EP1673166A4 - ZIEGLER-NATTA CATALYST FOR POLYOLEFINS - Google Patents
ZIEGLER-NATTA CATALYST FOR POLYOLEFINSInfo
- Publication number
- EP1673166A4 EP1673166A4 EP04783311A EP04783311A EP1673166A4 EP 1673166 A4 EP1673166 A4 EP 1673166A4 EP 04783311 A EP04783311 A EP 04783311A EP 04783311 A EP04783311 A EP 04783311A EP 1673166 A4 EP1673166 A4 EP 1673166A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- reaction product
- halogenating
- agent
- contacting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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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
- C08F4/02—Carriers therefor
-
- 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
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- 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
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
- B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
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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
- C08F110/02—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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/06—Catalyst characterized by its size
Definitions
- the present invention relates generally to catalysts, to methods of making catalysts, to methods of using catalysts, to methods of polymerizing, and to polymers made with such catalysts. More particularly, the present invention relates to polyolefin catalysts and to Ziegler-Natta catalysts, to methods of making such catalysts, to methods of using such catalysts, to polyolefin polymerization, and to polyolefins.
- Olefins also called alkenes
- alkenes are unsaturated hydrocarbons whose molecules contain one or more pairs of carbon atoms linked together by a double bond.
- olefins can be converted to polyolefins, such as polyethylene and polypropylene.
- One commonly used polymerization process involves contacting an olefin monomer with a Ziegler-Natta type catalyst system.
- Many Ziegler-Natta type polyolefin catalysts their general methods of making, and subsequent use, are well known in the polymerization art.
- these systems include a Ziegler-Natta type polymerization catalyst component; a co-catalyst; and an electron donor compound.
- a Ziegler-Natta type polymerization catalyst component can be a complex derived from a halide of a transition metal, for example, titanium, chromium or vanadium, with a metal hydride and/or a metal alkyl that is typically an organoaluminum compound.
- the catalyst component is usually comprised of a titanium halide supported on a magnesium compound complex ed with an alkylaluminum.
- Conventional Ziegler-Natta catalysts comprise a transition metal compound generally represented by the formula: MR X where M is a transition metal compound, R is a halogen or a hydrocarboxyl, and x is the valence of the transition metal.
- M is selected from a group TV to VII metal such as titanium, chromium, or vanadium, and R is chlorine, bromine, or an alkoxy group.
- transition metal compounds are TiCl 4 , TiBr 4 , Ti(OC 2 H 5 ) 3 Cl, Ti(OC H 7 ) 2 Cl 2 , Ti(OC 6 H ⁇ 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Br 2 , and Ti(OC ⁇ 2 H 25 )Cl 3 .
- the transition metal compound is typically supported on an inert solid, e.g., magnesium chloride.
- Ziegler-Natta catalysts generally are provided on a support, i.e. deposited on a solid crystalline support.
- the support can be an inert solid, which is chemically unreactive with any of the components of the conventional Ziegler-Natta catalyst.
- the support is often a magnesium compound.
- the magnesium compounds which can be used to provide a support source for the catalyst component are magnesium halides, dialkoxymagnesiums, alkoxymagnesium halides, magnesium oxyhalides, dialkylmagnesiums, magnesium oxide, magnesium hydroxide, and carboxylates of magnesium.
- the properties of the polymerization catalyst can affect the properties of the polymer formed using the catalyst.
- polymer mo ⁇ hology typically depends upon catalyst mo ⁇ hology.
- Good polymer mo ⁇ hology includes uniformity of particle size and shape and an acceptable bulk density.
- Another polymer property affected by the type of catalyst used is the molecular weight distribution (MWD), which refers to the breadth of variation in the length of molecules in a given polymer resin.
- MWD molecular weight distribution
- One embodiment of the present invention provides a process for making a catalyst comprising: a) contacting a magnesium dialkoxide compound with a halogenating agent to form a 5 reaction product A; b) contacting reaction product A with a first halogenating/titanating agent to form reaction product B;. c) contacting reaction product B with a second halogenating/titanating agent to form reaction product C; and d) contacting reaction product C with a third halogenating/titanating agent to form reaction product D.
- the second and third halogenating/titanating agents can comprise titanium tetrachloride.
- the second and third o halogenating/titanating steps can each comprise a titanium to magnesium ratio in the range of about 0.1 to 5.
- the reaction products A, B and C can each be washed with a hydrocarbon solvent prior to subsequent halogenating/titanating steps.
- the reaction product D can be washed with a hydrocarbon solvent until titanium species [Ti] content is less than about 100 mmol/L.
- Another embodiment of the present invention provides a polyolefin catalyst produced by a5 process generally comprising contacting a catalyst component of the invention together with an organometallic agent.
- the catalyst component is produced by a process as described above.
- the catalysts of the invention can have a fluff mo ⁇ hology amenable to polymerization production processes, and may provide a polyethylene having a molecular weight distribution of at least 5.0 and may provide uniform particle size distributions with low levels of particles of less than about 125 0 microns.
- the activity of the catalyst is dependent upon the polymerization conditions. Generally the catalyst will have an activity of at least 5,000 gPE/g catalyst, but the activity can also be greater than 50,000 gPE/g catalyst or greater than 100,000 gPE/g catalyst.
- Even another embodiment of the present invention provides a polyolefin polymer produced by a process comprising: a) contacting one or more olefin monomers together in the presence of a5 catalyst of the invention, under polymerization conditions; and b) extracting polyolefin polymer.
- the monomers are ethylene monomers and the polymer is polyethylene.
- Yet another embodiment of the present invention provides a film, fiber, pipe, textile material or article of manufacture comprising polymer produced by the present invention.
- the article of manufacture can be a film comprising at least one layer comprising a polymer produced by a process o comprising a catalyst of the invention.
- Another embodiment of the invention provides a process for making a catalyst comprising: altering the precipitation of a catalyst component from a catalyst synthesis solution by controlling the viscosity of a catalyst synthesis solution with the addition of aluminum alkyls, wherein the average particle size of the catalyst component increases with an increased concentration of aluminum alkyl in the synthesis solution.
- the process can further comprise contacting the catalyst component with an organometallic preactivating agent to form a catalyst, wherein the average particle size of the catalyst increases with an increased concentration of aluminum alkyl in the 5 synthesis solution.
- Another embodiment of the present invention provides a process for making a catalyst comprising: a) contacting a magnesium dialkoxide compound with a halogenating agent to form a reaction product A; b) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; c) contacting reaction product B with a second halogenating/titanatingo agent to form reaction product C; d) contacting reaction product C with a third halogenating/titanating agent to form reaction product D; and e) contacting reaction product D with an organometallic preactivating agent to form a catalyst.
- the magnesium dialkoxide compound is a reaction product of a reaction comprising a magnesium alkyl compound of the general formula MgRR', wherein R and R' are alkyl groups of 1-10 carbon atoms and may be the same or different,5 an alcohol of the general formula R'OH wherein the alcohol is linear or branched and wherein R" is an alkyl group of 2-20 carbon ajtoms, and an aluminum alkyl of the formula A1R'" 3 wherein at least one R'" is an alkyl or alkoxide having 1-8 carbon atoms or a halide, and wherein each R'" may be the same or different.
- the average particle size of the catalyst increases with an increased aluminum alkyl to magnesium alkyl ratio.
- the second and third halogenating/titanating agents can comprise titanium tetrachloride.
- the second and third halogenating/titanating steps can each comprise a titanium to magnesium ratio in the range of about 0.1 to 5.
- the reaction products A, B and C can each be washed with a hydrocarbon solvent prior to subsequent halogenating/titanating steps.
- the reaction product D can be washed with a hydrocarbon solvent until titanium species [Ti] content is less than about 100 5 mmol/L.
- Even another embodiment of the present invention provides a polyolefin polymer produced by a process comprising: a) contacting one or more olefin monomers together in the presence of a catalyst of the invention, under polymerization conditions; and b) extracting polyolefin polymer.
- the average particle size of the polymer increases with an increased aluminum alkyl to magnesium o alkyl ratio utilized in the catalyst preparation.
- the monomers are ethylene monomers and the polymer is polyethylene.
- Yet another embodiment of trie present invention provides a film, fiber, pipe, textile material or article of manufacture comprising polymer produced by the present invention.
