CA2077744C - Homogeneous-heterogeneous catalyst system for polyolefins - Google Patents
Homogeneous-heterogeneous catalyst system for polyolefins Download PDFInfo
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- CA2077744C CA2077744C CA002077744A CA2077744A CA2077744C CA 2077744 C CA2077744 C CA 2077744C CA 002077744 A CA002077744 A CA 002077744A CA 2077744 A CA2077744 A CA 2077744A CA 2077744 C CA2077744 C CA 2077744C
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- 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
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- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63904—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with another component of C08F4/62
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
Abstract
This invention concerns a catalyst system comprising at least one homogeneous catalyst and at least one heterogeneous catalyst, specifically, a metallocene catalyst and a conventional Ziegler-Natta catalyst, respectively. This invention is useful in the polymerization of any polymer in which separate polymerizations with a homogeneous catalyst and with a heterogeneous catalyst are possible, but preferably, polymerization of olefins, more preferably, a-olefins, and, most preferably, propylene. This invention provides a catalyst system which facilitates use of a homogeneous catalyst but eliminates the disadvantages of such a system. This invention produces a polymer with molecular weight distribution (MWD) as broad or broader than the MWD of the heterogeneous catalyst alone. Hydrogen can be used to control molecular weight distribution of a polymer produced with this invention.
Description
~~~~r~r~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 HOMOGENEOUS-HETEROGENEOUS CATALYST SYSTEM FOR POLYOLEFINS
SPECIFICATION
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION: This invention relates to a catalyst system which is a combination of at least one homogeneous catalyst and at least one heterogeneous catalyst. Changing the homogeneous catalyst used with the heterogeneous catalyst effects the molecular weight distribution of the resulting polymer.
DESCRIPTION OF THE PRIOR ART: It is known that two or more homogeneous catalysts, such as those based on metallocene com pounds, may be combined to effect properties, such as molecular weight distribution. U.S. Patent No. 4,530,914 discloses use of a catalyst system comprising two or more metallocenes in the polymerization of a-olefins, primarily ethylene, to obtain a broad molecular weight distribution. The metallocenes each have different propagation and termination rate constants. The metallocenes are mixed with an alumoxane to form the catalyst system.
It is also known that metallocenes may be affixed to a support to simulate a heterogeneous. catalyst. In U.S. Patent No. 4,808,561 discloses reacting a metallocene with an alumoxane and forming a reaction product in the presence of a support. The support is a porous material like talc, inorganic oxides such as Group IIA, IIIA
IVA OR IVB metal oxides like silica, alumina, silica-alumina, magnesia, titania, zirconia and mixtures thereof, and resinous ~ 0'~'~'~ 4 ~~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 material such as polyolefins like finely divided polyethylene. The metallocenes and alumoxanes are deposited on the dehydrated support material.
In U.S. Patent No. 4,701,432 a support is treated with at least one metallocene and at least one non-metallocene transition metal compound. To form a catalyst system a cocatalyst comprising an alumoxane arid an organometallic compound of Group IA, IIA, IIB
and IIIA is added to the supported metallocene/non-metallocene.
The support is a porous solid such as talc or inorganic oxides or resinous materials, preferably an inorganic oxide, such as silica, alumina, silica-alumina, magnesia, titania or zirconia, in finely divided form. By depositing the soluble metallocene on the support material it is converted to a heterogeneous supported catalyst.
The transition metal compound, such as TiCl4, is contacted with the support material prior to, after, simultaneously with or separately from contacting the metallocene with the support.
An advantage of a homogeneous (metallocene) catalyst system is the very high activity of the catalyst and the narrow molecular weight distribution of the polymer produced with a metallocene catalyst system. The metallocene catalysts suffer from a disadvan-tage in that the ratio of alumoxane cocatalyst to metallocene is high, requiring extensive treatment of the polymer product to remove the aluminum. Another disadvantage of the homogenous catalyst system is that the polymer product has small particle size P ~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 and low bulk density. Another disadvantage of the homogeneous catalyst system is that the reactor fouls during polymerization.
It would be advantageous to provide a catalyst system which facilitates use of a homogeneous catalyst but eliminates the disadvantages of such a system. A combination of a homogeneous catalyst with a heterogeneous catalyst in a single reactor will eliminate the disadvantages of the homogeneous catalyst alone and will facilitate use of a homogeneous catalyst. A combination of a homogeneous catalyst with a heterogeneous catalyst in a single reactor will also provide a means to control molecular weight distribution and polydispersity.
DESCRIPTION OF THE DRAWINGS
Figure 1 is a chart of gel permeation chromatography (GPC) of a polymer produced with a conventional Ziegler-Natta heterogeneous catalyst.
Figure 2 is a chart of GPC of a polymer produced with a metallocene homogeneous catalyst.
Figure 3 is an overlay of Figures 1 and 2.
Figure 4 is a chart of GPC of a polymer produced with a homogeneous-heterogeneous catalyst system.
Figure 5 is a chart of GPC of a polymer produced with ~a homogeneous-heterogeneous catalyst system and a low level of hydrogen (3.9 mmol).
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 HOMOGENEOUS-HETEROGENEOUS CATALYST SYSTEM FOR POLYOLEFINS
SPECIFICATION
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION: This invention relates to a catalyst system which is a combination of at least one homogeneous catalyst and at least one heterogeneous catalyst. Changing the homogeneous catalyst used with the heterogeneous catalyst effects the molecular weight distribution of the resulting polymer.
DESCRIPTION OF THE PRIOR ART: It is known that two or more homogeneous catalysts, such as those based on metallocene com pounds, may be combined to effect properties, such as molecular weight distribution. U.S. Patent No. 4,530,914 discloses use of a catalyst system comprising two or more metallocenes in the polymerization of a-olefins, primarily ethylene, to obtain a broad molecular weight distribution. The metallocenes each have different propagation and termination rate constants. The metallocenes are mixed with an alumoxane to form the catalyst system.
