Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0204—Ethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• • 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

Definitions

• the present invention is directed to an olefin polymerization catalyst system based upon a member of the class of conventional titanium trichloride catalysts, in association with a novel cocatalyst based upon an aluminum trialkyl and a silane component as further described herein.
• the cocatalyst provides isotactic olefin polymers with higher catalytic activity than catalyst systems of the prior art.
• Ziegler-Natta catalyst systems developed for use in the polymerization of olefins, especially alpha-olefins such as ethylene and propylene, were catalyst systems that include titanium and aluminum in the form of titanium trihalide catalysts and organoaluminum compounds as cocatalysts.
• the relatively simple nature of these systems provided a compelling case for their use compared to more complex so-called 'high activity' Ziegler-Natta solid catalyst components which include titanium (IV) and magnesium.
• the polymerization of propylene among other stereochemical monomers concerns itself with the structural ordering of the resulting polymer.
• the most desirable polymers for industrial use are isotactic, those where in recurring triads, the depending methyl groups are on the same side of the molecule, affording long term order and hence properties related to developed crystallinity.
• polypropylene of greater than 95 to 97% heptane insolubles can be sustainably produced at an activity in excess of 6000- 8000 lb/lb catalyst with a crystalline melting point of at least 160 to 165°C and bulk densities in excess of 24.
• the selected electron donor will exhibit an ultraviolet absorption wavelength of less than about 250 nanometers, reflective of the strength of electron bonding and hence the relative ease of donative coordination. The lower wavelengths are associated with more strongly bound electron pairs and thus evidence more moderate donative potential.
• the coordinate use of a selected internal donor, and the trialkyl aluminum/alkoxysilane cocatalysts moderates and modulates the oxidation reduction reaction in polymerization so as to maintain and stabilize in a relative steady state the active form of the Ti ""3 catalyst, preventing overreduction of the active species while directing and ordering the production of the desired isotactic product in the case of propylene.
• the internal donor is believed as well to assist in the forming of the desired ff or ⁇ crystalline form of the TiCl 3 component.
• a catalyst system which comprises, as a catalyst, a titanium (III) containing component, such as TiX 3 .rMX m , where X and X are the same or different and are halogen; M is a metal of Group III of the Periodic Table of the Elements; ⁇ is an integer of 3; and r is 0 to 0.7.
• a titanium (III) containing component such as TiX 3 .rMX m , where X and X are the same or different and are halogen; M is a metal of Group III of the Periodic Table of the Elements; ⁇ is an integer of 3; and r is 0 to 0.7.
• the titanium (III) component is associated with a selected electron donor of moderate donative potential, preferably an ether or an ester.
• a selected electron donor of moderate donative potential preferably an ether or an ester.
• catalyst component X and X are chlorine; and is aluminum. More preferably, r is 0 to 0.33.
• the cocatalyst component comprises a trialkyl aluminum compound modified with a silane compound having the structural formula (OR )- a _ E ,-. 3 SiR a ss R 3 ⁇ - t , where R x is hydrocarbyl; and R 2 and R 3 are the same or different and are hydrocarbyl; p is 0 or an integer of 1 or 2; and g is an integer of 1 to 3, with the proviso that the sum of p and g does not exceed 3.
• the trialkylaluminum compound which functions as a cocatalyst has the structural formula
• R is to C e alkyl. More preferably, in this component R is C ⁇ to C 4 alkyl. Most preferably, this component is triethylaluminum.
• the TiCl 3 or TiCl 3 .AA component is associated with an electron donor, preferably an organic ether or ester.
• This titanium (III) component may comprise as prepared the electron donor, as described, for example in U.S. Patent Nos. 4,060,593 or 4,115,533 incorporated herein by reference.
• titanium tetrachloride may be reduced in situ, for example, with an aluminum alkyl, reacted with an electron donor and activated with titanium tetrachloride to form the active TiCl 3 component, preferably in the 8 " or ⁇ form.
• the preferred electron donor is an organic ether such as a di-alkyl ether, preferably C 6 - C 12 alkyl, and most preferably di- isoamyl ether, di-n-octyl ether or di-n-dodecyl ether.
• organic ether such as a di-alkyl ether, preferably C 6 - C 12 alkyl, and most preferably di- isoamyl ether, di-n-octyl ether or di-n-dodecyl ether.
• the electron donor is employed in an amount of 0.1 to 0.4 mm/mol TiCl 3 , preferably 0.2 to 0.3 mm/mol TiCl 3 .