- the article of manufacture can be a film comprising at least one layer comprising a polymer produced by the present invention.
- Other embodiments include a process for forming a catalyst for use in the polymerization of olefins.
- This process comprises reacting a chlorinating agent with a magnesium alkoxide compound 5 to form a magnesium-titanium-alkoxide adduct and reacting the magnesium-titanium-alkoxide adduct with an alkylchloride compound to form a magnesium chloride support.
- the support is then reacted with titanium tetrachloride (TiCl ) to form a highly active catalyst useful for the production of polyolefins.
- TiCl titanium tetrachloride
- the magnesium alkoxide compound is first formed byo reacting butylethylmagnesium (BEM) with an alcohol generally represented by the formula ROH, where R is an alkyl group containing, e.g., about 1 to 20 carbon atoms.
- BEM butylethylmagnesium
- ROH an alcohol
- R is an alkyl group containing, e.g., about 1 to 20 carbon atoms.
- the magnesium alkoxide compound is then combined with a chlorinating agent generally represented by the formula:
- a magnesium-titanium-alkoxides adduct is formed as a result of mixing the magnesium alkoxide compound and the chlorinating agent.
- An alkylchloride compound is reacted with the magnesium-titanium-alkoxide adduct to form a magnesium chloride (MgCl 2 ) support and one or more by-products such as an ether and/or an alcohol.
- MgCl 2 is treated with TiCl 4 to form a Ziegler-Natta catalyst supported by o MgCl 2 .
- Polyolefins produced using this catalyst have narrow molecular weight distributions and thus may be formed into end use articles such as barrier films, fibers, and pipes.
- FIG. 1 illustrates the settling efficiency curves for polymer made using a catalyst of the invention (Example 1), and polymer made using a conventional catalyst (Comparative Example 4).
- FIG. 2 depicts the particle size distributions of the catalysts described in Comparative Examples 1A-2A and Examples 1 A-2A.
- FIG. 3 depicts the particle size distributions of the catalysts described in Comparative o Examples 1 A-2A and in Example 4A.
- FIG. 4 depicts catalyst yield as a function of the amount of PhCOCl used for Examples 4A- 10 A.
- FIGS. 5-6 depict the particle size distributions of the catalysts formed in Examples 4A-10A.
- FIG. 7 depicts average catalyst particle size (D 50 ) as a function of the amount of PhCOCl used for Examples 4A-10A.
- FIG. 8 depicts the particle size distributions of the catalysts described in Comparative Examples 1 A-2A and in Examples 4 A and 11 A.
- FIG. 9 depicts the fluff particle size distributions of the polymer resins described in Comparative Examples 3A-4A and in Example 12 A.
- FIG. 10 depicts the fluff particle size distributions of the polymer resins described ino Comparative Examples 3A-4A and in Example 13 A.
- FIG. 11 depicts the particle size distributions of the catalysts described in Example 14A.
- FIG. 12 depicts the particle size distributions of the catalysts described in Example 15 A.
- a method for making a catalyst component generally includes the steps of forming a metal dialkoxide from a metal dialkyl and an alcohol, halogenating the metal dialkoxide to form a reaction product, contacting the reaction product with one or more halogenating/titanating agent in three or more steps to form a catalyst component, and o then treating the catalyst component with a preactivation agent such as an organoaluminum.
- a preactivation agent such as an organoaluminum.
- M can be any suitable metal, usually a Group ELA metal, typically Mg.
- R, R 1 , R", R'", and R"" are each independently hydrocarbyl or substituted hydrocarbyl moieties, with R and R' having from 1 to 20 carbon atoms, generally from 1 to 10 carbon atoms, typically from 2 to 6 carbon atoms, and can have from 2 to 4 carbon atoms.
- R" generally comprises from 3 to 20 carbon atoms
- R"' generally comprises from 2-6 carbon atoms
- R"" generally comprises from 2-6 carbon atoms and is typically butyl.
- A is a nonreducing oxyphilic compound which is capable of exchanging one chloride for an alkoxide
- R'" is a hydrocarbyl or substituted hydrocarbyl
- x is the valence of A minus 1.
- Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, typically is titanium or silicon wherein x is 3.
- Examples of0 R"' include methyl, ethyl, propyl, isopropyl and the like having 2-6 carbon atoms.
- Nonlimiting examples of a chlorinating agent that can be used in the present invention are ClTi(O'Pr) 3 and ClSi(Me) 3 .
- the metal dialkoxide of the above embodiment is chlorinated to form a reaction product "A". While the exact composition of product "A” is unknown, it is believed that it contains a partiallys chlorinated metal compound, one example of which may be ClMg(OR").
- Reaction product "A” is then contacted with one or more halogenating/titanating agent, such as for example a combination of TiCl 4 and Ti (OBu) 4 , to form reaction product "B". Reaction product "B” which is probably a complex of chlorinated and partially chlorinated metal and titanium compounds.
- Reaction product "B” can comprise a titanium impregnated MgCl 2 support and for o example, may possibly be represented by a compound such as (MCl 2 ) y (TiCl x (OR) 4-x ) z .
- Reaction product “B” can be precipitated as a solid from the catalyst slurry.
- the second halogenation/titanation step produces reaction product, or catalyst component, "C” which is also probably a complex of halogenated and partially halogenated metal and titanium compounds but different from “B” and may possibly be represented by (MCl 2 ) y (TiCl ⁇ (OR) 4-X' ) Z' .
- the third halogenation/titanation step produces a reaction product, or catalyst component, "D" which is also probably a complex of halogenated and partially halogenated metal and titanium compounds but different from “B” and “C", and may possibly be represented by (MCl 2 ) y o (TiCl ⁇ " (OR) . X ") 2" . It is expected that the level of halogenation of "D” would be greater than that of product "C”. This greater level of halogenation would produce a different complex of compounds.
- Metal dialkyls and the resultant metal dialkoxides suitable for use in the present invention can include any that can be utilized in the present invention to yield a suitable polyolefin catalyst.
- These metal dialkoxides and dialkyls can include Group IIA metal dialkoxides and dialkyls.
- the metal dialkoxide or dialkyl can be a magnesium dialkoxide or dialkyl.
- Non-limiting examples of 5 suitable magnesium dialkyls include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butylethylmagnesium, etc.
- Butylethylmagnesium is one suitable magnesium dialkyl.
- the metal dialkoxide can be a magnesium compound of the general formula Mg(OR") 2 where R" is a hydrocarbyl or substituted hydrocarbyl of 1 to 20 carbon atoms.0
- the metal dialkoxide can be soluble and is typically non-reducing.
- a non-reducing compound has the advantage of forming MgCl 2 instead of insoluble species that can be formed by the reduction of compounds such as MgRR', which can result in the formation of catalysts having a broad particle size distribution.
- Mg(OR") 2 which is less reactive than MgRR', when used in a reaction involving chlorination with a mild chlorinating agent, followed by subsequent 5 halogenation/titanation steps, can result in a more uniform product, e.g., better catalyst particle size control and distribution.
- species of metal dialkoxides which can be used include magnesium butoxide, magnesium pentoxide, magnesium hexoxide, magnesium di(2-ethylhexoxide), and any alkoxide suitable for making the system soluble.
- magnesium dialkoxide such as magnesium di (2-ethylhexoxide
- MgRR' alkyl magnesium compound
- ROH alcohol
- MgRR' + 2 ROH ⁇ Mg(OR") 2 + RH + R'H5 The reaction can take place at room temperature and the reactants form a solution.
- R and R' may each be any alkyl group of 1-10 carbon atoms, and may be the same or different.
- Suitable MgRR' compounds include, for example, diethyl magnesium, dipropyl magnesium, dibutyl magnesium and butyl ethyl magnesium.
- the MgRR' compound can be BEM, wherein RH and R'H o are butane and ethane, respectively.
- any alcohol yielding the desired metal dialkoxide may be utilized.
- the alcohol utilized may be any alcohol of the general formula ROH where R" is an alkyl group of 2-20 carbon atoms, the carbon atoms can be at least 3, at least 4, at least 5, or at least 6 carbon atoms.
