Alumoxane-enhanced, supported ziegler-natta polymerization catalysts, methods of making same, processes of using same and polymers produced therefrom

Supporting catalysts for polymerization of the Ziegler-Natta type, improved - alumoxane, methods

Its manufacture, use processes, and resulting polymers

Full description

Background of the invention:

Reference has been made to pending US Application No. 08/999035 filed on December 29, 1997, which is incorporated herein by reference.

The invention relates to transition metal-based catalysts of the Ziegler-Natta type and a supporting rate, methods of manufacturing them, methods of using them and the polymeric products resulting from them.

Many publications have been consulted in this request. These references describe the state this invention has reached, and are incorporated here by reference.

The field of olefin catalysis has witnessed many remarkable discoveries over the past fifty years. In particular, there are two broad scopes of the invention that are of exceptional industrial importance. First, in 1950, Ziegler-Natta catalysts were discovered and exploited in many applications. To date, these catalytic systems are used in many commercially important processes. Secondly, and more recently, the discovery of metallocene-type transition metal catalysts prepared by various derivatives of cyclopentadiene and substituted penta diene derivatives provided another important benefit in polyolefin research and commercial products.

However, each of the important discoveries mentioned has certain limitations as recognized by those experienced in the field. Conventional Ziegler-Nata (hereinafter referred to as Z-N) catalysts suffer from limited productivity, i.e. the monomer-to-polymer conversion efficiency decreases per unit of catalyst consumed. One method to attempt to improve the yield of conventional ZN catalysts involves pre-treating or pre-activating various transition metal catalyst compositions using conventional aluminum alkyls.

In contrast, metallocene-type catalysts have relatively high rates of productivity. However, many commercial units cannot use large rates of productivity and the processing of such industrial units will often be more expensive. The amount of polymer produced increases with equipment capacity in the direction of Bottom line to process the product. Ultimately, large amounts of expensive alumoxane co-catalysts are required to initiate and enhance the metallocene polymerization processes. As a result, these types of catalytic systems are often modified by adding traditional z-N catalysts (non-myallocene catalysts) to reduce productivity rates and thus modify the properties of the produced polymers to give useful commercial products. These modifications are assumed to improve the molecular weight distributions and physical properties of the polymers produced using these catalysts.

Thus, there is a significant need in the field of transition metal catalytic polymerization of olefin, where the productivity or efficiency of the catalysts will be improved economically without compromise.

Properties used for the resulting refrigerator. In particular, improvements in productivity will mean less consumption of catalyst, giving an economic saving on the cost associated with producing a given amount of polymer.

US Patent Nos. 4,701,432 and 5,183,867 belong to Wilburn, Jr. And his companions, related to catalysts supporting olefin polymerization and the processes of using them. Such catalysts may contain at least one metallocene of a group IVB, VB or VIB metal (4b, 5b, 6b) of the periodic table, a non-metallocene transition metal containing compound of group VB, IVB or VIB and alumoxane, the catalytic product formed. In the presence of a supporter. The catalyst is used for the polymerization of olefins, especially ethylene, and specifically for the copolymerization of ethylene and other mono- and di-olefins. In particular, the patents describe olefin-supporting catalytic systems wherein the catalyst components consist of a metallocene, a non-metallocene transition metal component, alumoxane and optionally, a cocatalytic system of an organometallic compound of groups I-III of the periodic table, known to those experienced in the art as aluminiumalkylates.

Wilburn's US Patent No. 5,183,867 also relates to a two-component transition metal complex for the preparation of polymers with polymorphic molecular weight distributions (MWB). US patent No. 4,303,771 by Louanier and his colleagues relates to a catalytic method for preparing ethylene polymers with a density between about 0.94 and 0.97 and a melt flow ratio between about 22 and 32. Polymers are prepared in a low-pressure reactor with a yield greater than or equal to 50,000 Ibs of polymer per pound of Ti. The method uses a catalyst

It consists of selected organic aluminum compounds and the composition is adapted to be the reaction product of THF, MgCl2, and TiCl3 as an electron donor compound (ED) in specific proportions. Alkyl aluminum is used as a partial activation material before introducing the catalyst into the reactor.