It is also known that metallocenes may be affixed to a support to simulate a heterogeneous. catalyst. In U.S. Patent No. 4,808,561 discloses reacting a metallocene with an alumoxane and forming a reaction product in the presence of a support. The support is a porous material like talc, inorganic oxides such as Group IIA, IIIA
IVA OR IVB metal oxides like silica, alumina, silica-alumina, magnesia, titania, zirconia and mixtures thereof, and resinous ~ 0'~'~'~ 4 ~~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 material such as polyolefins like finely divided polyethylene. The metallocenes and alumoxanes are deposited on the dehydrated support material.
In U.S. Patent No. 4,701,432 a support is treated with at least one metallocene and at least one non-metallocene transition metal compound. To form a catalyst system a cocatalyst comprising an alumoxane arid an organometallic compound of Group IA, IIA, IIB
and IIIA is added to the supported metallocene/non-metallocene.
The support is a porous solid such as talc or inorganic oxides or resinous materials, preferably an inorganic oxide, such as silica, alumina, silica-alumina, magnesia, titania or zirconia, in finely divided form. By depositing the soluble metallocene on the support material it is converted to a heterogeneous supported catalyst.
The transition metal compound, such as TiCl4, is contacted with the support material prior to, after, simultaneously with or separately from contacting the metallocene with the support.
An advantage of a homogeneous (metallocene) catalyst system is the very high activity of the catalyst and the narrow molecular weight distribution of the polymer produced with a metallocene catalyst system. The metallocene catalysts suffer from a disadvan-tage in that the ratio of alumoxane cocatalyst to metallocene is high, requiring extensive treatment of the polymer product to remove the aluminum. Another disadvantage of the homogenous catalyst system is that the polymer product has small particle size P ~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 and low bulk density. Another disadvantage of the homogeneous catalyst system is that the reactor fouls during polymerization.
It would be advantageous to provide a catalyst system which facilitates use of a homogeneous catalyst but eliminates the disadvantages of such a system. A combination of a homogeneous catalyst with a heterogeneous catalyst in a single reactor will eliminate the disadvantages of the homogeneous catalyst alone and will facilitate use of a homogeneous catalyst. A combination of a homogeneous catalyst with a heterogeneous catalyst in a single reactor will also provide a means to control molecular weight distribution and polydispersity.
DESCRIPTION OF THE DRAWINGS
Figure 1 is a chart of gel permeation chromatography (GPC) of a polymer produced with a conventional Ziegler-Natta heterogeneous catalyst.
Figure 2 is a chart of GPC of a polymer produced with a metallocene homogeneous catalyst.
Figure 3 is an overlay of Figures 1 and 2.
Figure 4 is a chart of GPC of a polymer produced with a homogeneous-heterogeneous catalyst system.
Figure 5 is a chart of GPC of a polymer produced with ~a homogeneous-heterogeneous catalyst system and a low level of hydrogen (3.9 mmol).
~A ~ ~~ y9 ~
SERTAL N0. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 Figure 6 is a chart of GPC of a polymer produced with a homogeneous-heterogeneous catalyst system and a high level of hydrogen (15.7 mmol).
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide a catalyst system which eliminates extensive treatment of the polymer product to remove impurities.
And, an object of this invention is to provide a catalyst system which produces polymer with little or no small particle size and high bulk density.
Also, an obj ect of this invention is to provide a catalyst system which eliminates reactor fouling during polymerization.
Further, an object of this invention is to provide a catalyst system which controls the molecular weight distribution by varying the catalyst.
Additionally, an object of this invention is to provide a catalyst system which produces polymer with a bimodal molecular weight distribution.
As well, an object of this invention is to provide a catalyst 2p system which produces a reactor blend of polymer with a broad molecular weight distribution in a single reactor.
In addition, an object of this invention is to provide a process for using hydrogen to control molecular weight distribu-tion.
..
SERTAL N0. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 Figure 6 is a chart of GPC of a polymer produced with a homogeneous-heterogeneous catalyst system and a high level of hydrogen (15.7 mmol).
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide a catalyst system which eliminates extensive treatment of the polymer product to remove impurities.
And, an object of this invention is to provide a catalyst system which produces polymer with little or no small particle size and high bulk density.
Also, an obj ect of this invention is to provide a catalyst system which eliminates reactor fouling during polymerization.
Further, an object of this invention is to provide a catalyst system which controls the molecular weight distribution by varying the catalyst.
Additionally, an object of this invention is to provide a catalyst system which produces polymer with a bimodal molecular weight distribution.
As well, an object of this invention is to provide a catalyst 2p system which produces a reactor blend of polymer with a broad molecular weight distribution in a single reactor.
In addition, an object of this invention is to provide a process for using hydrogen to control molecular weight distribu-tion.
..
~.',~'~r~N~~~~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDX, RAUSCHER COS627 These and other objects are accomplished by a catalyst system comprising at least one homogeneous catalyst arid at least one heterogeneous catalyst, i.e, metallocene catalyst and conventional Ziegler-Natta catalyst, respectively.
DETAILED DESCRIPTION OF THE INVENTION
The multi-catalyst system of the present invention is useful in the polymerization of any polymer in which separate polymeriza-tions with a homogeneous catalyst and with a heterogeneous catalyst are possible. Preferably, the mufti-catalyst system is useful in the polymerization of olefins, more preferably, a-olefins, and, most preferably, propylene.
The mufti-catalyst system of the present invention is obtained by mixing the components of at least one homogeneous catalyst system and at least one heterogeneous system. The components may be combined in any order. Generally, the components of a homoge-neous catalyst system are a metallocene compound and an ionizing agent. Generally, the components of a heterogeneous catalyst system are an aluminum alkyl and a transition metal compound with, optionally, an electron donor.