- suitable alcohols include ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol, 2-ethylhexanol, etc. While it is believed that almost any alcohol may be utilized, linear or branched, a higher order branched alcohol, for example, 2-ethyl-l-hexanol, can be utilized.
- the amount of alcohol added can vary, such as within a non-exclusive range of 0 to 10 equivalents, is generally in the range of about 0.5 equivalents to about 6 equivalents (equivalents are relative to the magnesium or metal compound throughout), and can be in the range of about 1 to about 3 equivalents.
- Alkyl metal compounds can result in a high molecular weight species that is very viscous in o solution. This high viscosity may be reduced by adding to the reaction an aluminum alkyl such as, for example, triethylaluminum (TEA1), which can disrupt the association between the individual alkyl metal molecules.
- TAA1 triethylaluminum
- the typical ratio ofalkyl aluminum to metal can range from 0.001:1 to 1:1, can be 0.01 to 0.5:1 and also can range from 0.03:1 to 0.2:1.
- an electron donor such as an ether, for example, diisoamyl ether (DIAE)
- the typical ratio of electron donor to metal ranges from 0: 1 to 10: 1 and can range from 0.1:1 to 1:1.
- Agents useful in the step of halogenating the metal alkoxide include any halogenating agent which when utilized in the present invention will yield a suitable polyolefin catalyst.
- the halogenating step can be a chlorinating step where the halogenating agent contains a chloride (i.e, is 0 a chlorinating agent).
- Halogenating of the metal alkoxide compound is generally conducted in a hydrocarbon solvent under an inert atmosphere.
- suitable solvents include toluene, heptane, hexane, octane and the like.
- the mole ratio of metal alkoxide to halogenating agent is generally in the range of about 6:1 to about 1 :3, can be in the range of about 5 3 : 1 to about 1 :2, can be in the range of about 2: 1 to about 1 :2, and can also be about 1:1.
- the halogenating step is generally carried out at a temperature in the range of about 0°C to about 100°C and for a reaction time in the range of about 0.5 to about 24 hours.
- the halogenating step can be carried out at a temperature in the range of about 20°C to about 90°C and for a reaction time in the range of about 1 hour to about 4 hours.
- the halide product "A" can be subjected to two or more halogenating/titanating treatments.
- the halogenation/titanation agents utilized can be blends of two tetra-substituted titanium compounds with all four substituents being the same and the substituents being a halide or an alkoxide or phenoxide with 2 to 10 carbon atoms, such as TiCl 4 or Ti(OR"") 4 .
- the halogenation/titanation agent utilized can be a chlorination/titanation agent.
- the halogenation/titanation agent may be a single compound or a combination of 5 compounds.
- the method of the present invention provides an active catalyst after the first halogenation/titanation; however, there are desirably a total of at least three halogenation/titanation steps.
- the first halogenation/titanation agent is typically a mild titanation agent, which can be a blend of a titanium halide and an organic titanate.
- the first halogenation/titanation agent can be a o blend of TiCl 4 and Ti(OBu) 4 in a range from 0.5 : 1 to 6: 1 TiCl 4 /Ti(OBu) 4 , the ratio can be from 2: 1 to 3:1.
- the blend of titanium halide and organic titanate react to form a titanium alkoxyhalide, Ti(OR) a X b , where OR and X are alkoxide and halide, respectively and a + b is the valence of titanium, which is typically 4.
- the first halogenation/titanation agent may be a single compound.
- Examples of a first halogenation/titanation agent are Ti(OC 2 H 5 ) 3 Cl, Ti(OC 2 H 5 ) 2 Cl 2 , Ti(OC 3 H 7 ) 2 Cl 2 , Ti(OC 3 H 7 ) 3 Cl, Ti(OC 4 H 9 )Cl 3 , Ti(OC 6 H )3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Br 2 , and Ti(OC 12 H 5 )Cl 3 .
- the first halogenation/titanation step is generally carried out by first slurrying the halogenation product "A" in a hydrocarbon solvent at room temperature/ambient temperature.
- Nonlimiting examples of suitable hydrocarbons solvent include heptane, hexane, toluene, octane and o the like.
- the product "A” can be at least partially soluble in the hydrocarbon solvent.
- a solid product "B” is precipitated at room temperature following the addition of the halogenation/titanation agent to the soluble product "A".
- the amount of halogenation/titanation agent utilized must be sufficient to precipitate a solid product from the solution.
- the amount of halogenation/titanation agent utilized, based on the ratio of titanium to metal will 5 generally be in the range of about 0.5 to about 5, typically in the range of about 1 to about 4, and can be in the range about 1.5 to about 2.5.
- the solid product "B” precipitated in this first halogenation/titanation step is then recovered by any suitable recovery technique, and then washed at room/ambient temperature with a solvent, such as hexane. Generally, the solid product “B” is washed until the [Ti] is less than about 0 1 OOmmol/L.
- [Ti] represents any titanium species capable of acting as a second generation Ziegler catalyst, which would comprise titanium species that are not part of the reaction products as described herein.
- the resulting product "B” is then subjected to a second and third halogenating/titanating steps to produce products "C" and "D".
- the solid product can be washed until the [Ti] is less than a desired amount. For example, less than about 1 OOmmol/L, less than about 50mmol/L, or less than about 5 1 Ommol/L.
- the product can be washed until the [Ti] is less than a desired amount, for example, less than about 20mmol/L, less than about 1 Ommol/L, or less than about 1.Ommol/L. It is believed that a lower [Ti] can produce improved catalyst results by reducing the amount of titanium that can act as a second generation Ziegler species.
- the second halogenation/titanation step is generally carried out by slurrying the solid product recovered from the first titanation step, solid product "B", in a hydrocarbon solvent. Hydrocarbon solvents listed as suitable for the first halogenation/titanation step maybe utilized.
- the second and third halogenation/titanation steps can utilize a different compound or combination of 5 compounds from the first halogenation/titanation step.
- the second and third halogenation/titanation steps can utilize the same agent at a concentration that is stronger than that used in the first halogenation/titanation agent, but this is not a necessity.
- the second and third halogenating/titanating agents can be a titanium halide, such as titanium tetrachloride (TiCl 4 ).
- TiCl 4 titanium tetrachloride
- the halogenation/titanation agent is added to the slurry. The addition can be carried out at ambient/room o temperature, but can also be carried out at temperatures and pressures other than ambient.
- the second and third halogenation/titanation agents comprise titanium tetrachloride.
- the second and third halogenation/titanation steps each comprise a titanium to magnesium ratio in a range of about 0.1 to 5, a ratio of about 2.0 can also be used, and a ratio of about 1.0 can be used.
- the third halogenation/titanation step is generally carried out at room 5 temperature and in a slurry, but can also be carried out at temperatures and pressures other than ambient.
- the amount of titanium tetrachloride utilized, or alternate halogenation/titanation agent may also be expressed in terms of equivalents, an equivalent herein is amount of titanium relative to the magnesium or metal compound.
- the amount of titanium of each of the second and third o halogenating/titanating steps will generally be in the range of about 0.1 to about 5.0 equivalents, can be in the range of about 0.25 to about 4 equivalents, typically is in the range of about 0.3 to about 3 equivalents, and it can be desirable to be in the range of about 0.4 to about 2.0 equivalents.
- the amount of titanium tetrachloride utilized in each of the second and third halogenation/titanation steps is in the range of about 0.45 to about 1.5 equivalent.
- the catalyst component "D” made by the above described process may be combined with an organometallic catalyst component (a "preactivating agent") to form a preactivated catalyst system suitable for the polymerization of olefins.
- a preactivating agent an organometallic catalyst component
- the preactivating agents which are used together with the transition metal containing catalyst component “D” are organometallic compounds such as aluminum alkyls, aluminum alkyl hydrides, lithium aluminum alkyls, zinc alkyls, magnesium alkyls and the like.
- the preactivating agent is generally an organoaluminum compound.
- the organoaluminum preactivating agent is typically an aluminum alkyl of the formula A1R wherein at least one R is an alkyl having 1-8 carbon atoms or a halide, and wherein each of the R may be the same or different.
- the organoaluminum preactivating agent can be a trialkyl aluminum such as, for example, trimethyl aluminum (TMA), triethyl aluminum (TEA1) and triisobutyl aluminum (TiBAl).