US Patent No. 4,302,566 by Carroll and his associates relates to the preparation of transition metal catalysts diluted with an inert carrier and consisting of selected organic aluminum compounds. Additionally, Carroll's patent mentions specific activation sequences for the catalytic presence.

US Patent No. 4,124,532 by Giannini and his associates mentioned the utility of incorporating complex compounds of various alkaline and alkaline earth metals, such as MgCl2, into catalysts for the polymerization of an olefinic transition metal. These complex compounds have a positive effect on the polymerization activity of ethylene and alpha-olefins, as they are less active than the corresponding transition metal halides.

It is advantageous to provide a catalyst for olefin polymerization processes with a useful range of productivity that is greater than the ideal z-N catalyst while lower than that of many metallocene systems. At the same time, it is also useful to improve several physical properties of the resulting polymers, such as molecular weight and bulk density distributions. Another advantage is the improved flexibility of selecting conjugates of catalytic–copolymer systems used to preactivate and subsequently activate the catalytic systems, while the productivity and physical properties of the resulting polymers and copolymers are maintained or improved.

None of the mentioned patents previously reported or hypothesized beneficial effects of circulating sequences for pre-activation followed by complete activation of the catalysts using either

Aluminoxanes alone or in combination with conventional alkyl aluminum transition metal polymerization activators.

General description of the invention:

The aim of the invention is to overcome the previously mentioned defects.

Another goal of the invention is to provide a catalyst used in olefin polymerization processes with a developed and useful productivity range.

An additional objective of the invention is to provide a method for manufacturing advanced catalysts for use in olefin polymerization processes.

The goal of the invention is still to provide methods for manufacturing improved polymer products from olefin polymerization processes with improved physical properties, including improved molecular weight distributions and/or bulk densities, and methods for manufacturing them.

The previous objectives and other objectives of the invention will be mentioned and will be clear through the following explanation.

The invention relates to catalysts based on a transition metal-based modified support modifier of the Ziegler-Natta type, methods of manufacturing them, methods of using them and polymeric products resulting from them. Innovators have discovered modern, surprising and unexpected catalytic systems, methods for polymerizing olefin monomers, especially ethylene, and copolymers with various copolymers, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl pentene and their counterparts. New catalysts have improved catalytic productivity over

Many conventional ZN catalytic systems meet other necessary properties of these drilling materials. Depending on the specific embodiment of the invention, the activity may be increased by a factor of 40% over conventional Ziegler-Natta catalysts.

The inventors have discovered, surprisingly and unexpectedly, that when certain conjugates of TiCl3, THF, and MgCl2 react and then activate-prime the polymerization with aluminoxanes alone or with various other aluminum alkyl alkylates, and this is followed by activation with other various aluminum alkyl alkylates, either alone or in combination, the catalysts have The resulting improved polymerization productivity.

The polymerization processes of the invention can be performed in either a gas phase or a gas phase

Liquid paste, as it is known to those experienced in the field, can be made at a temperature range from 30 to 110 C. Polymers produced using several embodiments of the present invention have a wide range of distributions and molecular weights, while the method of manufacturing the polymers provides increased throughput. In addition, polymers maintain relatively constant bulk properties, such as bulk density.

Furthermore, the catalytic systems of the invention reduce the amount of expensive alumoxanes required in metallocene systems.

Detailed description:

The supporting transition metal catalytic systems of this invention are preferably obtained by preparing a precursor containing the reaction product of at least one transition metal compound, an alkaline earth halide or one alkali metal halide complex, respectively.

The lowest and electron donor, supporting the prepared material on a suitable support, and pre-activating the prepared material with aluminoxane or mixtures of aluminoxane and alkyl aluminum.

The reaction product of at least one transition metal compound, one alkaline earth halide or alkali metal halide and at least one electron donor (ED), preferably chosen from the ethers or esters groups.

The catalyst may be a solution or supported on a suitable support (such as silica). The catalyst is produced by treating the catalyst with methylaluminoxane (MAO) before injecting the preparation into the reaction vessel. Preferably, teal is used as a catalyst and added to the reactor before catalyst injection. It is believed that the order of operation gives the optimal system for ethylene polymerization.

