf or CrCl 3 or CrCl 2 *2thf or CrCl 2 or mixtures thereof.
• solvent ligands e.g. thf
• the molecular precursor chromium compounds may be used to being grafted to silica.
• the silica used for preparing the chromium on silica catalyst may be pretreated to generate a predetermined number of reactive surface SiOH groups for binding catalyst.
• a chromium on silica catalyst precursor that still has ligands bound to the Cr center may be prepared by treating silica with a molecular precursor chromium compound, said compound being a Cr(II) and/or a Cr(III) and/or a Cr(IV) molecular precursor chromium compound.
• a chromium(II) on silica catalyst precursor that has no ligands bound to the Cr center can be prepared by heat treating a chromium on silica catalyst precursor that still has ligands bound to the Cr center, e.g.
• the reaction may be performed for > 1 minute, like >30 minutes, preferably > 1.5 hours, often > 2 hours .
• a chromium on silica catalyst may be prepared by either oxidizing a chromium(II) on silica catalyst precursor that has no ligands bound to the Cr center or by heat treating a chromium(III) on silica catalyst precursor that still has ligands bound to the Cr center for a time and at a temperature suitable for removing all the ligands, in particular under vacuum, like a pressure of 500 mbar or lower, in particular 10 "5 mbar, or in a flow of an inert gas, like He, Ar, N 2 , at a temperature comprised between 100 and 900 °C, preferably between 200 and 700 °C and more preferably between 220 and 500 °C.
• the reaction may be performed for > 1 minute, like >30 minutes, preferably > 1.5 hours, often > 2 hours.
• a chromium on silica catalyst may be prepared in a similar manner starting from Cr (IV).
• the molecular precursors are Cr(IV) compounds with ligands as described above and the grafting and further processing can be done in a similar manner as described herein.
• a molecular Cr(IV) precursor, a Cr(IV) on silica catalyst precursor and a catalyst that is formed from the Cr(IV) on silica catalyst precursor by mere heat treatment as described herein is found in Figure 1.
• the structure of the final catalyst has not yet been finally determined and it is not yet sure whether the active catalyst is Cr(IV), Cr(III) or a mixture of Cr(IV) and Cr(III).
• the chromium on silica catalyst obtained starting from Cr(IV) molecular precursor is active.
• chromium compounds used as molecular chromium precursor compounds as such are known, but not for producing silica catalyst precursors of the present invention.
• Such known compounds are Cr(OSi(OtBu)3)3*2thf (67), Cr(O l Bu) 4 (68)
• N 2 preferably at a temperature comprised between 20 to 300°C, more preferred between 20 to 150 °C, most preferred at about 100 °C.
• the reaction will usually be finished within ⁇ 30 minutes, at 150 °C within about 30 minutes and at 100 °C within about 1 hour.
• temperatures close to 20°C reaction times of about 14 hours have been found.
• the precursors of the invention can easily be prepared and grafted to the silica surface in predetermined amounts and then converted to the active catalyst.
• the inventive method allows the silica to be loaded with a predetermined amount of catalyst thereby generating catalysts with more or less
• polymerization activating centers so that the polymerization can be regulated/controlled to some extent.
• an object of the present invention is a method for producing polyethylene (PE) said method comprising polymerizing ethylene at a pressure of 100 mbar to 50 bar, preferably 1 bar to 25 bar, in particular 6 bar and in the presence of a chromium(III) on silica catalyst of the present invention.
• PE polyethylene
• Still a further object of the present invention is the use of a chromium(III) on silica catalyst for producing polyethylene (PE), in particular for producing polyethylene (PE) in the gas phase or in a slurry containing an organic solvent. Besides of the easy manufacturing and the surface coverage that can be
• a further advantage of the inventive catalysts is the absence of any organic ligand. This absence of organic ligands results in a very pure polyethylene since no ligand can act as chain terminator.
• Figure 1 shows formulas of some specific precursors and catalysts of the present invention, wherein Figure la gives general formulas of some molecular precursor chromium compounds, Figure lb specific examples of dimeric compounds and Figure lc specific examples of monomelic compounds.
• Figure 2 shows reaction of Cr(HMDS) 2 *2thf with HOSi(O l Bu)3 to give
• Figure 3 shows grafting of (1) on Si0 2-7 oo to form [( ⁇ SiO)Cr 2 (OSi(0 , Bu) 3 ) 3 ] (2) followed by thermal decomposition under high vacuum to yield [( ⁇ SiO)4Cr 2 ] (3).
• Figure 5 shows reaction of (1) with N 2 0 to give (5).
• the solid-state structure of (5) obtained from X-Ray diffraction is also shown.
• Methyl groups from the -OSi(O l Bu) 3 ligands, and all H-atoms are removed for clarity.
• Figure 6 shows ethylene polymerization activity of chromium catalysts at low ethylene pressure monitored by IR spectroscopy; a) [( ⁇ SiO)Cr 2 (OSi(O t Bu)3)3]), b) [( ⁇ SiO) 4 Cr 2 ], c) [( ⁇ SiO) 6 Cr 2 ], d) CO reduced Phillips catalyst.