- TMA trimethyl aluminum
- TEA1 triethyl aluminum
- TiBAl triisobutyl aluminum
- the ratio of Al to titanium can be in the range from 0.1 : 1 to 2: 1 and typically is 0.25: 1 to 1.2: 1.
- the Ziegler-Natta catalyst may be pre-polymerized.
- a prepolymerization process is affected by contacting a small amount of monomer with the catalyst after the catalyst has been contacted with the co-catalyst.
- a pre-polymerization process is described in U.S. Patent Nos. 5,106,804; 5,153,158; and 5,594,071, hereby inco ⁇ orated by reference.
- the catalyst of the present invention may be used in any process for the homopolymerization or copolymerization of any type of ⁇ -olefins.
- the present catalyst can be useful for catalyzing ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and other ⁇ -alkenes having at least 2 carbon atoms, and also for mixtures thereof.
- Copolymers of the above can produce desirable results such as broader MWD and multi-modal distributions such as bimodal and trimodal properties.
- the catalysts of the present invention can be utilized for the polymerization of ethylene to produce polyethylene.
- Various polymerization processes can be employed with the present invention, such as for example, single and/or multiple loop processes, batch processes or continous processes not involving a loop-type reactor.
- An example of a multiple loop process that can employ the present invention is a double loop system in which the first loop produces a polymerization reaction in which the resulting polyolefin has a lower MW than the polyolefin produced from the polymerization reaction of the second loop, thereby producing a resultant resin having broad molecular weight distribution and/or bimodal characteristics.
- a multiple loop process that can employ the present invention is a double loop system in which the first loop produces a polymerization reaction in which the resulting polyolefin has a greater MW than the polyolefin produced from the polymerization reaction of the second loop, thereby producing a resultant resin 5 having broad molecular weight distribution and/or bimodal characteristics.
- the polymerization process may be, for example, bulk, slurry or gas phase.
- a catalyst of the invention can be used in slurry phase polymerization.
- Polymerization conditions e.g., temperature and pressure
- the0 temperature will be in a range of about 50-110°C, and the pressure in a range of about 10-800 psi.
- the activity of the resulting catalyst of embodiments of the present invention is at least partially dependent upon the polymerization process and conditions, such as, for example, equipment utilized and temperature of reaction.
- the catalyst will have an activity of at least 5,000 g PE/g catalysts but can have an activity of greater than 50,000 g PE/g catalyst, and the activity may be greater than 100,000 g PE/g catalyst.
- the resulting catalyst of the present invention can provide a polymer with improved fluff mo ⁇ hology.
- the catalyst of the present invention can provide for large polymer particles with a uniform distribution of sizes, wherein fine particles (less than about 125 o microns) are only present in low concentrations, such as for example, less than 2% or less than 1 %.
- the catalysts of the present invention which include large, readily transferred powders with high powder bulk densities, are amenable to polymerization production processes.
- the catalysts of the invention provide polymer with fewer fines and higher bulk densities (B.D.) wherein the B.D. value can be greater than about 0.31 g/cc, can be greater than about 0.33 g/cc, and can even be 5 greater than about 0.35 g/cc.
- the olefin monomer may be introduced into the polymerization reaction zone in a diluent that is a nonreactive heat transfer agent that is a liquid at the reaction conditions.
- a diluent examples include hexane and isobutane.
- the second alpha-olefin may be present at 0.01-20 mole o percent, and can be present at between about 0.02-10 mole percent.
- an electron donor may be added with the halogenation agent, the first
- Electron donors for use in the preparation of polyolefin catalysts are well known, and any suitable electron donor may be utilized in the present invention that will provide a suitable catalyst.
- Electron donors, also known as Lewis bases, are organic compounds of oxygen, nitrogen, phosphorous, or sulfur which can donate an electron pair to the catalyst.
- the electron donor may be a monofunctional or polyfunctional compound, can be selected from among the aliphatic or aromatic carboxylic acids and their alkyl esters, the aliphatic or cyclic ethers, ketones, vinyl esters, acryl derivatives, particularly alkyl acrylates or methacrylates and silanes.
- An example of a suitable electron donor is di-n-butyl phthalate.
- a generic example of a suitable electron donor is an alkylsilylalkoxide of the general formula RSi(OR') 3 , e.g., methylsilyltriethoxide [MeSi(OEt 3 )], where R and R' are alkyls with 1-5 carbon atoms and may be the same or different.
- an internal electron donor can be used in the synthesis of the catalyst and an external electron donor or stereoselectivity control agent (SCA) to activate the catalyst at polymerization.
- An internal electron donor may be used in the formation reaction of the catalyst during the halogenation or halogenation /titanation steps.
- Compounds suitable as internal electron donors for preparing conventional supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, electron donors compounds withN, P and/or S atoms and specific classes of esters.
- esters of phthalic acid such as diisobutyl, dioctyl, diphenyl and benzylbutylphthalate
- esters of malonic acid such as diisobutyl and diethylmalonate
- alkyl and arylpivalates alkyl, cycloalkyl and arylmaleates
- alkyl and aryl carbonates such as diisobutyl, ethyl-phenyl and diphenylcarbonate
- succinic acid esters such as mono and diethyl succinate.
- External donors which may be utilized in the preparation of a catalyst according to the present invention include organosilane compounds such as alkoxysilanes of general formula SiR m (OR') 4- m where R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group; R' is an alkyl group; and m is 0-3, wherein R may be identical with R'; when m is 0, 1 or 2, the R' groups may be identical or different; and when m is 2 or 3, the R groups may be identical or different.
- organosilane compounds such as alkoxysilanes of general formula SiR m (OR') 4- m where R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group; R' is an alkyl group; and m is 0-3, wherein R may be identical with R'; when m is 0, 1 or 2, the R' groups may be
- the external donor of the present invention can be selected from a silane compound of the following formula:
- Ri and R are both an alkyl or cycloalkyl group containing a primary, secondary or tertiary carbon atom attached to the silicon, Ri and Rj being the same or different; R 2 and R 3 are alkyl or aryl groups.
- Ri may be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl;
- R2and R 3 may be methyl, ethyl, propyl, or butyl groups and not necessarily the same; and R may also methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl.
- CMDS cyclohexylmethydimethoxy silane
- DIDS diisopropyldimethoxysilane
- CLOS dicyclopentyldimethoxysilane
- CPDS dicyclopentyldimethoxysilane
- DTDS di-t-butyl dimethoxysilane
- Polyethylene produced using the above described catalyst can have an MWD of at least 5.0, and can be greater than about 6.0.
- the polyolefins of the present invention are suitable for use in a variety of applications such as, for example, an extrusion process, to yield a wide range of products.
- extrusion processes include, for example, blown film extrusion, cast film extrusion, slit tape extrusion, blow molding, pipe extrusion, and foam sheet extrusion. These processes may comprise mono-layer extrusion or multi-layer coextrusion.
- End use applications that can be made utilizing the present invention can include, for example, films, fibers, pipe, textile material, articles of manufacture, diaper components, feminine hygiene products, automobile components and medical materials.
- Example J In the nitrogen purge box, 1412.25 g (2.00 moles) of BEM-1 , 27.60 g (0.060 moles) of TEA1 5 (24.8% in heptane), and 189.70 g (1.20 moles) of DIAE were added to a 3 L round bottom flask. The contents were then transferred to the 20 L Buchi reactor via cannula under a nitrogen flow.
- the flask was then rinsed with approximately 400 ml of hexane which was transferred to the reactor.
- the stirrer was set to 350 ⁇ m.
- the 2-ethylhexanol (543.60 g, 4.21 moles) was added to a 1 L bottle and capped. It was then o diluted to a total volume of 1 L with hexane prior to addition to the reactor. This solution was transferred to the reactor via cannula using the mass flow controller.
- the initial head temperature was 25.3 °C and reached a maximum temperature of 29.6 °C.
- the bottle was rinsed with 400 ml of hexane which was trans erce to the reactor.
- the reaction mixture was left stirring at 350 ⁇ m overnight under a nitrogen pressure of 0.5 bar and the heat exchanger was turned off. [0087] The heat exchanger was turned on and set to 25 °C.