Any of the conventional heterogeneous Ziegler-Natta transition metal compound catalyst components can be used as the heterogeneous catalyst of the catalyst system of the present invention. The compound is preferably of the general formula MR'~X where M is the metal, R is a halogen or a hydrocarboxyl and x is the valence of ~~ ~ ~1~~~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 the metal. Preferably, M is a Group IVB, VB or VIB metal, more preferably a Group IVB, and most preferably titanium. Preferably, R is chlorine, bromine, an alkoxy or a phenoxy, more preferably chlorine or ethoxy and most preferably, chlorine. Illustrative examples of the transition metal compound catalyst components are TiCl4, TiBr4, Ti (OCZHS) 3C1, Ti (OCZHS) C13, Ti (OC4H9) 3C1, Ti (OC3H~) ZClZ, Ti (OC6H~3) ZCl2, Ti (OCZHS) zBrz and Ti (OC~ZHZS) C13. Mixtures of the transition metal compounds may be used. No restriction on the number of transition metal compounds is made as long as at least one transition metal compound is present.
The transition metal compound may be either supported or unsupported. If supported, the support should be an inert solid which is chemically unreactive with any of the components of the heterogeneous or homogeneous catalyst.
The aluminum alkyl is of the general formula A1R'3 where R' is an alkyl of from 1-8 carbon atoms and R' may be the same or different. Examples of aluminum alkyls are trimethyl aluminum (TMA), triethyl aluminum (TEA1) and triisobutyl aluminum (TiBAl).
The preferred aluminum alkyl is TEA1.
The electron donor is any one of the electron donors which are effective with Ziegler-Natta catalysts. Typically, an electron donor is an organosilicon compound. Examples of electron donors are methylcyclohexyldimethyoxysilane (MCMS), diphenyldimethoxy silane (DPMS) and isobutyltrimethoxysilane (IBMS). Other examples of electron donors are disclosed in U.S. Patent Nos. 4,21F3,339;
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDX, RAUSCHER COS627 These and other objects are accomplished by a catalyst system comprising at least one homogeneous catalyst arid at least one heterogeneous catalyst, i.e, metallocene catalyst and conventional Ziegler-Natta catalyst, respectively.
DETAILED DESCRIPTION OF THE INVENTION
The multi-catalyst system of the present invention is useful in the polymerization of any polymer in which separate polymeriza-tions with a homogeneous catalyst and with a heterogeneous catalyst are possible. Preferably, the mufti-catalyst system is useful in the polymerization of olefins, more preferably, a-olefins, and, most preferably, propylene.
The mufti-catalyst system of the present invention is obtained by mixing the components of at least one homogeneous catalyst system and at least one heterogeneous system. The components may be combined in any order. Generally, the components of a homoge-neous catalyst system are a metallocene compound and an ionizing agent. Generally, the components of a heterogeneous catalyst system are an aluminum alkyl and a transition metal compound with, optionally, an electron donor.
Any of the conventional heterogeneous Ziegler-Natta transition metal compound catalyst components can be used as the heterogeneous catalyst of the catalyst system of the present invention. The compound is preferably of the general formula MR'~X where M is the metal, R is a halogen or a hydrocarboxyl and x is the valence of ~~ ~ ~1~~~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 the metal. Preferably, M is a Group IVB, VB or VIB metal, more preferably a Group IVB, and most preferably titanium. Preferably, R is chlorine, bromine, an alkoxy or a phenoxy, more preferably chlorine or ethoxy and most preferably, chlorine. Illustrative examples of the transition metal compound catalyst components are TiCl4, TiBr4, Ti (OCZHS) 3C1, Ti (OCZHS) C13, Ti (OC4H9) 3C1, Ti (OC3H~) ZClZ, Ti (OC6H~3) ZCl2, Ti (OCZHS) zBrz and Ti (OC~ZHZS) C13. Mixtures of the transition metal compounds may be used. No restriction on the number of transition metal compounds is made as long as at least one transition metal compound is present.
The transition metal compound may be either supported or unsupported. If supported, the support should be an inert solid which is chemically unreactive with any of the components of the heterogeneous or homogeneous catalyst.
The aluminum alkyl is of the general formula A1R'3 where R' is an alkyl of from 1-8 carbon atoms and R' may be the same or different. Examples of aluminum alkyls are trimethyl aluminum (TMA), triethyl aluminum (TEA1) and triisobutyl aluminum (TiBAl).
The preferred aluminum alkyl is TEA1.
The electron donor is any one of the electron donors which are effective with Ziegler-Natta catalysts. Typically, an electron donor is an organosilicon compound. Examples of electron donors are methylcyclohexyldimethyoxysilane (MCMS), diphenyldimethoxy silane (DPMS) and isobutyltrimethoxysilane (IBMS). Other examples of electron donors are disclosed in U.S. Patent Nos. 4,21F3,339;
4,395,360; 4,328,122; 4,473,660; 4,55?,,173 aild 4,547,552 The homogeneous catalyst component may be a metallocene or cyclopentadienide, i.e., a 'metal derivative of a cyclopentadiene.
The metallocene should ccnt~~:in two cyclopentadiene rings and be of the general formula:
R"b ( CpR4 ) ( CpR ~ 4 ) MR*~-2 where R" is a bridge imparting stereoridigity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 ~~r 1, Cp is a cyclopentadi~~nyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being the same or different, ea~~h (CpR4) and (CpR'~.) being the same or different, M is a Group IIIB, IVB, VB or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carhop atoms, v is the valence of M.
Pr~sferably, b is 1 and R" is a hydrocarbyl radical, more prefera-bl:~ an alkenyl radical having one to four carbon atoms, a dialkyl germanium, a dialkyl silicon., an alkyl phosphine or amine radical, such as a dimethyl silyl radical, an ethylenyl radical or a isopropenyl radical and, most preferably, is an ethylenyl radical.
Prf~ferably, (CpR4) is an substituted cyclopentadienyl ring such that it is 3-t-butyl-cyclopentadienyl, indenyl or cyclopentadienyl and (CpR'4) is a substituted cyclopentadienyl ring such that it is fluorenyl, indenyl or fluox-enyl, respectively; most preferably, (CpR4) is indenyl and (CpR'4) is indenyl. Preferably, M is a Group IVB metal, most preferably zirconium, which has a valence of 4.
Preferably, R* is a halogen or alkyl, most preferably chlorine or met:hyl .