• Figure 7 shows the X-band (9.5 GHz) EPR spectrum of [(SiO)3Cr], measured at 8 mW and 110 K with modulation amplitude of 5 G.
• Figure 8 shows the X-band (9.5 GHz) EPR spectrum of [( ⁇ SiO) 6 Cr 2 ], measured at 8 mW and 110 K with modulation amplitude of 5 G.
• Figure 9 shows the X-band (9.5 GHz) EPR spectrum of [( ⁇ SiO) 3 Cr] prepared from Cr(0'Bu) 4 , measured at 32 mW and 1 10K with modulation amplitude of 1 G.
• a suitable decomposable ligand is trz ' -tert-butoxysilanolate (-OSi(O l Bu) 3 ).
• Chromium complexes such as (tBuO) 3 CrOSi(OtBu) 3 or (tBuO) 2 Cr(OSi(OtBu) 3 ) 2 (69) containing this ligand are known to decompose at relatively low temperatures (ca. 200 °C) to yield bulk silicate materials. Therefore this ligand was used in the following experiments.
• the solid-state structure of (1) is shown in Figure 2.
• (1) crystallizes as two independent molecules in the unit cell with similar bond lengths and angles, one of which is shown in Figure 2.
• (1) contains the two chromium atoms in slightly distorted square planar geometries, typical for high spin Cr(II) species, with a butterflied diamond ⁇ 2 -disiloxy-dicromium core.
• the Cr-Cr distance in (1) is 2.884(2) A, which is outside the range of significant metal-metal bonding.
• the terminal Cr(2A)-0(lA) and Cr(lA)-0(4A) bonds are 1.934(4) and 1.984(4) A, respectively.
• the bridging Cr-0(2A) and Cr-0(3 A) distances are slightly longer than the terminal Cr-0 bonds.
• the -OSi(O l Bu) 3 ligand can also coordinate through the -O l Bu fragments, which occurs to satisfy the distorted Cr(II) square planar geometry; these distances are significantly longer (2.109(4) and 2.167(4) A, respectively).
• These Cr-0 bond distances are similar to other chromium siloxide complexes.
• bipyramidyl which is typical of five-coordinate metal species.
• the Cr-Cr distance in (5) is 2.966(1 ), slightly longer than for (1).
• the Cr K-edge XANES spectrum of the Cr(III) dimer (5) shows similar edge and pre- edge featuies as the N 2 0 oxidized material (4).
• the results indicate that the chromium centers are in the +3 oxidation state and have a similar coordination geometry as the Cr(IIT) dimer (5) thereby supporting for (4) the structure [( ⁇ Si0)6Cr 2 ].
• the results of the EXAFS analysis for (5) and [( ⁇ Si0)6Cr 2 ] are also compiled in Table 1. Both of these species must contain a Cr-Cr scattering path to obtain reasonable quality EXAFS fits.
• the polymerization activity of these materials was monitored in a glass-reactor equipped with an IR cell. In order to accurately determine the polymerization activities
• Sylopol-948 an amorphous silica support composed of very small particles that can fragment when polymer is formed avoiding mass transfer limitations, was used as a support for the chromium dimers.
• ethylene ca. 300 mbar
• the decay of ethylene was monitored by IR spectroscopy.
• [( ⁇ SiO)6Cr 2 ] (4) had initial ethylene polymerization activity of 19 kg PE (mol Cr*h) _1 , a value close to the productivity typically reported for Phillips catalyst.( 7) In contrast, [( ⁇ SiO) 4 Cr 2 ] (3) had initial polymerization activity of 1.6 kg PE (mol Cr*h) _1 , an activity that is one order of magnitude less than Phillips catalyst and
• Hexamethyldisiloxane was distilled from CaH 2 under Ar and stored over molecular sieves. C 6 D 6 was vacuum distilled from purple Na/benzophenone. NaHMDS was synthesized from HMDS and NaH in refluxing toluene. HOSi(OtBu) 3 was obtained from Sigma- Aldrich and used as received. N 2 0 was passed through activated 4A molecular sieves prior to use. Ethylene was passed through activated 4 A molecular sieves and BASF
• the combined C63 ⁇ 4 washings contained 0.23 mmol of HOSi(O l Bu) 3 that was quantified by 1H NMR with Cp 2 Fe internal standard. Elemental analysis: 6.70 % C; 1.20 % H; 1.60 % Cr.
• Si0 2 _ ( 7oo ) (1.00 g, 0.26 mmol surface SiOH) and Cr(O l Bu)4 (108 mg, 0.31 mmol, 1.2 equiv) dissolved in a few mL of benzene were stirred for 3 h at RT in a double-Schlenk. Filtration and washing with benzene until the washings were colorless yielded a deep blue colored silica. To the washings, ferrocene (37.9 mg, 0.2 mmol) was added for a mass balance analysis by 1 H-NMR. Quantification of the signals assigned to ferrocene and tert-butanol showed, that 0.17 mmol of l BuOH was released.