- the chlorotitanium triisopropoxide was 5 added to two 1 L bottles (774.99 and 775.01 g, 2.00 total moles) to give a total of two liters.
- the contents of each bottle were transferred to the reactor via cannula using the mass flow controller.
- the initial head space temperature was 24.6°C and reached a maximum temperature of 25.9 °C during the addition of the second bottle.
- the addition times were 145 and 125 minutes for bottles 1 and 2, respectively.
- the bottle was rinsed with 200 ml of hexane and transferred to the reactor.
- a 1 L measuring cylinder 440 ml (-760 g, 4.00 moles) of TiCl 4 was diluted to a total volume of 1 L with hexane.
- the solution in the 5 liter flask was stirred and the TiCl 4 solution was added to the reactor dropwise under N 2 pressure via cannula.
- the 1 L cylinder was rinsed with 200 ml of hexane which was transferred to o the reactor.
- the reaction mixture was diluted to 4 L total volume with hexane and stored in the flask prior to use.
- the heat exchanger was turned on and set to 25 °C.
- the TiCVTi(OBu) 4 mixture was transferred to the 20 liter reactor via cannual and mass flow controller.
- the initial head space temperature was 24.7 °C and reached a maximum temperature of 26.0 °C during the 225 minute 5 addition.
- the vessel was rinsed with one liter of hexane and allowed to stir for 1 hour. [0090] The stirrer was turned off and the solution allowed to settle for 30 minutes. The solution was decanted by pressuring the reactor to 1 bar, lowering the dip tube, and making sure no solid catalyst came through the attached clear plastic hose. The catalyst was then washed three times using the o following procedure.
- the supernatant was decanted, and the catalyst was washed once with hexane following the procedures described above. After the wash was complete, 2.0 kg of hexane was transferred to the reactor and the agitation was resumed. The second TiCl 4 drop was completed in a similar manner to that described above using the remaining 500 milliliters of solution. Following the addition, the cylinder was rinsed with 400 milliliters of hexane, which was added to the Buchi. After one hour of reaction, the stirrer was turned off and the solids were allowed to settle for 30 minutes. The supernatant was then decanted, and the catalyst washed three times with hexane. 2.0 kg of hexane was then transferred to the reactor.
- composition in weight percent was: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti at 7.9%. Observed ranges for each element were; Cl at 48.6 - 55.1 %; Al at 2.3 - 2.5%; Mg at
- Table 1 lists the [Ti] measured from samples after the TiC14/Ti(OBu) addition, three washes, a first TiCl 4 addition, one wash and the second TiCl addition and three subsequent washes. Decants 1 - 4 are following the TiC14/Ti(OBu) 4 addition. Decants 5 and 6 are following the first TiCl 4 addition. Decants 7-10 follow the second TiC addition.
- Comparative Example 1 Comparative Example 1 was prepared in a similar manner to that of Example 1 except the third titanation was omitted and the second titantion was carried out employing one fourth of the quantity of TiCl 4
- Comparative Example 2 Comparative Example 2 was prepared in a similar fashion to Example 1 except a second and third titantion step was performed employing 0.5 equivalents of TiCl 4 during each titanation step.
- Comparative Example 3 was prepared in a similar manner to Comparative Example 1 except the quantity of TiCU employed during the second titanation was approximately four times that used during Comparative Example 1. One hexane wash was performed following the second titanation. In one embodiment the composition in weight percent was: Cl at 57.0%; Al at 2.0%; Mg at 9.5% and Ti at 10.0%. Ranges for each element can be; Cl at 55.0 - 57.0%; Al at 2.0 - 2.6%; Mg at 8.9 - 9.5%; and Ti of 10.0 - 11.0%.
- Comparative Example 4 was prepared in a similar manner to Comparative Example 3 except two hexane washes were performed following the second titanation.
- the composition in weight percent was: Cl 53.0%; Al 2.3%; Mg 9.7% and Ti at 9.5%. Ranges for each element can be; Cl at 52.6 - 53.0%; Al at 2.0 - 2.3%; Mg at 9.7 - 10.6%; and Ti of 8.7 - 9.5%.
- Table 2 lists the catalysts prepared.
- Table 3 gives the MWD data provided for polymers made with Example 1 and
- the data show that a narrower MWD can be attained by increasing the numbers of washes or addition of a third titanation step with TiCLi.
- the polymer resin intrinsic MWD increases in the following order Comparative Example 1 ⁇ Comparative Example 2 ⁇ Comparative Example 4 ⁇ Example 1 ⁇ Comparative Example 3.
- Table 3 Comparative Example 3
- each of the catalysts provides powder with low levels of fines
- catalysts of the invention prepared with two titanation steps consistently provide fluff with higher bulk densities.
- Example 2 The synthesis employed is as follows with all ratios relative to BEM: 1. (BEM + X TEAl + 0.6 DIAE)+ (2+3X) 2-ethylhexanol ⁇ Mg(O-2-ethhex) 2 * [Al(O-2-ethhex) 3 ] 2.
- the relative amount of 2-ethylhexanol was adjusted during each catalyst synthesis to prevent the reduction of titanium complexes by any unreacted aluminum or magnesium alkyl species.
- the following table lists the catalysts synthesized, the relative amounts of BEM, TEAl, and 2-ethylhexanol employed, the average particle size for the catalysts and the average particle size of polyethylene resin produced using each catalyst. [00108]
- the following table provides the particle size distribution data that was obtained for each catalyst. As shown, the average particle size distribution increases with increasing TEAl levels.
- the average particle size of both the catalyst and the resulting fluff increase with increasing TEAl levels utilized in the initial solutions of the catalyst synthesis.
- the viscosity of the catalyst synthesis solution can be altered.
- the variance of the solution viscosity can thereby alter the precipitation properties of the catalyst component from the solution, which can affect the resulting average particle size of the catalyst component and the resulting polymer produced from this catalyst.
- the average particle size of the catalyst component increases with an increased concentration of aluminum alkyl in the synthesis solution.
- the average particle size of the resulting polymer resin produced by the catalyst increases with an increased concentration of aluminum alkyl in the synthesis solution.
- the quantity of aluminum alkyl can be measured in terms of the ratio of aluminum alkyl to magnesium alkyl, which can range from about 0.01 :1 to about 10:1.
- Polyethylene produced using the above described catalyst can have an MWD of at least 4.0, and can be greater than about 6.0.
- Catalyst 101 in Table 5 is the same as Example 1 as described above. In one embodiment the composition in weight percent was: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti at 7.9%. Ranges for each element can be: Cl at 40.0 - 65.0%; Al at 0.0 - 6.0%; Mg at 6.0 - 15.0%; and Ti of 2.0 - 14.0%.
- Catalyst 102 in Table 5 had in one embodiment: Cl 47.0%; Al 3.4%; Mg 13.1% and Ti at 4.0%. Ranges for each element can be: Cl at 40.0 - 65.0%; Al at 0.0 - 6.0%; Mg at 6.0 - 15.0%; and Ti of 2.0 - 14.0%.
- Catalyst 103 in Table 5 had in one embodiment: Cl 50.0%; Al 2.4%; Mg 12.1% and
- Catalyst 104 in Table 5 had in one embodiment: Cl 53.0%; Al 3.1%; Mg 12.8% and
- Ranges for each element can be: Cl at 40.0 - 65.0%; Al at 0.0 - 6.0%; Mg at 6.0 - 15.0%; and Ti of 2.0 - 14.0%.
- the polyolefins of the present invention are suitable for use in a variety of applications such as, for example, an extrusion process, to yield a wide range of products.
- extrusion processes include, for example, blown film extrusion, cast film extrusion, slit tape extrusion, blow molding, pipe extrusion, and foam sheet extrusion. These processes may comprise mono-layer extrusion or multi-layer coextrusion.
- End use applications that can be made utilizing the present invention can include, for example, films, fibers, pipe, textile material, articles of manufacture, diaper components, feminine hygiene products, automobile components and medical materials.
- a polyolefin polymerization catalyst is formed using a process comprising several reactions.
- a magnesium alkyl compound i.e., Mg(R * ) 2 , where R * may be the same or different alkyl group having about 1 to 20 carbon atoms
- BEM a magnesium alkyl compound
- R * may be the same or different alkyl group having about 1 to 20 carbon atoms
- R is an alkyl group containing, e.g., about 1 to 20 carbon atoms.