The ionizing agent is an alumoxane, an aluminum alkyl, other Lewis acid or a combination thereof which will ionize a neutral met:allocene compound to form a cationic metallocene catalyst.
Examples of such ionizing agents are methyl alumoxane (MAO), tri.ethyl aluminum (TEAL) and. tris(pentafluorophenyl)boron. Other ionizing agents are disclosed in European Patent Publication Nos.
0-~'.77-003 and 0-277-004.
By using a multi-catalyst system having at least one homoge-neous catalyst and at least one heterogeneous catalyst a polymer can be produced with molecular weight distribution (MWD) as broad or broader than the MWD of the heterogeneous catalyst alone. MWD
can be represented by a chart of gel permeation chromatography (GF~C). The homogeneous catalyst produces a polymer with a MWD
which is narrow relative to ~~ polymer produced by a heterogeneous.
For example, using a heterogeneous catalyst alone produces a polymer with a MWD of approximately 5-7 (Figure 1) and using a homogeneous catalyst alone produces a MWD of approximately 2-3.5 (Fi.gure 2). By superimposing Figure 1 on Figure 2 (Figure 3), it can be predicted that using 'the two catalysts together will result in a polymer having a MWD of 5-7. When the two catalysts are used together in an actual polymerization, a polymer having a MWD of 5-7 ~~~~~ a~~i SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 results, as shown is Figure 4. A comparison of Figures 3 and 4 show a near identity in the shape and location of the plot.
By using different ratios of the homogeneous: heterogeneous catalysts, the polydispersity, i.e., the distribution of molecular weights, can be effected. Since the molecular weight of the polymer produced with the homogeneous catalyst is different from that of the heterogeneous catalyst, changing the relative amount of one catalyst to another in a multi-catalyst system of this invention will change the polydispersity of the polymer produced.
The effect of hydrogen on a catalyst system having one or more homogeneous catalysts alone is known to be negligible. The effect of hydrogen on a catalyst system having one or more heterogeneous catalysts alone is known to have an inverse proportional effect on the peak molecular weight of the polymer, but there is no effect on molecular weight distribution. However, when a catalyst system comprises one or more homogeneous catalysts and one or more heterogeneous, the effect of hydrogen in decreasing the peak molecular weight of the polymer produced by the heterogeneous cataly$t while the polymer produced by the homogeneous catalyst remains unaffected results in on overall change in the molecular weight distribution. The effect of using a relative low amount of hydrogen compared to using a relative high amount of hydrogen is shown in Figures 5 and 6, respectively. Therefore, hydrogen can be used to control molecular weight distribution of a polymer produced by a multi-catalyst of the present invention.
The metallocene should ccnt~~:in two cyclopentadiene rings and be of the general formula:
R"b ( CpR4 ) ( CpR ~ 4 ) MR*~-2 where R" is a bridge imparting stereoridigity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 ~~r 1, Cp is a cyclopentadi~~nyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being the same or different, ea~~h (CpR4) and (CpR'~.) being the same or different, M is a Group IIIB, IVB, VB or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carhop atoms, v is the valence of M.
Pr~sferably, b is 1 and R" is a hydrocarbyl radical, more prefera-bl:~ an alkenyl radical having one to four carbon atoms, a dialkyl germanium, a dialkyl silicon., an alkyl phosphine or amine radical, such as a dimethyl silyl radical, an ethylenyl radical or a isopropenyl radical and, most preferably, is an ethylenyl radical.
Prf~ferably, (CpR4) is an substituted cyclopentadienyl ring such that it is 3-t-butyl-cyclopentadienyl, indenyl or cyclopentadienyl and (CpR'4) is a substituted cyclopentadienyl ring such that it is fluorenyl, indenyl or fluox-enyl, respectively; most preferably, (CpR4) is indenyl and (CpR'4) is indenyl. Preferably, M is a Group IVB metal, most preferably zirconium, which has a valence of 4.
Preferably, R* is a halogen or alkyl, most preferably chlorine or met:hyl .
The ionizing agent is an alumoxane, an aluminum alkyl, other Lewis acid or a combination thereof which will ionize a neutral met:allocene compound to form a cationic metallocene catalyst.
Examples of such ionizing agents are methyl alumoxane (MAO), tri.ethyl aluminum (TEAL) and. tris(pentafluorophenyl)boron. Other ionizing agents are disclosed in European Patent Publication Nos.
0-~'.77-003 and 0-277-004.
By using a multi-catalyst system having at least one homoge-neous catalyst and at least one heterogeneous catalyst a polymer can be produced with molecular weight distribution (MWD) as broad or broader than the MWD of the heterogeneous catalyst alone. MWD
can be represented by a chart of gel permeation chromatography (GF~C). The homogeneous catalyst produces a polymer with a MWD
which is narrow relative to ~~ polymer produced by a heterogeneous.
For example, using a heterogeneous catalyst alone produces a polymer with a MWD of approximately 5-7 (Figure 1) and using a homogeneous catalyst alone produces a MWD of approximately 2-3.5 (Fi.gure 2). By superimposing Figure 1 on Figure 2 (Figure 3), it can be predicted that using 'the two catalysts together will result in a polymer having a MWD of 5-7. When the two catalysts are used together in an actual polymerization, a polymer having a MWD of 5-7 ~~~~~ a~~i SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 results, as shown is Figure 4. A comparison of Figures 3 and 4 show a near identity in the shape and location of the plot.
By using different ratios of the homogeneous: heterogeneous catalysts, the polydispersity, i.e., the distribution of molecular weights, can be effected. Since the molecular weight of the polymer produced with the homogeneous catalyst is different from that of the heterogeneous catalyst, changing the relative amount of one catalyst to another in a multi-catalyst system of this invention will change the polydispersity of the polymer produced.