• the source of titanium (III) may be free of an electron donor, for example, it may be a coground TiCl 3 /AlCl 3 as is known and available in the art.
• the titanium (III) containing component is associated with an electron donor prior to use.
• the preferred electron donor is an organic ester such as a compound having the structural formula
• R 4 is hydrogen, C x to C 4 alkyl or C ⁇ to C 4 alkoxy; R 5 is C a. to C 4 alkyl; and n is 0 or an integer of 1 to 3.
• This electron donor component more preferably, is a compound where R 4 is hydrogen; R 5 is C z to C 4 alkyl; and n is 1. Most preferably, this component is butyl benzoate.
• the molar ratio of the titanium component to ester is in the range of between about 1:1 and about 20rl. More preferably, this molar ratio is in the range of between about 3:1 and about 6:1.
• the electron donor component is preferably introduced into the catalyst system by being intimately blended together with the titanium (III) component.
• this intimate blending is provided by milling or simple mixing. More preferably, this blending is accomplished by milling, especially by ballmilling.
• R x is hydrocarbyl; 2 and R 3 are the same or different and are hydrocarbyl; p is 0 or an integer of 1 or 2; and q is an integer of 1 to 3, with the proviso that the sum of p and q does not exceed 3.
• R x is alkyl; and R 2 and R 3 are the same or different and are alkyl or cycloalkyl. More preferably, this component is a silane compound where R is C ⁇ to C ⁇ alkyl; and R 2 and R 3 are the same or different and are C to C s alkyl or cycloalkyl.
• R x is C-**. to C 4 alkyl; and R 2 and R 3 are the same or different and are alkyl or cycloalkyl. Even still more preferably, p is 0 or 1; and q is 1.
• the silane cocatalyst modifier is one or more of isobutyltrimethoxysilane, isobutylisopropyldimethoxysilane, diisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane or dicyclopentyldimethoxysilane.
• the second catalyst component is isobutylisopropyldimethoxysilane or diisopropyldimethoxy- silane.
• the components of the catalyst system are present in concentrations such that the molar ratio of the titanium-(III)-containing compound to the silane compound is in the range of between about 1:0.2 and about 1:1.2. Preferably, this molar ratio is in the range of between about 1:0.4 and about 1:1.1. Still more preferably, this molar ratio is in the range of between about 1:0.5 and about 1:0.9.
• the molar ratio of the trialkylaluminum compound, to the silane compound is in the range of between about 5:1 and about 20:1. Preferably, this molar ratio is in the range of between about 7:1 and about 15:1. Still more preferably, the molar ratio of the trialkylaluminum component to the silane compound is in the range of between about 8:1 and about 12:1.
• the present invention is also directed to a process for polymerizing an olefin, generally in slurry or gas phase.
• an olefin is polymerized under olefinic polymerization conditions in the presence of the catalyst system of the subject invention.
• Olefinic polymerization conditions are preferably those that involve conducting the polymerization reaction at a temperature in the range of between about 20°C and about 150°C and at a pressure in the range of between about atmospheric and about 2,000 pounds per square inch gauge (psig) .
• the process of polymerizing an olefin is directed to alpha-olefins which are polymerized in the presence of a catalyst system within the scope of the present invention under alpha-olefin polymerization conditions which include a temperature in the range of between about 40°C and about 110°C and a pressure in the range of between about 100 psig and about 1000 psig.
• alpha-olefin polymerization conditions which include a temperature in the range of between about 40°C and about 110°C and a pressure in the range of between about 100 psig and about 1000 psig.
• the process of this invention is directed to the polymerization of an alpha-olefin having 2 to 8 carbon atoms under alpha-olefin polymerization conditions which include a polymerization reaction temperature in the range of between about 50°C and about 100°C and a polymerization reaction pressure of between about 200 psig and about 800 psig.
• the process of this invention involves the polymerization of an alpha-olefin having 2 to . 6 carbon atoms under alpha-olefin polymerization conditions comprising a temperature of -9-
• the process of the subject invention concerns the polymerization of an alpha-olefin selected from the group consisting of ethylene and propylene under alpha-olefin polymerization conditions comprising a temperature in the range between about 62°C and about 80°C and a pressure in the range of between about 350 psig and about 550 psig.
• the process of the present invention is directed to the polymerization of propylene under propylene polymerization conditions which involve a reaction at a temperature in the range of between about 65°C and about 90°C and at a pressure in the range between about 400 psig and about 500 psig.