- the alcohol represented by the formula ROH may be branched or non-branched.
- An example of a suitable alcohol is 2- ethylhexanol.
- Any suitable reaction conditions and addition sequence for converting the BEM and alcohol reactants to a magnesium alkoxide compound may be used.
- the alcohol is added to a BEM solution to form a reaction mixture, which is maintained at ambient temperature and pressure. The reaction mixture is stirred for a period of time sufficient to form the soluble magnesium alkoxide compound.
- magnesium alkoxide compound is mixed with a mild chlorinating agent to form a magnesium-titanium-alkoxide adduct in accordance with the following equation: Mg(OR) 2 + TiCln(OR') -n ⁇ [Ti(OR')4-nCl n »Mg(OR) 2 ] m
- R' is an alkyl, cycloalkyl, or aryl group
- n is from 1 to 3
- m is at least 1, and can be greater than 1. Desirably, n is 1.
- Any suitable conditions for forming the magnesium-titanium-alkoxide adduct may be employed for this process. In one embodiment, the process is carried out at ambient temperature and pressure. The reactants are mixed for a period of time sufficient to form the magnesium-titanium-alkoxide adduct.
- the adduct forms because the magnesium-titanium-alkoxide compound is sterically hindered, making it difficult for the chloride atoms of the titanium compound to metathesize with the magnesium alkoxide ligands. In essence, the adduct is almost, but not completely converted to MgCl 2 .
- the magnesium-titanium-alkoxide adduct is mixed with an alkylchloride compound such that it converts to an MgCl 2 support. The reaction proceeds as follows: [Ti(OR') 4 . n Cl n Mg(OR) 2 ] m + R"C1 ⁇ "TiMgCl 2 " + R'OR
- R" is an alkyl group containing, e.g., about 2 to 18 carbon atoms and where "TiMgCl 2 " represents titanium impregnated MgCl 2 support. While R" may be branched or unbranched, it can be desirable in some embodiments to have R" unbranched.
- Possible alkylchloride compounds include benzoyl chloride, chloromethyl ethyl ether, and t-butyl chloride, with benzoyl chloride being desirable in particular embodiments.
- the amount of alkylchloride added to the magnesium alkoxide o adduct can be in excess of that required for the reaction.
- the ratio of the amount of benzoyl chloride to the amount of Mg (e.g., BEM) in the reaction mixture can range from about 1 to 20 (i.e., from about 1 :1 ratio up to about 20:1 ratio), or from about 1 to 10, and it can be desirable to range from about 4 to 8.
- the reaction may be carried out at any suitable conditions for precipitating the magnesium chloride support.
- the reactants are refluxed for a period of time 5 sufficient to precipitate the MgCl 2 support.
- the reactants can be heated during reflux.
- benzoyl chloride or chloromethyl ethyl ether the reactants can be at room temperature during reflux.
- One or more by-products such as an ether (shown in the above reaction) are also produced by the reaction. It is believed that the presence of Ti during the precipitation of the MgCl 2 plays a major role in producing a highly active catalyst. o [00119] After separating the MgCl 2 support from the reaction mixture, the support may be washed with, e.g., hexane, to remove any contaminants therefrom.
- the MgCl 2 support is then treated with TiCl 4 to form a catalyst slurry in accordance with the following equation: "TiMgCl 2 " + 2 TiCl 4 ⁇ Catalyst [00120]
- This treatment may be performed at any suitable conditions, e.g., at ambient 5 temperature and pressure, for forming a catalyst slurry.
- the catalyst slurry is washed with, e.g., hexane, and then dried.
- the resulting catalyst may be pre-activated using an alkyl aluminum compound, such as triethylaluminum (TEAL), to prevent the catalyst from corroding the polymerization reactor.
- TEAL triethylaluminum
- titanium chlorides in the catalyst are converted to titanium alkyls when reacted with an alkyl aluminum compound. Otherwise, the titanium chlorides 0 might be converted to HCl when exposed to moisture, resulting in the corrosion of the polymerization reactor.
- Hexane was purchased from Phillips and passed through a 3A molecular sieve column, a F200 alumina column, and a column filled with BASF R3-11 copper catalyst at a rate of 12 mL/min. for purification.
- An Autoclave Engineer reactor was employed for the polymerization o of ethylene in the presence of each of the catalyst samples. This reactor has a four liter capacity and is fitted with four mixing baffles having two opposed pitch propellers. Ethylene and hydrogen were introduced to the reactor while maintaining the reaction pressure using a dome loaded back pressure regulator and the reaction temperature using steam and cold water. Hexane was introduced to the reactor as a diluent.
- Comparative catalyst Sample A was prepared by charging a one-liter reactor with the heptane0 solution containing 15.6 wt.% BEM (70.83 g, 100 mmol). Next, 26.45 g (203 mmol) of 2- ethylhexanol was slowly added to the BEM-containing solution. The reaction mixture was stirred for one hour at ambient temperature.
- the precipitate was washed three times with approximately 200 mL of hexane.
- the solid was re- slurried in approximately 150 mL of hexane and 50 mL of a hexane solution containing TiCl 4 (18.97 g, 100 mmol) was added.
- the slurry was allowed to stir for one hour at ambient temperature.
- the solid was allowed to settle, and the supernatant was decanted.
- the solid was washed once with 200 mL of hexane.
- About 150 mL of hexane was then added to the precipitate.
- the catalyst was treated again with 50 mL of a hexane solution containing TiCl 4 (18.97 g, 100 mmol).
- the slurry was stirred for one hour at ambient temperature. The solid was allowed to settle, and the supernatant was decanted. The catalyst was washed twice with 200 mL of hexane. About 150 mL of hexane was then added to the precipitate. The final catalyst was obtained by reacting with 7.16 g(15.6 mmol) of 25wt% heptane solution of TEAL for one hour at ambient temperature.
- COMPARATIVE EXAMPLE 2A Comparative catalyst Sample B was prepared by introducing 330 ml of 15 wt% heptane solution of dibutylmagnesium, 13.3 mL of 20 wt% pentane solution of tetraisobutylaluminoxane, 3 ml of diisoamyl ether, and 153 ml of hexane to a one liter flask. The mixture was stirred for 10 hours at 50 °C. Next, 0.2 ml of TiCL t and the mixture of t-butylchride (96.4 mL) and DIAE (27.7 mL) were added. The mixture was stirred at 50 °C for 3 hours.
- the precipitate was settled and the supernatant was decanted.
- the solid was washed three times with hexane (100 mL) at room temperature.
- the solid was reslurried in 100 mL of hexane.
- Anhydrous HCl was introduced to the reaction mixture for 20 minutes.
- the solid was filtered and washed with 100 mL hexane twice.
- the solid was again suspended in hexane.
- 50 mL of pure TiCl was added to the slurry and the mixture was stirred for two hours at 80 °C.
- the supernatant was decanted and the catalyst was washed with 100 ml of hexane ten times.
- the catalyst was dried at 50 C under N 2 flow.
- EXAMPLE 1A Catalyst sample C was prepared according to the present invention as follows: a three neck, 250 mL round bottom flask equipped with a dropping funnel, a septum and a condenser was charged with the heptane solution containing 15.6 wt.% BEM (17.71 g, 25 mmol). Next, 6.61 g (51 mmol) of 2-ethyl hexanol were slowly added to the BEM-containing solution, and the reaction mixture was stirred for one hour at ambient temperature. To this solution was next added 19.38 g (25 mmol) of ClTi(O'Pr) (1 M in hexanes).
- the reaction mixture was stirred for one hour at ambient temperature to form a [Mg(O-2-ethylhexyl) 2 ClTi(O 1 Pr) 3 ] adduct.
- 18.51 g (200 mmol) of t-butyl chloride were added to the resulting solution such that the molar ratio of t-butyl chloride to BEM was about 8:1.
- the reaction mixture was heated for 24 hours at reflux temperature, i.e., about 80°C, to form a MgCl 2 precipitate (i.e., ensuing catalyst support).
- the white precipitate was allowed to settle, and the yellowish supernatant was decanted.
- the precipitate was washed three times with about 100 mL of hexane.