The effect of hydrogen on a catalyst system having one or more homogeneous catalysts alone is known to be negligible. The effect of hydrogen on a catalyst system having one or more heterogeneous catalysts alone is known to have an inverse proportional effect on the peak molecular weight of the polymer, but there is no effect on molecular weight distribution. However, when a catalyst system comprises one or more homogeneous catalysts and one or more heterogeneous, the effect of hydrogen in decreasing the peak molecular weight of the polymer produced by the heterogeneous cataly$t while the polymer produced by the homogeneous catalyst remains unaffected results in on overall change in the molecular weight distribution. The effect of using a relative low amount of hydrogen compared to using a relative high amount of hydrogen is shown in Figures 5 and 6, respectively. Therefore, hydrogen can be used to control molecular weight distribution of a polymer produced by a multi-catalyst of the present invention.
~~rjr~r~~~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 The invention having been generally described, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims to follow in any manner.
5.0 mg of conventional Ziegler-Natta catalyst was placed in a stainless steel bomb with 0.2 mmol CMDS. 5.0 mg of Et{Ind)ZZrClZ
were placed in a mixing bottle with 2.0 mmol TEA1. The metallo cene-TEA1 mixture was placed in the bomb. 2.5 ml of MAO were placed in a second stainless steel bomb. 1.0 liter of propylene was placed in a 2 liter Zipperclave reactor at 30°C. Contents of the first bomb were charged to the reactor with 0.3 liter of propylene and 15.7 mmol of hydrogen. Contents of the second bomb were charged to the reactor with 0.3 liter of propylene. The reactor temperature was increased from 30°C to 60°C. Polymeriza-tion continued for one hour during which time the reactor was maintained at the polymerization temperature. At the end of this time polymerization was terminated by rapidly venting the reactor of unreacted monomer. The polymer yield and analysis is shown in Table I.
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 The procedure of Example 1 was followed except 2.5 mg of conventional Ziegler-Natter catalyst and 5.0 mg of Et(Ind)zZrClZ and 3.9 mmol of hydrogen was used. The polymer yield and analysis is shown in Table I.
5.0 mmol of conventional Ziegler-Natter catalyst were placed in a bomb with 2.0 mmol of TEAL and 0.2 mg of CMDS. 2.5 mg of Et(Ind)2ZrC12 were placed in a second bomb with 2.5 ml of MAO. 1.0 liter of propylene was placed in a 2 liter Zipperclave reactor at 32°C. Contents of the first bomb were charged to the reactor with 0.3 liter of propylene and 4 mmol of hydrogen. The contents of the second bomb were charged to the reactor with 0.3 liter of propyl-ene. The reactor temperature was increased from 32°C to 60°C.
Polymerization continued for one hour during which time the reactor was maintained at the polymerization temperature. At the end of this time polymerization was terminated by rapidly venting the reactor of unreacted monomer. The polymer yield and analysis is shown in Table I.
5.0 mg of conventional Ziegler-Natter catalyst were placed in a stainless steel bomb with 2.0 mmol TEA1 and 0.2 mmol of CMDS.
2.5 mg of Et(Ind)ZZrCl2 were placed in a mixing bottle with 2.5 ml of MAO. The metallocene-MAO mixture was placed in the bomb. 1.0 ~U~'~'~!~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCI3ER COS627 liter of propylene was placed in a 2 liter Zipperclave reactor at 31°C. Contents of the bomb were charged to the reactor with 0.3 liter of propylene and 4 mmol of hydrogen. The reactor temperature was increased from 31°C to 60°C. Polymerization continued for one hour during which time the reactor was maintained at the polymer-ization temperature. At the end of this time polymerization was terminated by rapidly venting the reactor of unreacted monomer.
The polymer yield and analysis is shown in Table I.
The procedure of Example 1 was followed except 2.5 mg of conventional Ziegler-Natta catalyst, 5.0 mg of MeZSi(t-b-Cp)(Flu)ZrClz and 4 mmol of hydrogen were used and the initial reactor temperature was 33°C. The polymer yield and analysis is shown in Table I.
z~
O
N
H
~0 U = M N ~O ~t U ~
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L
o ~ M oo s r N N
E
U
~O ~O $ ~ .p V
J V M ~ ~ M
W O O O O O
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J
v d ~
W
I
n N
U
L
Np H: ~' A P a x Fs u1 M M M M
,,, C
v L
w u1 1f1N U1 U1 N N N N N
W
m L A
4 ~
.,, v o T
a _N
\
U
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\ N
W 1I1O 1!11!1y ~ v z \ \ '~ r J L
~ V 1.1~.7V N
H
NV N N N
(V N
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_ _ _ v v v v N
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W W N W t ~~ , W N
-W
z ~
W
J
n h~ O 1I1O O V1 W 1f1N U1W N t ~
v y N 6 O
N
N
r N N N N N L
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O ,~ a z~ L
a a N
_ O O O O O N~' t (f~H N N N N N
~ N . J
~r H ~ .
~
W Z
~I ~ ~- N M d V) 2~~'~~1 SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 Obviously, numerous modifications arid variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifi-cally described herein.
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 The invention having been generally described, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims to follow in any manner.
5.0 mg of conventional Ziegler-Natta catalyst was placed in a stainless steel bomb with 0.2 mmol CMDS. 5.0 mg of Et{Ind)ZZrClZ
were placed in a mixing bottle with 2.0 mmol TEA1. The metallo cene-TEA1 mixture was placed in the bomb. 2.5 ml of MAO were placed in a second stainless steel bomb. 1.0 liter of propylene was placed in a 2 liter Zipperclave reactor at 30°C. Contents of the first bomb were charged to the reactor with 0.3 liter of propylene and 15.7 mmol of hydrogen. Contents of the second bomb were charged to the reactor with 0.3 liter of propylene. The reactor temperature was increased from 30°C to 60°C. Polymeriza-tion continued for one hour during which time the reactor was maintained at the polymerization temperature. At the end of this time polymerization was terminated by rapidly venting the reactor of unreacted monomer. The polymer yield and analysis is shown in Table I.
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 The procedure of Example 1 was followed except 2.5 mg of conventional Ziegler-Natter catalyst and 5.0 mg of Et(Ind)zZrClZ and 3.9 mmol of hydrogen was used. The polymer yield and analysis is shown in Table I.
