FI70419B - SEALER CATALYST CONTAINER WITH OVERFLOWER WITH POLYMERIZATION AV 1-OLEFINER - Google Patents

Description

1 70419

Supported Ziegler catalyst for the polymerization of 1-olefins

The invention relates to a supported Ziegler catalyst for the polymerization of 1-olefins, which is optionally used in the presence of a Ziegler catalyst activator and which is prepared by the following successive steps: (A) heating together a refractory oxide support having several surface hydroxyl groups and 10 metal derivatives, wherein the metal contained in the halogen-free metal derivative is titanium, aluminum or nickel; (B) reacting the reaction product of step (A) with one or more organometallic compounds of the general formula MR10. wherein M is a metal atom, R 1 is a hydrocarbon group, Q is a halogen or oxyhydrocarbon group, b is the valence of M and a is an integer from 1 to b, and wherein the metal atom M is aluminum, and (C) is absorbed into the solid product of step (B) one or more halogen-containing transition metal compounds, wherein the transition metal is titanium and / or vanadium.

It has long been known that 1-olefins, such as ethylene, can be polymerized by treating them under polymerization conditions with a catalyst prepared by activating a transition metal-containing component, for example a titanium compound such as titanium tetrachloride, an activator or a co-catalyst, for example a cocatalyst. Catalysts consisting of a transition metal surface component and a co-catalyst or activator are commonly referred to as "Ziegler-30 catalysts", and this term is used herein.

The Ziegler catalyst component containing the transition metal can be used either without a support or attached to a support (such as silicon carbide, calcium phosphate, silica, magnesium carbonate or sodium carbonate).

2,70419 GB 1,256,851 discloses a catalyst for low pressure polymerization and copolymerization of olefins comprising: (a) an organometallic or organosilicon compound having at least one Si-H bond, and (b) a solid product obtained by substantially reacting an anhydrous support consisting of a solid divalent metal compound to react with an organometallic compound or an organosilicon compound having at least one Si-H bond, which is the same or different from the compound mentioned in (a), by isolating the product obtained from the reaction, reacting this product with a halogenated derivative of a transition metal and isolating the final solid product; (a) and the support having a chemically bonded transition-15 metal molar ratio of at least 2.

GB patent publication 1,306,044 relates e.g. a process for polymerizing oi-olefins using a catalyst containing an organometallic compound and a solid product prepared by reacting silica or alumina-di with an excess of a compound of formula MRnXm_n, wherein M is aluminum or magnesium, R is a hydrocarbon group, X is hydrogen or halogen, m is the valence of M and n is an integer less than or equal to m by separating and washing the solid product and reacting it with an excess of the halogen-containing transition metal compound and isolating the solid reaction product.

The improved supported Ziegler catalyst according to the invention is characterized in that in step (A) the heating is carried out at a temperature of 250-1100 ° C and that the metal derivative or derivatives are hydrides and / or organic derivatives which do not contain halogen.

In step (A), the refractory oxide support may be any particulate oxide or oxide mixture, preferably silica, having surface hydroxyl groups capable of reacting with a halogen-free metal derivative.

Preferred carriers are those suitable for use in the well-known Phillips process for the polymerization of ethylene (see, for example, GB Patents 790,195; 804,641 and 853,414; FR Patents 2,105,128 and 1,015,130 and BE Patents 741 437). Particularly preferred supports are microcrystalline silicas and silicon aluminas having an average particle diameter of 30-300 μm, a surface area of 50-100 m 2 and a pore volume of 0.5-3.5 cm / g.

The metal contained in the halogen-free metal derivative may be titanium, aluminum or nickel.

The halogen-free metal derivative contains one or more hydride "atoms" and / or one or more organic groups. By organic group is meant a group containing at least carbon and hydrogen and optionally oxygen and / or nitrogen. Examples of suitable organic groups are alkyl, alkoxy and carboxylate groups. The organic group may be monovalent or multivalent. Examples of halogen-free metal derivatives are titanium tetraisopropylate, titanium acetylacetonate, titanosene diacetate, triethylaluminum, diethylaluminum hydride, dibutylaluminum hydride, aluminum isopropylate, nickel acetate, nickelacetate acetone.

The amount of the halogen-free metal derivative used in step (A) is 0.005 to 2.0 moles, preferably 0.1 to 0.2 moles per mole of surface hydroxyls in the refractory oxide-25 support.

If the halogen-free metal derivative reacts with water, it is preferable to dry the refractory oxide support before performing step (A) and to carry out step (A) under substantially anhydrous conditions.