Supporting materials include silica, alumina, silica-alumina composites and mixtures thereof, as known to those experienced in the field. The catalysts the subject of this invention are ideally supported by silica supports (preferably silica pre-dehydrated and treated by TEAL), either surface modified or not in a manner known to those experienced in the field of olefin polymerization catalysts. Additionally, other suitable backing materials can be used, for example, finely divided polyethylene or polystyrene. The silica support is completely dehydrated to reduce the density of the surface hydroxyl group to make the inactive support move toward the catalyst matrix. These treatments can be carried out in vacuum or by liquefaction with an inert gas such as nitrogen or argon and the like at a temperature between about 200 to 1000 C, preferably from 400 to 600 C. It may be treated

This temperature is required for any sufficient period of time, but preferably from 2 to 20 hours. Silica may be selected whenever necessary, in an unspecified diameter size range from 1 to 500 microns.

A weight percentage from 2 to 10 can be used for the supporting material. Pretreatment of the support can be carried out at a temperature from 30°C to the boiling point of the solvent, preferably from 40°C to 60°C, for 2 to 8 hours. A suitable low-boiling hydrocarbon diluent, such as hexane, heptane or isopentane and their like, can be used as a liquid paste medium to complete this treatment.

To increase the productivity of the catalyst, the support material can be modified with organic magnesium and/or organic aluminum compounds, such as alkyl aluminum or alkyl magnesium compounds and their counterparts.

Innovative catalyst systems containing at least one transition metal 0 Illustrative, but non-specific, examples of transition metal adapter compounds used include TiCl3

, TiCl4, Ti(OC2H5)3Cl, VOCl3, VCl4, ZrCl4, (ZrCl3(OC2H5)) and their counterparts.

The innovative catalytic systems also contain at least one alkali metal compound.

Examples of alkali metal compounds include CaBr2, CaCl2, MgCl2 and MgBr2. It is MgCl2

It is the preferred compound and non-aqueous MgCl2 is the most preferred. It is preferable to use approximately 1 to 10 moles of magnesium chloride per mole of titanium compounds.

The innovative catalytic systems also include at least one electron donor compound.

Non-exclusive illustrative examples of electron donor compounds include aliphatic esters

Aromatics, aliphatic ethers, cyclic ethers and aliphatic ketones. Preferred electron donors include tetrahydrofuran, dioxane, acetone, methyl formate, and ethyl ether. The most preferred electron donor compound is tetrahydrofuran. The electron donor compound is preferably from 2 to 20, and preferably from about 5 to 15 moles of electron donor per mole of Ti-containing compound.

The supporting catalytic precursors are preactivated with an activator, eg alumoxane, with an activator to Ti molar ratio of about 100 to 1, preferably about 10 to 1 and preferably a 3 to 1 molar ratio to titanium. Pre-activation is achieved using a hydrocarbon paste medium ideally at about 15-30°C with continuous mixing followed by drying at a temperature between about 40°C to 100°C and preferably 50°C to 80°C to obtain a free-flowing solid. Illustrative, but not limited to, examples of preactivators used in the present invention include but are not limited to polymeric methyl aluminoxane (MAO), diethyl aluminum chloride, trihexyl normal aluminum, triethyl aluminum and mixtures thereof.

The pre-activated catalyst is fed into a suitable reactor under a nitrogen atmosphere, ideally in a liquid paste with a free hydrocarbon diluent such as hexane, heptane, isopentane, toluene, mineral oil or other HC as known in the art. The cocatalyst (e.g. TEAL) is diluted from about 2 to 40% by weight in a similar hydrocarbon solvent as

It is used to make a paste of the pre-activated catalyst, followed by its addition to the reactor as a solution. TEAL optimizes the alkylation step, alkylation of titanium to produce metal-carbon bonds (active sites). Other organaluminum compounds can also be used as a co-catalyst added to the reactor prior to aluminoxane pre-treatment with the catalyst. Suitable organoaluminum compounds include triethyl aluminum, diethyl aluminum chloride, trisobutyl aluminum, methyl alumoxane, and mixtures thereof. The Ti/Al molar ratio of the system is preferably 25 to 100, preferably 35 to 75 depending on the specific embodiment. The most preferable range is about 45 to 60. The polymerization reaction is carried out by introducing the monomer and hydrogen into the reactor. The reaction temperature should preferably be between 50°C to 120°C, preferably 70°C to 100°C, and most preferably 80-90°C. The total reactor pressure is 5 to 30 bar, preferably 7 to 20 bar. Using the reaction, the optimal catalyst yield may be 170,000 grams or more of polymer per gram of Ti-containing catalyst.