5.0 mmol of conventional Ziegler-Natter catalyst were placed in a bomb with 2.0 mmol of TEAL and 0.2 mg of CMDS. 2.5 mg of Et(Ind)2ZrC12 were placed in a second bomb with 2.5 ml of MAO. 1.0 liter of propylene was placed in a 2 liter Zipperclave reactor at 32°C. Contents of the first bomb were charged to the reactor with 0.3 liter of propylene and 4 mmol of hydrogen. The contents of the second bomb were charged to the reactor with 0.3 liter of propyl-ene. The reactor temperature was increased from 32°C to 60°C.
Polymerization continued for one hour during which time the reactor was maintained at the polymerization temperature. At the end of this time polymerization was terminated by rapidly venting the reactor of unreacted monomer. The polymer yield and analysis is shown in Table I.
5.0 mg of conventional Ziegler-Natter catalyst were placed in a stainless steel bomb with 2.0 mmol TEA1 and 0.2 mmol of CMDS.
2.5 mg of Et(Ind)ZZrCl2 were placed in a mixing bottle with 2.5 ml of MAO. The metallocene-MAO mixture was placed in the bomb. 1.0 ~U~'~'~!~
SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCI3ER COS627 liter of propylene was placed in a 2 liter Zipperclave reactor at 31°C. Contents of the bomb were charged to the reactor with 0.3 liter of propylene and 4 mmol of hydrogen. The reactor temperature was increased from 31°C to 60°C. Polymerization continued for one hour during which time the reactor was maintained at the polymer-ization temperature. At the end of this time polymerization was terminated by rapidly venting the reactor of unreacted monomer.
The polymer yield and analysis is shown in Table I.
The procedure of Example 1 was followed except 2.5 mg of conventional Ziegler-Natta catalyst, 5.0 mg of MeZSi(t-b-Cp)(Flu)ZrClz and 4 mmol of hydrogen were used and the initial reactor temperature was 33°C. The polymer yield and analysis is shown in Table I.
z~
O
N
H
~0 U = M N ~O ~t U ~
H
a w a.
L
o ~ M oo s r N N
E
U
~O ~O $ ~ .p V
J V M ~ ~ M
W O O O O O
O
O
O
J
v d ~
W
I
n N
U
L
Np H: ~' A P a x Fs u1 M M M M
,,, C
v L
w u1 1f1N U1 U1 N N N N N
W
m L A
4 ~
.,, v o T
a _N
\
U
L V
\ N
W 1I1O 1!11!1y ~ v z \ \ '~ r J L
~ V 1.1~.7V N
H
NV N N N
(V N
N
_ _ _ v v v v N
N N 4J C!
W W N W t ~~ , W N
-W
z ~
W
J
n h~ O 1I1O O V1 W 1f1N U1W N t ~
v y N 6 O
N
N
r N N N N N L
W w v O O O O O
O ,~ a z~ L
a a N
_ O O O O O N~' t (f~H N N N N N
~ N . J
~r H ~ .
~
W Z
~I ~ ~- N M d V) 2~~'~~1 SERIAL NO. PATENT APPLICATION
SHAMSHOUM, ELDER, REDDY, RAUSCHER COS627 Obviously, numerous modifications arid variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifi-cally described herein.
Claims (15)
1. A catalyst system for the polymerization of olefins comprising a combination of at least one metallocene catalyst, wherein said metallocene catalyst comprises:
a) a neutral metallocene of the general formula R" b (CpR4) (CpR'4) MR*v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, Cp is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being the same or different, each (CpR9) and (CpR'4) being the same or different, M is a group IIIB, IVB, VB, or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and b) an ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst wherein the ionizing agent is methyl alumoxane;
and at least one heterogeneous catalyst, wherein the heterogeneous catalyst comprises:
i) a transition metal of the general formula MR+x where M is a Group IIIB, IVB, VB, or VIB metal, R+ is a halogen or a hydrocarbyl and x is the valence of the metal; and ii) an aluminum alkyl of the general formula A1R#3 where R# is an alkyl of from 1-8 carbon atoms and R" may be the same or different.
a) a neutral metallocene of the general formula R" b (CpR4) (CpR'4) MR*v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, Cp is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being the same or different, each (CpR9) and (CpR'4) being the same or different, M is a group IIIB, IVB, VB, or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and b) an ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst wherein the ionizing agent is methyl alumoxane;
and at least one heterogeneous catalyst, wherein the heterogeneous catalyst comprises:
i) a transition metal of the general formula MR+x where M is a Group IIIB, IVB, VB, or VIB metal, R+ is a halogen or a hydrocarbyl and x is the valence of the metal; and ii) an aluminum alkyl of the general formula A1R#3 where R# is an alkyl of from 1-8 carbon atoms and R" may be the same or different.
2. A catalyst system as recited in Claim 1 wherein b is 1, R" is a hydrocarbyl radical chosen from the group consisting of an alkenyl radical having one to four carbon atoms, a dialkyl geranium, a dialkyl silicon, an alkyl phosphine and an amine radical, M is a Group IVB metal, R* is a halogen or alkyl.
3. A catalyst system as recited in Claim 2, wherein R" is a dimethyl silyl radical, an ethylenyl radical or a isopropenyl radical.
4. A catalyst system as recited in Claim 3, wherein R" is an ethylenyl radical.
5. A catalyst system as recited in Claim 1 wherein (CpR4) is an substituted cyclopentadienyl ring such that it is 3-t-butyl-cyclopentadienyl, indenyl or cyclopentadienyl and (CpR'4)is a subsituted cyclopentadienyl ring such that it is fluorenyl, indenyl or fluorenyl, respectively.