• the blue material (202.7 mg, 0.03 mmol Cr) was thermally decomposed (ramp to 300 °C in 1 h, 300 °C for 1 h, ramp up to 400 °C in 20 min, 400 °C for 3 h) while trapping all volatiles. A color change from deep blue to a dark greyish blue was observed.
• the volatiles were analyzed by GC and by 1H NMR with ferrocene (9.9 mg, 0.05 mmol) as internal standard for a mass balance. Quantification of the signals assigned to ferrocene, isobutylene and tert- butanol respectively showed, that 3.7 equiv of isobutylene and 0.5 equiv of l BuOH was released per chromium grafted. From this procedure [( ⁇ SiO) 3 Cr] (170 mg) was obtained. ///. Analytical Procedures
• X-ray absorption spectroscopy (XAS) measurements at Cr K-edge were performed at the SuperXAS beamline at the Swiss Light Source (Paul Scherrer Institute, Villigen, Switzerland).
• the SLS is a third generation synchrotron, which operates under top up mode, 2.4 GeV electron energy, and a current of 400 mA.
• the SuperXAS beamline is positioned on one of three super-bent ports.
• the incident beam was collimated by Si-coated mirror at 2.8 mrad, monochromatized using a double crystal Si(l 1 1) monochromator, and focused with Rh coated toroidal mirror (at 2.8 mrad) down to 100x100 ⁇ .
• the beam intensity was of 4-
• Powder samples for fluorescence detection were sealed in quartz capillaries (0.01mm wall thickness, 0.9mm outer diameter, Hilgenberg GmbH) in a glovebox using vacuum grease (Apiezon Products) and wax, and stored in sealed glass tubes under argon that were opened just before the measurements.
• XANES data were collected in transmission mode at 298 K. Several scans using fast shutter, short acquisition time and reduced beam intensity were performed to be sure that X- ray beam damage did not take place. EXAFS data in fluorescence mode were acquired for (1), [( ⁇ SiO)Cr 2 (OSi(O t Bu) 3 ) 3 ] (2), [( ⁇ SiO) 4 Cr 2 ] (3), and [( ⁇ SiO) 6 Cr 2 ] (4) at 100 K, and in transmission mode for (5) at 298 K. XANES data for all compounds is measured at 298 K in transmission mode to minimize self absorption effects.
• EXAFS data was taken from 5900 - 6800 eV, with a scan time of approximately 30 minutes, multiple scans performed on fresh spots (to avoid the beam damage) were averaged to reduce the noise.
• XANES and EXAFS data were analysed using the Ifeffit program package. (62)
• the X-Ray crystal structures of (1) contains a first coordination shells with four different Cr-oxygen bonds lengths.
• UV-Vis spectra were collected on Agilent Technologies, Cary Series UV-Vis-NIR Spectrophotometer in DRIFT mode. The measurements were taken from 200 nm to 1100 nm at a scanning rate of 50 nm/min.
• EPR Electro paramagnetic resonance spectroscopy
• X-band EPR spectra (9.5 GHz) were measured at RT and at 110 K with a centre field of 2500 G with bandwidth 4000 G and with 8 mW or 32 mW and modulation amplitudes of 1 or 5 G.
• Infrared of adsorbed CO is a good method to check the catalyst. IR spectra were recorded at room temperature on each material presented in Figure 10 on self-supporting disks (ca. 10 mg) that were exposed to 10 mbar of CO.
• the chromium catalyst (100 mg, 120 ⁇ Cr) was mixed with NaCl (ca 2 g, average particle size: 50 ⁇ ) in a glovebox and loaded into a fixed bed reactor that has been described previously. (63) The apparatus was preheated at 70 °C under a flow of Ar until the internal temperature stabilized, and a mixture of ethylene (6 bar) and He (3 bar) was passed through the fixed bed reactor for 75 sec. Short reaction times were used to ensure accurate
• High temperature SEC High temperature SEC
• High-temperature size exclusion chromatography (HT-SEC) measurements were performed using a Viscotek High Temperature Triple Detection GPC (HT-GPC) system that incorporated a differential refractive index, a viscometer, and a light scattering detector.
• HT-GPC Viscotek High Temperature Triple Detection GPC
• 1 ,2,4-Trichlorobenzene (TCB) was used as the mobile phase at a flow rate of 1 mL min "1 .
• TCB was stabilized with 2,6-di(tert-butyl)-4-methylphenol. All polymers were injected at a concentration of 5 mg mL _1 .
• the separation was carried out on three mixed bed columns (300x7.8 mm from Malvern Instrument) and a guard column (75x7.5 mm). Columns and detectors were maintained at 150°C.
• the Omnisec software was used for data acquisition and data analysis. The molar masses were measured using the triple detection. The mo

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