The molecular weight of the polyethylene homopolymers produced according to the present invention varies over a wide range, preferably from 1,000 to 700,000. The multiple distribution coefficient (molecular weight distribution) expressed as Mw/Mn may vary from 2.5 to 8. Molecular weight distributions Molecular weight dependent

In addition, the hydrogen concentration, catalyst systems and polymerization temperature used are known to those with experience in the field.

The density of the resulting polymer may vary from about 0.9 to 0.97 g/cm3,

Depending on the particular embodiment of the catalyst and the reaction conditions of the monomer used, or the co-monomer used. Polymers produced using the catalyst the subject of this invention have a bulk density of about 0.3 to 0.43 g/cm3 and preferably about 0.35 to 0.39 g/cm3 (as measured by ASTM testing), depending on the specific embodiment.

1For examples

The following examples are illustrative of some products and their manufacturing methods that fall within the scope of the present invention. The invention is not just peeled off in any way. Numerous changes and modifications may be made to the overall invention.

Preparation of the catalyst:

Inside a round-bottom flask, 44 g of porous silica was dehydrated in a flow of dry nitrogen (N2) at 600 °C. After cooling, a liquid silica paste was made from 120 ml of hexane at room temperature for 30 minutes under an N2 atmosphere using a magnetic stirrer. An amount of 22 ml of triethyl aluminum (teal) was added and mixed with the dough for 30 minutes at room temperature, then dried at about 70°C. A free-flowing dry solid was obtained from silica containing 5.7% teal (chemical A).

Inside a round-bottom flask, 1 g of titanium trichloride (TiCl3) was dissolved. AlCl31/3) and 1.14 g of anhydrous magnesium chloride (MgCl2) in 120 ml of freshly distilled tetrahydrofuran (THF) under reflux using a magnetic stirrer. The mixture was stirred at a temperature of 65-70°C for about two hours to form a prepared solution. In another round-bottomed flask, a paste was made of 14.6 grams of silica (chemical A) in THF before adding the composition prepared for imbibition. The mixture was mixed for about 30 minutes at a temperature of 50°C under an N2 atmosphere, then dried at about 50-70°C under very low vacuum. Free-flowing dry solid was obtained from the preparator impregnated with silica containing 12.7 wt% THF (Chemical B) 0

Comparison example (1)

A liquid paste of 4 g of chemical (B) was made with hexane at

30 m in a round-bottom flask using a magnetic stirrer under a cushion of nitrogen

8.4 ml of a 20% solution of diethyl aluminum chloride (DEAC) in hexane was added to the dough and mixed at 30 C for 30 minutes. 3.5 ml of solution was added

20% of trihexyl normal aluminum (TnHAL) in hexane to the mixture and mixed when

30 m for 30 minutes to give 0.7 molar ratio of Al/THF. This mixture was dried for two hours at a temperature of about 70°C to give a free-flowing dry solid (catalyst A).

Homogeneous polymerization of the paste

The paste phase polymerization was carried out inside a 2 L autoclave reactor equipped with a magnetic stirrer, an external temperature control water jacket, a catalytic injection pump and hydrogen, nitrogen and ethylene gas supply streams. Leave the reactor for 90 minutes at 150°C, then purge repeatedly with nitrogen. 900 ml of hexane was added into the reactor, followed by about 3 ml of triethyl aluminum (TEAL) as a catalyst in order to maintain the Ti/Al ratio of 50. The reactor components were stirred at 50 C for 5 minutes with zero psig nitrogen pressure. Hydrogen was fed to raise the reactor pressure to 50 psig, after which the reactor pressure was increased to 220 psig with ethylene. The reactor temperature was raised to 580°C and 0.24 grams of catalyst A (Ti 0.06 mm) was injected into the reactor using a high-pressure injection pump. The resulting polymerization continued for 60 minutes while maintaining the reaction vessel at 85°C and 220 psig with a constant ethylene flow. The resulting polyethylene has a weight average molecular weight of 151,000, an average weight and molecular number of 46,000, a molecular weight distribution of 3.3, and a density

Volumetric 0.42 g/cm. The polymerization activity was 1033 g of polymer/g of catalyst.