- Example 2 A As compared to Example 1 A.
- Table 1A below provides the compositions of the catalysts formed in Comparative Examples 1 A and 2 A and Examples 1 A and 2 A. TABLE 1A
- T e amounts of Mg and Cl in the samples C and D were similar to t ose amounts n sample A.
- the amounts of Ti in samples C and D were between the amount of Ti in samples A and B.
- FIG. 1 A illustrates the particle size distributions of samples A-D. Both the sample A and B catalysts have narrow particle distributions. The average particle size of the sample B catalyst is slightly larger than that of sample A.
- the catalyst samples C and D prepared with t-butyl chloride have a broader bimodal distribution.
- EXAMPLE 3A The procedure of Example 1 A was followed except that a primary chloride, «-butyl chloride, was added to the flask instead of t-butyl chloride to form a solution having a w-butyl chloride/BEM molar ratio of about 16:1 (16 equivalents to BEM).
- w-butyl chloride was not able to precipitate [Ti(O i Pr) 3 ClMg(OR) 2 ] n after heating for 24 hours at 50 °C. It is postulated that this observation suggests that the chlorination mechanism involves an dissociative elimination (El) step requiring a stable carbocation species.
- EXAMPLE 4A Catalyst sample K was prepared as follows: A three-neck, 500 mL round bottom flask equipped with a dropping funnel, a septum, and a condenser was charged with a heptane solution containing 15.6 wt.% BEM (8.85 g, 12.5 mmol) and 100 mL of hexane. Next, 3.31 g (25 mmol) of 2-ethylhexanol were slowly added to the BEM-containing solution, and the reaction mixture was stirred for one hour at ambient temperature.
- the reaction for forming the MgCl 2 support from PhCOCl did not require heating as did the reaction with t-butyl chloride.
- the particle size distribution of catalyst sample K formed using PhCOCl was comparable to the particle size distributions of catalyst samples A and B.
- Example 4A The procedure of Example 4A was followed to prepare six more samples (samples E-J), except that the amount of PhCOCl was varied each time such that the molar equivalence to BEM ranged from 1.2 to 7.2.
- FIG. 4 shows catalyst yield as a function of the amount of PhCOCl used in Examples
- the catalyst yield first increased as the PhCOCl concentration was increased and then became constant at an equivalent of about 7.0, achieving a maximum yield of about 1.7 g.
- Table 2A below provides the compositions of the catalysts formed in Examples 4A-10A.
- the titanium content decreased with increasing PhCOCl concentration up to 6.0 equivalents and remained constant at higher equivalents.
- the Ti content of catalyst samples H-K was similar to that of the catalyst sample B and lower than that of catalyst sample A.
- a possible explanation for this decrease in titanium amount may involve the benzoyl ester product or unreacted 5 PhCOCl.
- NMR and GCMS analyses confirmed that the major by-products of the chlorination reaction are 2-ethylhexyl benzoate and isopropyl benzoate. These esters and the unreacted PhCOCl, all Lewis bases, are capable of complexing with electron-deficient titanium or magnesium. It is believed that the formation of such a complex would permit more extraction of titanium from the support.
- Sample E which was formed from the lowest concentration of PhCOCl (1.2 equivalents to BEM), exhibited a broad bimodal distribution. Increasing the levels of PhCOCl produced catalysts with narrower unimodal distributions and thus improved catalyst mo ⁇ hology. Further, as shown in FIG. 7, the o average particle size (D 50 ) decreased slightly with increasing PhCOCl concentration. It is postulated that both the PhCOCl and the ester products are capable of complexing with the unsaturated magnesium sites on the developing MgCl 2 support. As described above, these Lewis bases could aid in the extraction of titanium from the developing support.
- EXAMPLE HA Catalyst sample L was prepared as follows: A three-neck, 250 mL round bottom flask equipped with a dropping funnel, a septum, and a condenser was charged with a heptane solution containing 15.6 wt.% BEM (4.43 g, 6.25 mmol) and with 30 mL of hexane (30 mL). Then, 1.66 g (12.5 mmols) of 2-ethyl hexanol were slowly added to the BEM-containing solution, and the reaction o mixture was stirred for one hour at ambient temperature.
- FIG. 9 depicts the particle size distributions of the CMEE-based catalyst sample L, the PhCOCl-based catalyst sample K, and catalyst samples A and B.
- the CMEE-based catalyst sample has a slightly broader particle size distribution than does the sample A, sample B, and the PhCOCl-based catalyst sample K.
- the particle size distribution of the CMEE-based catalyst has a shoulder of about 7 microns.
- COMPARATIVE EXAMPLE 4A Ethylene was polymerized in the presence of catalyst sample B and a TEAL co-catalyst under the conditions set forth in Table 3 A.
- EXAMPLE 12A Ethylene was polymerized using the catalyst sample C and D prepared with t-butyl chloride under conditions set forth in Table 3 A.
- FIG. 9 illustrates the fluff particle size distributions of the polymers prepared in Example 12A and in Comparative Examples 3 A and 4 A.
- the particle size distributions obtained using catalyst samples C and D are very broad. In contrast, the distributions obtained from catalyst samples A and B are relatively narrow.
- the fluff made from samples C and D contained more fines than did the fluff made from samples A and B.
- the fluff made from samples C and D also had a relatively low bulk density.
- Table 4A below provides the properties of the polymer resins produced using catalyst samples A, B, C, and D. TABLE 4A
- the magnesium-based activity of each catalyst sample was determined by first dissolving the catalyst and the polymer formed therefrom in acid to extract the remaining Mg. Catalyst activity was determined based on residual Mg content. As shown in Table 4A, the Mg based activity of catalyst sample C was slightly lower than that of catalyst sample A and higher than that of catalyst sample B. The activity of catalyst sample D was higher than the activities of catalyst samples A and B. The shear responses of the polymers produced using the catalyst samples were calculated by finding the ratio of the high load melt index (HLMI) to the melt index. The shear responses of the polymers produced from catalysts samples C and D were similar to the shear responses of the sample B polymer but slightly lower than the shear responses of the sample A polymer.
- HLMI high load melt index
- EXAMPLE 13A Ethylene was polymerized using catalyst samples E-K prepared using benzoyl chloride under the conditions set forth in Table 3 A.
- FIG. 10A illustrates the fluff particle size distributions of the polymers prepared in this example (samples G-K). The average particle sizes (D 50 ) of the PhPOCl based resins were large compared to those of the sample A and sample B resins.
- Table 5A below compares the mo ⁇ hologies of the PhPOCl catalyst samples to the mo ⁇ hologies of the polymers formed using the PhPOCl catalyst samples.
- polymer mo ⁇ hology can be related to catalyst mo ⁇ hology. However, the polymer mo ⁇ hology does not appear to conespond (i.e., are not proportional) to the catalyst mo ⁇ hology for samples F-K, whereas such appears to correspond for samples A and B.
- Table 6A below provides the properties of the polymers produced using the PhPOCl catalyst samples (samples E-K) and catalyst samples A and B.
- the Mg-based activities of the samples E-K are higher than the activities of samples A and B.
- the activity generally decreased as the equivalents of PhCOCl was increased with the exception of sample K, which has an equivalence of 10.
- the densities of the sample E-K polymers were similar to those of the sample A and B polymers.
- the melt flow rates (i.e., melt indexes) of the sample E-K polymers and the sample A polymer were higher than those of the sample B polymer.
- the shear responses of the samples E-K polymers were similar to those of the sample B polymer but slightly lower than those of the sample A polymer.
- the amount of wax produced was comparable for all polymers.
- EXAMPLE 14A As described previously, the PhCOCl-based catalyst sample I (hereafter known as "sample Ii") was prepared by washing the MgCl 2 precipitate with hexane. This example compares catalyst sample Ii to another catalyst sample I 2 that was prepared in the same manner as sample minus the washing step. It is believed that the elimination of the washing step could provide significant time and cost reduction in the catalyst production. Table 7A below shows the catalyst compositions of samples Ii and I 2 . TABLE 7A
- Table 8A further supports the conclusion that particle size distribution is unaffected by the washing step.
- the number of fines formed in the polymer increased significantly when the washing step was eliminated. This increase in fines may have been due to lower productivity.