6. A catalyst system as recited in Claim 5 wherein (CpR4)is indenyl and (CpR'4) is indenyl.
7. A catalyst system as recited in Claim 1 wherein M is a Group IVB, R is chlorine, bromine, an alkoxy or a phenoxy.
8. A catalyst system as recited in Claim. 7 wherein M is titanium and R is chlorine or ethoxy.
9. A catalyst system as recited in Claim 8 wherein the heterogeneous catalyst chosen from the group consisting of TiCl4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)C1-3, Ti(OC4H9) 3C1, Ti (OC3H,),C12, Ti (OC6H13)2Cl2, Ti(0CHS)2Br2 and Ti (OC12H25)C13.
10. A catalyst system as recited in Claim 1 wherein the aluminum alkyl is chose from the group consisting of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum.
11. A catalyst. system as recited in Claim 1 further comprising an electron donor organosilion compound.
12. A catalyst system as recited in Claim 11 wherein the electron donor is chosen from the group consisting of methylcyclohexyl dimethyoxysilane, diphenyldimethoxysilane and isobutyltrimethoxy silane.
13. A method of making a catalyst system comprising:
a) mixing in any order the components of at least one homogenous catalyst, wherein the components of the homogeneous catalyst comprise:
a) a neutral metallocene of the general formula R"b(CpR4)(CpR'4)MR'v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, Cp is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl form 1-9 carbon atoms, each R and R' being the same or different, each (CpR4) and (CpR'4) being the same or different, M is a group IIIB, IVB, VB, or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and b) an ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst wherein the ionizing agent is methyl alumoxane;
and the components of at least one heterogenous catalyst, wherein the components of the heterogeneous catalyst comprises:
a) a transition metal of the general formula MR+X where M is a Group IIIB, IVB, VB, or VIB metal, R+ is a halogen or a hydrocarbyl and.x is the valence of the metal and b) an aluminum alkyl of the general formula AIFt~3 where R~ is an alkyl of from 1-8 carbon atoms and R~ may be the same or different.
a) mixing in any order the components of at least one homogenous catalyst, wherein the components of the homogeneous catalyst comprise:
a) a neutral metallocene of the general formula R"b(CpR4)(CpR'4)MR'v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, Cp is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl form 1-9 carbon atoms, each R and R' being the same or different, each (CpR4) and (CpR'4) being the same or different, M is a group IIIB, IVB, VB, or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and b) an ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst wherein the ionizing agent is methyl alumoxane;
and the components of at least one heterogenous catalyst, wherein the components of the heterogeneous catalyst comprises:
a) a transition metal of the general formula MR+X where M is a Group IIIB, IVB, VB, or VIB metal, R+ is a halogen or a hydrocarbyl and.x is the valence of the metal and b) an aluminum alkyl of the general formula AIFt~3 where R~ is an alkyl of from 1-8 carbon atoms and R~ may be the same or different.
14. A process of producing a polymer with a catalyst system having at least one homogeneous catalyst and at least one heterogeneous catalyst, said polymer having a molecular weight distribution as broad or broader thatn that produced by the same heterogeneous catalysts(s), comprising:
a) selecting a polymer with a preselected molecular weight distribution;
b) choosing one or more heterogeneous catalysts which produces polymers) with known molecular weight distributions) that is contained within the preselected molecular weight distribution wherein the heterogeneous catalyst comprises:
i) a transition metal of the general formula MR+x where M is a Group IIIB, IVB, VB, VIB metal, R+ is a halogen or a hydrocarbyl and x is the valence of the metal and ii) an aluminum alkyl of the general formula AIR~3 where R~ is an alkyl of from 1-8 carbon atoms and R~ may be the same or different and c) choosing one or more homogeneous catalysts which produce polymer with known molecular weight distributions so that the sum of the molecular weight distributions(s) of the polymers) produced with the heterogeneous catalysts(s) and of the molecular weight distributions) of the polymers) produced with the homogeneous catalysts(s) is the preselected the molecular weight distribution, wherein said homogeneous catalyst comprises i) a neutral metallocene of the general formula R"b (C p R4) (C p R'4) MR*v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, C p is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being the same or different, each (C p R4) and (C p R'4) being the same or different, M is a group IIIB, IVB, VB, or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and ii) an ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst.
a) selecting a polymer with a preselected molecular weight distribution;
b) choosing one or more heterogeneous catalysts which produces polymers) with known molecular weight distributions) that is contained within the preselected molecular weight distribution wherein the heterogeneous catalyst comprises:
i) a transition metal of the general formula MR+x where M is a Group IIIB, IVB, VB, VIB metal, R+ is a halogen or a hydrocarbyl and x is the valence of the metal and ii) an aluminum alkyl of the general formula AIR~3 where R~ is an alkyl of from 1-8 carbon atoms and R~ may be the same or different and c) choosing one or more homogeneous catalysts which produce polymer with known molecular weight distributions so that the sum of the molecular weight distributions(s) of the polymers) produced with the heterogeneous catalysts(s) and of the molecular weight distributions) of the polymers) produced with the homogeneous catalysts(s) is the preselected the molecular weight distribution, wherein said homogeneous catalyst comprises i) a neutral metallocene of the general formula R"b (C p R4) (C p R'4) MR*v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, C p is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being the same or different, each (C p R4) and (C p R'4) being the same or different, M is a group IIIB, IVB, VB, or VIB metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and ii) an ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst.
15. A process of producing a polymer with a catalyst system having at least one homegeneous catalyst and at least one heterogeneous catalyst, said polymer having a molecular weight distribution as broad or broader than that produced by the same heterogeneous catalyst (s), comprising;
a) selecting a polymer with a.preselected molecular weight distribution;
b) choosing one or more heterogeneous catalysts which produces polymer(s) with known molecule weight distribution(s) that is contained within the preselected molecule weight distribution; wherein the heterogeneous catalyst comprises:
i) a transition metal of the general formula MR+x where M is a Group IIIB, IVB, VB, or VIB metal, R+
is a halogen or a hydrocarbyl and x is the valence of the metal and ii) an aluminum alkyl of the general formula AIR*3 where R# is an alkyl of from 1-8 carbon atoms and R# may be the same or different and c) choosing one or more homogeneous catalysts which produce polymer with known molecular weight distributions so that the sum of the molecular weight distribution(s) of the polymer(s) produced with the heterogeneous catalysts(s) and of the molecular weight distribution(s) of the polymer(s) produced with the homeogeneous catalyst(s) and of the molecular weight distribution(s) of the polymer(s) produced with the homogeneous catalyst(s) is less than the preselected molecular weight distribution wherein said homogeneous catalyst comprises i) a neutral metallocene of the general formula R"b(C p R4) (C p R'4)MR*v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, Cp is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being same or different, each (C p R4) and (C p R'4) being the same or different, M is a group IIIB, IVB, VB, or VIB
metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and ii) and ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst, and d) adding hydrogen during the polymerization to broaden the molecular weight distribution to the preselected molecular weight distribution.