• hydrogen may optionally be provided thereto.
• the reaction occurs in a so-called liquid pool wherein the only diluent is the olefin polymerized, preferably propylene.
• the reaction occurs in a stationary fluidized bed or a stirred bed.
• the polymerization may also be conducted in cascaded reactors, i.e., reactors whether for suspension, gas phase or high pressure polymerization, are linked functionally or in practice such that the polymerization product of the first reactor is further reacted, usually under different conditions, in a second reactor to -10-
• an aluminum alkyl or alkyl halide component is employed as a reductant; in consequence this component may have some catalyst reactivity before it is associated with the TEAL/silane cocatalyst component of this invention.
• This can be inconvenient for catalyst feed systems utilizing polymerizable monomer carrier such as is commonly the case in gas phase operations. Accordingly, in such instances it is typical to deactivate for example any residual aluminum chloride, which can conveniently be accomplished by reaction with butyl benzoate.
• the resulting coordination cocatalyst then relies solely upon the TEAL/silane system for cocatalyst function.
• a particular advantage of the present cocatalyst resides in its capacity to function effectively both with the titanium (III) catalysts and titanium (IV) catalysts, such that the respective catalysts used conjointly in a single reactor may be commonly cocatalyzed so to prepare polymer product of diverse characteristics, e.g., different molecular weight. These characteristics may then be controllably altered by suitable selection of catalyst ratio having regard for the individual characteristics such as activity levels, or stereoregulating capacity, etc.
• the invention is understood to relate as well to catalyst systems which include, in the broadest sense, transition metal (III) and (IV) combinations which are then commonly cocatalyzed with the disclosed TEAL/silane components.
• a catalyst system was prepared by combining titanium trichloride (0.04 g.),(itself prepared according to the protocol of Example 4 of U.S. Patent No. 4,115,533) isobutylisopropyldimethoxy-silane (IBIP) and triethylaluminum (TEAL) in a concentration such that the molar ratio of these components was 1.0:0.5:4.6, respectively.
• This catalyst system was introduced into a reactor free of air and water.
• the reactor into which the catalyst system was introduced was next charged with hydrogen gas (500 ml.) and liquid propylene (325 g., 650 ml.).
• the polymerization reaction was thereupon initiated by heating and pressurizing the reactor to a temperature of 70°C and a pressure of 460 psig. Concurrently with this heating and pressurizing step the stirrer, with which the reactor was equipped, was activated. The stirrer rotated at 400 revolutions per minute. The polymerization reaction, operated under these conditions, was continued for 1 hour. The reaction was terminated after 1 hour by venting the excess propylene.
• the polypropylene product of the polymerization reaction was weighed and analyzed.
• the polymer analysis constituted the determination of the concentration therein of titanium, a measure of undesirable catalyst incorporation therein, by quantitative analysis well known in the art.
• the polypropylene percent heptane insolubility was determined in a procedure wherein a finely ground sample (20 mesh) of the polypropylene obtained in the above-discussed polymerization reaction was heated at 100°C for 30 minutes in a vacuum oven. The heated sample, disposed in a tare container, i.e., a thimble, was then carefully weighed. The ground polymer, disposed in the thimble was thereupon disposed in an extraction flask already filled with approximately 150 ml. of n-heptane. The n-heptane was heated to boiling and refluxed, with the polypropylene sample disposed therein, for 90 minutes. After 90 minutes, reflexing ceased and the thimble containing the polypropylene sample was removed.
• the thimble containing the polypropylene sample was rinsed in acetone after which it was again heated in the same vacuum oven, at 100°C for 30 minutes.
• Percent heptane insolubility was determined as the ratio of the difference in net weight of the polypropylene before and after contact with boiling n- heptane for 90 minutes to the net polypropylene weight prior to such contact.
• melt flow rate determined in accordance with ASTM Test Procedure
• the activity of the catalyst in terms of polypropylene weight per unit weight of catalyst, was determined by weighing the polypropylene generated during the 1 hour polymerization run and dividing that number by the weight of catalyst charged into the reactor.
• Example 1 was identically reproduced but for the composition of the catalyst.
• Example 2 the molar ratio of titanium trichloride, to isobutylisopropyldimethoxysilane, to triethylaluminum, was 1:0.7:6.0. Again titanium trichloride, was present in an amount of 0.04 g.
• Example 1 was identically reproduced again but for the composition but for the relative amounts of the catalyst components of the catalyst system.