- the properties ofthe polymers formed using catalyst samples Ii and I 2 are shown in Table 9A below. TABLE 9A
- a second PhCOCL-based catalyst sample (sample M) was prepared using a BEM solution diluted with 20 mL of hexane.
- FIG. 12 shows the catalyst particle size distributions of catalyst samples L and M. The distributions of both catalysts are very similar.
- the compositions and properties of catalyst samples L and M and polymers made therefrom are presented below in Tables 10A and 11 A, respectively. TABLE 10A
- Tables 10A and 11 A show that there is essentially no effect of BEM concentration on the catalyst composition and polymer properties.
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/667,546 US6864207B2 (en) | 1997-01-28 | 2003-09-22 | Ziegler-Natta catalyst for polyolefins |
US10/667,578 US6930071B2 (en) | 1997-01-28 | 2003-09-22 | Ziegler-natta catalyst for polyolefins |
US10/685,643 US20050085601A1 (en) | 2003-10-15 | 2003-10-15 | Process for forming Ziegler-Natta catalyst for use in polyolefin production |
PCT/US2004/029019 WO2005032714A1 (en) | 2003-09-22 | 2004-09-07 | Ziegler-natta catalyst for polyolefins |
Publications (2)
Publication Number | Publication Date |
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EP1673166A1 EP1673166A1 (en) | 2006-06-28 |
EP1673166A4 true EP1673166A4 (en) | 2009-06-17 |
Family
ID=34426928
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP04783311A Withdrawn EP1673166A4 (en) | 2003-09-22 | 2004-09-07 | ZIEGLER-NATTA CATALYST FOR POLYOLEFINS |
Country Status (8)
Country | Link |
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EP (1) | EP1673166A4 (ko) |
JP (1) | JP4976129B2 (ko) |
KR (1) | KR20060126929A (ko) |
BR (1) | BRPI0414649A (ko) |
CA (1) | CA2536804A1 (ko) |
MX (1) | MXPA06003170A (ko) |
TW (1) | TW200528190A (ko) |
WO (1) | WO2005032714A1 (ko) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1860126A1 (en) | 2006-05-26 | 2007-11-28 | INEOS Manufacturing Belgium NV | Polyolefin powder |
US7473664B2 (en) * | 2006-06-23 | 2009-01-06 | Fina Technology, Inc. | Formation of Ziegler-Natta catalyst |
WO2007147714A1 (en) * | 2006-06-23 | 2007-12-27 | Basell Poliolefine Italia S.R.L. | Magnesium chloroalkolate-based catalyst precursors |
US20080051535A1 (en) * | 2006-08-23 | 2008-02-28 | Fina Technology, Inc. | Promoter system for polymerization processes and polymers formed therefrom |
US8063159B2 (en) | 2007-07-16 | 2011-11-22 | Fina Technology, Inc | Process for controlling morphology of Ziegler-Natta catalysts |
US7655590B2 (en) * | 2007-12-20 | 2010-02-02 | Fina Technology, Inc. | Ziegler-Natta catalyst for particle size control |
US7786237B2 (en) * | 2008-02-01 | 2010-08-31 | Fina Technology, Inc. | Polyethylene materials prepared using mixed ziegler-natta catalysts systems |
US8003741B2 (en) * | 2008-02-07 | 2011-08-23 | Fina Technology, Inc. | Ziegler-Natta catalyst |
US10351640B2 (en) | 2010-04-22 | 2019-07-16 | Fina Technology, Inc. | Formation of Ziegler-Natta catalyst using non-blended components |
US9650448B2 (en) * | 2014-06-13 | 2017-05-16 | Fina Technology, Inc. | Formation of a Ziegler-Natta catalyst |
EP3074464B1 (en) | 2014-07-10 | 2017-04-19 | Total Research & Technology Feluy | Process for producing high density polyethylene composition having high environmental stress crack resistance from post consumer plastic and articles made of said composition |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0357135A2 (en) * | 1988-08-26 | 1990-03-07 | Shell Internationale Researchmaatschappij B.V. | Solid alkene polymerization catalyst components and process for their preparation |
EP0763549A1 (en) * | 1995-06-07 | 1997-03-19 | Fina Technology, Inc. | Polyolefin catalyst from metal alkoxides or dialkyls, production and use |
EP0855409A1 (en) * | 1997-01-28 | 1998-07-29 | Fina Technology, Inc. | Improved Ziegler-Natta catalysts for olefin polymerization |
US20030018143A1 (en) * | 1997-01-28 | 2003-01-23 | Gray Steven D. | Hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith |
EP1308465A1 (en) * | 2001-11-06 | 2003-05-07 | Fina Technology, Inc. | Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making it, polymerisation process using it, and polyolefins made therewith |
US20040058803A1 (en) * | 1997-01-28 | 2004-03-25 | Knoeppel David W. | Ziegler-natta catalyst for polyolefins |
US20050085601A1 (en) * | 2003-10-15 | 2005-04-21 | Kayo Vizzini | Process for forming Ziegler-Natta catalyst for use in polyolefin production |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4914069A (en) * | 1987-05-04 | 1990-04-03 | Shell Oil Company | Preparation of olefin polymerization catalyst component |
JP2598287B2 (ja) * | 1988-01-20 | 1997-04-09 | 東邦チタニウム株式会社 | オレフイン類重合用固体触媒成分及び触媒 |
JPH0565311A (ja) * | 1991-09-05 | 1993-03-19 | Toho Titanium Co Ltd | オレフイン類重合用触媒 |
JP2003155305A (ja) * | 2001-11-21 | 2003-05-27 | Fina Technol Inc | ポリオレフィンのmwdを狭くするための改善された水素応答チーグラー−ナッタ触媒、その製造方法、使用方法、及びそれを用いて製造されたポリオレフィン |
-
2004
- 2004-09-07 KR KR1020067004852A patent/KR20060126929A/ko active IP Right Grant
- 2004-09-07 WO PCT/US2004/029019 patent/WO2005032714A1/en active Application Filing
- 2004-09-07 EP EP04783311A patent/EP1673166A4/en not_active Withdrawn
- 2004-09-07 JP JP2006526927A patent/JP4976129B2/ja not_active Expired - Fee Related
- 2004-09-07 BR BRPI0414649-2A patent/BRPI0414649A/pt not_active IP Right Cessation
- 2004-09-07 CA CA002536804A patent/CA2536804A1/en not_active Abandoned
- 2004-09-07 MX MXPA06003170A patent/MXPA06003170A/es unknown
- 2004-09-21 TW TW093128591A patent/TW200528190A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0357135A2 (en) * | 1988-08-26 | 1990-03-07 | Shell Internationale Researchmaatschappij B.V. | Solid alkene polymerization catalyst components and process for their preparation |
EP0763549A1 (en) * | 1995-06-07 | 1997-03-19 | Fina Technology, Inc. | Polyolefin catalyst from metal alkoxides or dialkyls, production and use |
EP0855409A1 (en) * | 1997-01-28 | 1998-07-29 | Fina Technology, Inc. | Improved Ziegler-Natta catalysts for olefin polymerization |
US20030018143A1 (en) * | 1997-01-28 | 2003-01-23 | Gray Steven D. | Hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith |
US20040058803A1 (en) * | 1997-01-28 | 2004-03-25 | Knoeppel David W. | Ziegler-natta catalyst for polyolefins |
EP1308465A1 (en) * | 2001-11-06 | 2003-05-07 | Fina Technology, Inc. | Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making it, polymerisation process using it, and polyolefins made therewith |
US20050085601A1 (en) * | 2003-10-15 | 2005-04-21 | Kayo Vizzini | Process for forming Ziegler-Natta catalyst for use in polyolefin production |
Non-Patent Citations (1)
Title |
---|
See also references of WO2005032714A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1673166A1 (en) | 2006-06-28 |
KR20060126929A (ko) | 2006-12-11 |
WO2005032714A1 (en) | 2005-04-14 |
TW200528190A (en) | 2005-09-01 |
JP2007505970A (ja) | 2007-03-15 |
CA2536804A1 (en) | 2005-04-14 |
JP4976129B2 (ja) | 2012-07-18 |
MXPA06003170A (es) | 2006-06-05 |
BRPI0414649A (pt) | 2006-11-14 |
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