The refractory oxide support and the halogen-free metal derivative are combined in step (A) in any desired manner. If the halogen-free metal derivative is solid, it is preferable to dissolve the solid in a suitable inert solvent, mix the solution with the sparingly melting oxide 35 and evaporate the solvent before or during the heating in step (A).

4,70419

In step (A), the heating is performed at a temperature of 250-1100 ° C, preferably 400-900 ° C. The heating can be continued for as long as desired, but preferably the heating lasts 30 minutes to 24 hours. The heating can be carried out, for example, under reduced pressure, in an inert shielding gas (for example nitrogen or argon) or in air. It is preferable to bring the mixture of the refractory oxide support and the halogen-free metal derivative to a fluidized state by heating with an inert gas or air in step (A).

The product obtained in step (A) is then treated with an organometallic compound as defined in step (B). The organo-metal compound should contain at least one metal-carbon bond. Preferred organometallic compounds are trihydrocarbon-aluminum compounds. Examples of organometallic compounds that can be used include triethylaluminum, isopropenylaluminum, diethylaluminum chloride and diethylaluminum ethoxide. Aluminum trialkyls are particularly preferred, especially those containing 1 to 10 carbon atoms in each alkyl group.

The amount of the organometallic compound used in step (B) is 0.1 to 10.0 mol, preferably 0.5 to 1.5 mol / l of surface hydroxyls in the initial sparingly melting oxide support.

The organometallic compound and the product of step (A) are reacted with each other in any desired manner, provided that the reaction mixture is substantially free of water and other impurities containing reactive groups which react with the organometallic compound. If desired, the reaction may be carried out in the presence of a suitable inert diluent or solvent for the organometallic compound. Examples of solvents are liquid hydrocarbons; for example cyclohexane and n-hexane. The reaction is preferably carried out in a solvent at a temperature of ambient temperature - the boiling point of the solvent, for example at 10 to 80 ° C, although temperatures higher or lower than said temperatures may also be used if desired.

5,70419

The reaction between the organometallic compound and the product of step (A) generally takes place rapidly at ambient temperature, and generally reaction times of one hour or less are sufficient, although longer reaction times may be used if desired.

When the reaction between the organometallic compound and the product of step (A) is substantially complete, the non-adsorbed organometallic compound, if any, can be separated from the product obtained in step (B), if desired. The separation can be carried out, for example, by washing the solid product as an anhydrous inert solvent, for example cyclohexane, n-hexane or petroleum ether. The solid product must be prevented from coming into contact with substances with which it may react adversely, for example with air.

In step (C), one or more halogen-containing transition metal compounds in which the transition metal is titanium and / or vanadium are impregnated into the solid product. Titanium is preferably in tetravalent form. These compounds are preferably compounds of the general formula DY, DOYjp_2j or D (OR ^) Y, wherein D is titanium or vanadium; Y is s p s „halogen, preferably chlorine; O is oxygen; R is a hydrocarbon group, for example alkyl, aryl or cycloalkyl, preferably containing 1 to 10 carbon atoms; p is the valence of D; 25 and s is an integer from 1 to (p-1). Examples of suitable titanium compounds are titanium tetrachloride, trichlorotitanium ethylate, dichlorotitanium diisopropylate and titanium oxychloride. Examples of suitable vanadium compounds are vanadyl chloride and vanadium tetrachloride. Titanium tetrachloride and vanadyl chloride or mixtures thereof are preferred.

The amount of transition metal used in the preparation of the catalyst according to the invention is 0.05 to 10 mol, preferably 0.1 to 1.5 mol / 1 mol of hydroxyl groups in the original support. When a mixture of titanium and vanadine compounds is used in step (C), the atomic ratio Ti: V used in the preparation of the catalyst is preferably 100: 1 to 1: 100, most preferably 10: 1 to 1:10.

6 70419

Absorption can be accomplished using plain (undiluted) transition metal (s) or by dissolving the transition metal compound (s) in an inert solvent, such as a liquid hydrocarbon solvent. The inert solvent must not contain functional groups that can react with the solid or transition metal compound (s) obtained in step (B). For example, cyclohexane is a suitable inert solvent. The impregnation can be advantageously carried out by treating the solid prepared in step (B) with the transition metal compound (s) at a temperature of 10 to 150 ° C. It is particularly preferred to carry out the impregnation by stirring a mixture of said solid and the transition metal compound (s) in an inert solvent at 10-30 ° C. The absorption step (C) preferably lasts 10 minutes to 24 hours. The catalyst obtained in step (C) is preferably separated from any remaining non-absorbable transition metal compound by conventional means, for example by washing with a dry inert solvent or, if a volatile transition metal compound (s) is used. by washing with an inert gas such as nitrogen, helium or argon. The separation is preferably carried out by washing the catalyst several times with equal amounts of dry hydrocarbon solvent. The catalyst may be stored dry in a suitable environment, for example argon, nitrogen or other inert gas, or as a slurry in an inert solvent.