• Example 3 the molar ratio of titanium trichloride to isobutylisopropyldimethoxy-silane to triethylaluminum was 1:0.9:7.5. Again, the weight of the titanium trichloride component of the catalyst system was 0.04 g.
• Example 1 was identically reproduced but for the composition of the catalyst system.
• the catalyst system of this comparative example omitted the silane component, isobutylisopropyldimethoxysilane.
• the molar ratio of titanium trichloride to triethylaluminum was identical to the molar ratio of these components in Example 1. That is, the molar ratio of titanium trichloride to triethylaluminum was 1:4.6. Otherwise, the polymerization reaction was conducted in exact accordance with the polymerization conditions that existed during the polymerization of Example 1.
• the polypropylene generated during the 20 minute run was weighed to provide catalyst activity, albeit over this abbreviated 20 minute period.
• the stickiness of the polypropylene product was such that the only physical property that could be measured was an analysis of percent heptane insolubility of the polypropylene product, which analysis was determined in accordance with the procedure set forth in Example 1. That result, in view of low crystallinity of the polypropylene product, could only be certain to the extent that the percent heptane insolubility of the polypropylene product was less than 85%.
• a brief summary of this example is included in the Table.
• propylene was polymerized in accordance with the procedure set forth in Example 1.
• the catalyst system utilized in this example substituted the complex TiCl 3 .0.33AlCl 3 .
• the other components were identical with those of Example 1, viz- isobutylisopropyl-dimethoxysilane (IBIP) and triethylaluminum (TEAL) , respectively.
• This catalyst system also differed from the catalyst system of Example 1 in that it included butyl benzoate (BBE) (0.25 mole).
• BBE butyl benzoate
• the molar ratio of titanium compound to silane to aluminum compound to BBE was 1:0.9:7.0:0.25, respectively.
• the TiCl 3 .033AlCl 3 complex was introduced into the polymerization reactor after being ballmilled with the BBE component.
• the first catalyst component in this example TiCl 3 .0.33AlCl 3 , was present in an amount of 40 mg.
• Example 4 The polymerization reaction of Example 4 was reproduced but the silane utilized was isobutyltrimethoxysilane.
• Example 6 The results of Example 6 are incorporated in the Table.
• Example 4 A polymerization in accordance with Example 4 was reproduced. However, although the catalyst system of this example included TiCl 3 . 1C1 3 , as well as IBIP and TEAL as components, this catalyst system did not include butyl benzoate (BBE) . This catalyst system also differed from the catalyst system of Example 4 in that the molar ratio of titanium compound to silane to aluminum compound was 1.0:0.9:10.0, respectively. Moreover, in this example the titanium (III) catalyst component was introduced into the polymerization reactor in an amount such that its total weight was 75 mg. Finally, the reaction time was 2 hours instead of the 1 hour duration employed in Example 4.
• BBE butyl benzoate
• Example 4 was identically reproduced except for the omission of the silane component. That is, the catalyst system comprised the complex TiCl 3 .0.33AlCl 3 (40 g.), ballmilled with BBE, and triethylaluminum present in a molar ratio of the Ti complex to TEAL to BBE of 1:7.0:0.25.
• Example 4 was reproduced except that it was conducted in accordance with prior art teachings. That is, although polymerization reaction conditions were identical with Example 4 and the catalyst system again comprised 40 milligrams of TiCl 3 .0.33A1C1 3 , the aluminum-containing compound was not triethylaluminum but rather, in accordance with prior art teachings, diethylaluminum chloride. As in Comparative Example 2, the molar ratio of the titanium compound to the organoaluminum compound, diethylaluminum chloride, was again 1:7.0 with no silane present.
• Example 7 differed by the presence in the catalyst system of Example 7 of the silane IBIP which silane was not present in the catalyst system of Comparative Example 3.
• the aluminum compound of Example 7, in accordance with the present invention was a trialkylaluminum compound, TEAL, whereas the aluminum compound of the catalyst system of Comparative Example 3 was diethylaluminum chloride.
• the catalyst system of Comparative Example 3 had marginally improved catalyst activity compared to the catalyst system of Example 7.
• the degree of polymerization of the polypropylene produced using the catalyst system of Comparative Example 3 was significantly lower than the polypropylene produced using the catalyst system of Example 7. This is manifested by the melt flow rate which, as those skilled in the art are aware, is a measure of polymer viscosity, which is proportional to the degree of polymerization. The lower the melt flow rate the greater the polypropylene viscosity.

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• 1993
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