a) selecting a polymer with a.preselected molecular weight distribution;
b) choosing one or more heterogeneous catalysts which produces polymer(s) with known molecule weight distribution(s) that is contained within the preselected molecule weight distribution; wherein the heterogeneous catalyst comprises:
i) a transition metal of the general formula MR+x where M is a Group IIIB, IVB, VB, or VIB metal, R+
is a halogen or a hydrocarbyl and x is the valence of the metal and ii) an aluminum alkyl of the general formula AIR*3 where R# is an alkyl of from 1-8 carbon atoms and R# may be the same or different and c) choosing one or more homogeneous catalysts which produce polymer with known molecular weight distributions so that the sum of the molecular weight distribution(s) of the polymer(s) produced with the heterogeneous catalysts(s) and of the molecular weight distribution(s) of the polymer(s) produced with the homeogeneous catalyst(s) and of the molecular weight distribution(s) of the polymer(s) produced with the homogeneous catalyst(s) is less than the preselected molecular weight distribution wherein said homogeneous catalyst comprises i) a neutral metallocene of the general formula R"b(C p R4) (C p R'4)MR*v-2 where R" is a bridge imparting stereorigidity to the structure to the metallocene by connecting the two cyclopentadienyl rings, b is 0 or 1, Cp is a cyclopentadienyl ring, R and R' are substituents on the cyclopentadienyl rings and can be a hydride or a hydrocarbyl from 1-9 carbon atoms, each R and R' being same or different, each (C p R4) and (C p R'4) being the same or different, M is a group IIIB, IVB, VB, or VIB
metal, R* is a hydride, a halogen or a hydrocarbyl from 1-20 carbon atoms, v is the valence of M and ii) and ionizing agent which will ionize a neutral metallocene compound to form a cationic metallocene catalyst, and d) adding hydrogen during the polymerization to broaden the molecular weight distribution to the preselected molecular weight distribution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76878391A | 1991-09-30 | 1991-09-30 | |
| US768,783 | 1991-09-30 |
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| CA2077744A1 CA2077744A1 (en) | 1993-03-31 |
| CA2077744C true CA2077744C (en) | 2003-04-15 |
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| CA002077744A Expired - Fee Related CA2077744C (en) | 1991-09-30 | 1992-09-08 | Homogeneous-heterogeneous catalyst system for polyolefins |
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| Country | Link |
|---|---|
| US (1) | US5395810A (en) |
| EP (1) | EP0536104A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025448A (en) | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
| US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
| US5847053A (en) * | 1991-10-15 | 1998-12-08 | The Dow Chemical Company | Ethylene polymer film made from ethylene polymer blends |
| US5677383A (en) * | 1991-10-15 | 1997-10-14 | The Dow Chemical Company | Fabricated articles made from ethylene polymer blends |
| US6316549B1 (en) | 1991-10-15 | 2001-11-13 | The Dow Chemical Company | Ethylene polymer fiber made from ethylene polymer blends |
| EP0646624B1 (en) * | 1993-01-11 | 1998-09-02 | Mitsui Chemicals, Inc. | Propylene polymer composition |
| PT681592E (en) * | 1993-01-29 | 2001-01-31 | Dow Chemical Co | ETHYLENE INTERPOLIMERIZATIONS |
| US5804524A (en) * | 1993-04-28 | 1998-09-08 | Fina Technology, Inc. | Process for a isotactic/syndiotactic polymer blend in a single reactor |
| DE4330667A1 (en) * | 1993-09-10 | 1995-03-16 | Basf Ag | Process for the preparation of multiphase homo- or copolymers of C¶2¶-C¶1¶¶0¶-Alk-1-enes in one reaction zone |
| US5817590A (en) * | 1993-10-14 | 1998-10-06 | Tosoh Corporation | Catalyst for αE --olefin polymerization containing a Lewis base |
| US5576259A (en) * | 1993-10-14 | 1996-11-19 | Tosoh Corporation | Process for producing α-olefin polymer |
| JPH07173214A (en) * | 1993-10-27 | 1995-07-11 | Nippon Oil Co Ltd | Catalyst component for olefin polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4701432A (en) * | 1985-11-15 | 1987-10-20 | Exxon Chemical Patents Inc. | Supported polymerization catalyst |
| JP2893743B2 (en) * | 1989-08-10 | 1999-05-24 | 三菱化学株式会社 | Production of α-olefin polymer |
| EP0436328A3 (en) * | 1989-12-13 | 1992-09-16 | Mitsui Toatsu Chemicals, Inc. | Method for polymerizing alpha-olefin |
| US5145818A (en) * | 1989-12-29 | 1992-09-08 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for the polymerization of olefins |
-
1992
- 1992-09-08 CA CA002077744A patent/CA2077744C/en not_active Expired - Fee Related
- 1992-09-17 JP JP27384592A patent/JP3435576B2/en not_active Expired - Fee Related
- 1992-09-23 EP EP19920870154 patent/EP0536104A1/en not_active Ceased
-
1993
- 1993-01-27 US US08/009,520 patent/US5395810A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0536104A1 (en) | 1993-04-07 |
| CA2077744A1 (en) | 1993-03-31 |
| US5395810A (en) | 1995-03-07 |
| JPH06122719A (en) | 1994-05-06 |
| JP3435576B2 (en) | 2003-08-11 |
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