The catalyst of the invention can be used to polymerize one or more 1-olefins by treating the monomer under polymerization conditions with a catalyst of the invention, preferably in the presence of a Ziegler Catalyst Activator. Ziegler catalyst activators and methods of using them to activate Ziegler catalysts are well known. Activators of Ziegler catalysts are organometallic compounds or hydrides of metals in groups I, II, III and IV of the Periodic Table of the Elements. Particularly preferred are trialkylaluminum compounds and alkylaluminum halides, for example triethylaluminum, tributylaluminum and diethylaluminum chloride. When the Ziegler catalyst activator is used, the ratio between the metal atoms of the activator and the total number of transition metal atoms attached to the catalyst support 5 is preferably 10: 1 or less.

The Ziegler catalyst according to the invention can be used for the homopolymerization of 1-olefins, for example ethylene or propylene, or mixtures of 1-olefins, for example ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1, For the copolymerization of 1,3-butadiene or isoprene. This catalyst is particularly well suited for the homopolymerization of ethylene or for the copolymerization of ethylene and comonomers (up to 40% of the total amount of monomers).

The polymerization conditions may be similar to the known methods used in Ziegler polymerization when a support is used. The polymerization can be carried out in the gas phase or in the presence of a dispersion medium in which the monomer is soluble. As the liquid dispersion medium, an inert hydrocarbon which is liquid under the polymerization conditions or the monomer or monomers themselves liquefied at their saturation pressure can be used. If desired, the polymerization may be performed to vary the molecular weight of the polymer to be prepared in the presence of hydrogen gas or other chain transfer agent.

The polymerization is preferably carried out under conditions in which the polymer is formed as solid particles suspended in a liquid diluent.

Diluents are generally C2_2Q paraffins or cyclo-paraffins. Suitable diluents are, for example, iso-pentane, isobutane and cyclohexane. Isobutane is most preferred.

Methods for isolating the resulting polyolefin are well known in the art.

The polymerization catalyst of the invention can be used in the preparation of large amounts of HD polyethylene polymers and copolymers with properties suitable for a variety of purposes.

In addition, the catalyst according to the invention is very hydrogen sensitive, i. the melt indexes 5 of the polyolefins prepared can be greatly varied by using hydrogen in various concentrations as a chain transfer agent in the polymerization process.

The following examples further illustrate the invention.

In the examples, the melt index (M i and the high load melt index (MI_.,) Were determined in accordance with 2 ± f b 10 ASTM D 1238 under conditions E and F, respectively, in g / 10 min.

Kd is a numerical measure of the molecular weight distribution of a polymer and is determined by the method of the following literature reference: Sabia, R., J. Appl. Polymer Sci. 7 15 (1963) 347.

Example 1

Catalyst manufacture

In catalyst preparation step (A), silica (Davison 951 Grade, 35 g) was slurried in petroleum ether (b.p.

40-60 ° C, 250 ml) in a flask containing nitrogen as a shielding gas and titanium tetraisopropylate (10.6 ml) was added. Stirring was continued for 1 h, after which the petroleum ether was evaporated off on a rotary evaporator. The dried support was heated at 750 ° C in an air-supplied fluidized bed for 5 h. In step (B), 10 g of the material obtained containing 6.0% by weight of titanium was mixed with dry cyclohexane (150 ml) in a flask containing nitrogen as a shielding gas. Triethylamine (10% solution in hexane, 43 mL, 3.0 g) was added dropwise with stirring. At the end of the addition, stirring was continued for 90 min.

The suspension was allowed to settle, the supernatant was discarded, and fresh dry cyclohexane (150 mL) was added. In step (C), a mixture of titanium tetrachloride (1.08 g) and vanadium oxychloride (1.25 g) in dry cyclohexane (60 ml) was added dropwise to the reaction vessel with stirring. At the end of addition 35, stirring was continued for 90 min. The catalyst was allowed to settle, the supernatant was decanted off and new 3,70419 dry cyclohexane was added to a volume of about 350 ml. The catalyst was used as a slurry and stored under nitrogen. The catalyst sample was dried and subjected to Elemental Analysis with 3.4% Al, 5.4% 5 Ti, 2.3% V and 9.5% Cl.

Polymerization

The polymerization was performed in a 2.3 L stainless steel autoclave equipped with a stirrer. The reaction vessel was purged with nitrogen, held for 2 h at 110 ° C and then cooled to 75 ° C.

Catalyst slurry (dry weight 118 mg) was added to the reaction vessel via syringe. Triethylaluminum (0.5 mL, 10 wt% AlEt in hexane) was added along with isobutane (1 L) to enhance the activity of the catalyst. The reaction vessel was heated to 90 ° C and hydrogen (6.9 bar) was introduced. Ethylene was then added to bring the total pressure in the reactor to 41.4 bar, and ethylene was added throughout the polymerization to keep the pressure at 41.4 bar. The polymerization temperature was 90 ° C.

At the end of the polymerization (about 1 h), the diluent and unreacted ethylene were released and the polyethylene powder was collected. The polyethylene yield was 348 g and the catalyst activity was 2950 kg / kg / h. The polyethylene was washed with acetone and treated with a conventional stabilizer, and the properties were determined by standard methods. The properties of the polymer were as follows: ΜΠ ^ ^ g was 1.0 g / 10 min, 6 ^ ^ 9/10 min and Kd 2.4. Screening with standard screens showed that the polymer contained only 0.7 wt% particles smaller than 106 yam.

30 Example 2

Catalyst manufacture

The silica (Davison 952 Grade, 40 g) was suspended in a toluene solution of aluminum isopropoxide (15.1 g) (500 ml) and the mixture was heated under reflux with stirring for 2.5 h. The solvent was removed on a rotary evaporator and the dry powder was calcined for 2 h at 500 ° C: in the air-supplied fluidized bed. The support was cooled in a dry stream of nitrogen and stored under nitrogen before use. A portion of this material was used for the remaining catalyst preparation steps / steps (B) and (CJ17; these were performed according to Example 1 except that the catalyst was washed with cyclohexane (250 mL) before final mixing with cyclohexane. Reagent amounts are shown in Table 1).

Polymerization

The polymerization was carried out according to Example 1.

The polymerization results and the properties of the polymer are shown in Table 2.

Example 3

Catalyst manufacture

Silica (Davison 952 Grade, 40 g) was suspended in an ethanolic solution of nickel acetate (8.47 g) (300 ml) and the mixture was stirred for 15 min. The solvent was removed on a rotary evaporator and the dried powder was calcined for 1 h at 550 ° C in an air-supplied fluidized bed. The support was cooled in a dry stream of nitrogen and stored under nitrogen before use. The applicant was found to contain 4.7% by weight of nickel. A portion of this material was used for the remaining catalyst preparation steps / steps (B) and (c) 7; these were performed according to Example 1 except that the alkylated support was washed with cyclohexane (250 ml) after decantation (end of step (B)) and the catalyst was washed twice with cyclohexane (250 ml at a time) after decantation (end of step (C)). Reagent amounts and analytical results obtained from the dried catalyst are shown in Table 1.

Polymerization The polymerization was carried out according to Example 1.

The polymerization results and polymer properties are summarized in Table 2.

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Claims (9)

1. A Ziegler catalyst on a support and useful in the polymerization of 1-olefins, which is desirable to be used in the presence of a Ziegler catalyst activator and which is prepared by the following successive steps: (A) is heated together with one or more metal derivatives, the metal of the halogen-free metal derivative being titanium, aluminum or nickel; (B) reacting the reaction product from step (A) with one or more organometallic compounds of the general formula MR Q. wherein M is a metal atom, R is a carbon atom. 2. Catalyst according to claim 1, characterized in that the molten oxide carrier is silica. Catalyst according to claim 1 or 2, characterized in that the halogen-free metal derivative contains one or more organic groups which are 3C alkyl, alkoxy or carboxylate groups. 3D "3, hydrogen group, Q is a halogen or an oxyhydrocarbon group, b denotes the valence of M and a is an integer 1-b, and in which the metal atom M is aluminum, and (C) the solid product from step ( B) is impregnated with one or more halogen-containing transition metal compounds, the transition metal being titanium and / or vanadium, characterized in that the heating in step (A) is carried out at a temperature of 250-1100 ° C and that the metal derivative or derivatives are hydrides and / or organic derivatives which do not contain halogen. Catalyst according to any of the preceding claims, characterized in that the amount of the halogen-free metal compound used in step (A) is 0.1 - 0.5 mol / 1 mol of surface hydroxyls in the molten oxide carrier. li