Example 2

A liquid paste of 4 g of chemical (B) was mixed with hexane at 30 °C and nitrogen in a round-bottomed flask using a magnetic stirrer. 3 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a ratio

Molarity of Al/THF 0.72. This mixture was dried for two hours at about 70 C to give a free-flowing dry solid (Catalyst B). Catalytic polymerization (B) was carried out using

The method mentioned in Example 1. The resulting polyethylene has a volume of 0.36 g/cm3. The polymerization activity was 1396 g of polymer/g of catalyst.

Example 3

A liquid paste of 4 g of chemical (B) was made with hexane at

30 °C under a cushion of nitrogen in a round-bottom flask using a magnetic stirrer. 0.78 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at 30°C for 30 minutes, and 1.55 ml of a 20% solution of tri-hexyl normal aluminum (TnHAL) in hexane was added to The mixture was stirred at 30°C for 30 minutes to give a molar ratio of THF/MAO of 0.47 and alum.

The molarity of TnHAL/THF is 0.23. This mixture was dried for two hours at

Temperature of about 70°C to give free dry solid - flow (catalyst C). The catalytic polymerization (C) was carried out as in Example 1.

The resulting polyethylene has an average molecular weight of 137,000, an average molecular weight of 33,500, a molecular weight distribution of 4.1, and a bulk density of 0.36 g/cm3. The polymerization activity was 1291 g of polymer/g of catalyst.

Example 4

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. Added 1.55

ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the paste and mixed at 30°C for 30 minutes, then added 3.11 ml of a 20% solution of MAO.

- Normal aluminum hexyl (TnHAL) was added to the mixture with hexane and stirred at 30°C for 30 minutes to give a molar ratio of MAO/THF of 0.23 and a molar ratio of TnHAL/THF of 0.47. This mixture was dried for two hours at a temperature of about 70°C to give a free-flowing dry solid (catalyst D). The polymerization was carried out with the catalyst (d) as in Example 1. The resulting polyethylene has a bulk density of 0.36 g/cm3. The polymerization activity was 1104 g of polymer/g of catalyst.

Example 5

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. An amount of 6 ml of a 30% solution of aluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a 1.44 molar ratio of A1/THF. This mixture was dried for two hours at about 70°C to give a free-flowing dry solid (catalytic e). The polymerization was carried out with catalyst (E) as in Example 1, except that 0.12 g of catalyst E was injected and a molar ratio of Al/Ti of 55 was used. The resulting polyethylene has an average molecular weight of 116,000, an average molecular weight of 26,800, a molecular weight distribution of 4.3, and a bulk density of 0.35 g/cm3. The polymerization activity was 1467 g of polymer/g of catalyst.

Example 6

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. An amount of 6.66 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a 3 molar ratio of A1/THF. This mixture was dried for 3 hours at about 70 °C to give a solid

Dry free-flowing (catalytic and). The catalytic polymerization (f) was performed as in Example 1 except that an Al/Ti molar ratio of 29 was used. The resulting polyethylene has an average molecular weight of 146,000, an average molecular weight of 34,000, a molecular weight distribution of 4.3, and a bulk density of 0.37 g/cm3. The polymerization activity was 859 g of polymer/g of catalyst.

Example 7

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. An amount of 13.33 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a 6 molar ratio of A1/THF. This mixture was dried for 3 hours at about 80 °C to give a free-flowing dry solid (catalytic g). The polymerization was carried out with the catalyst (g) as in Example 6. The resulting polyethylene has an average molecular weight of 143,000, an average molecular weight of 31,300, a molecular weight distribution of 4.6, and a bulk density of 0.37 g/cm3. The polymerization activity was 1277 g of polymer/g of catalyst.

Example 8

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. An amount of 24 ml of a 30% ml solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a 14.37 molar ratio of A1/THF. This mixture was dried for two hours at about 70 C to give a dry solid

Free - flow (catalyst H) 0 The polymerization was carried out with catalyst (H) as in Example 1. The polymerization activity was 208 g of polymer/g of catalyst.

Example 9

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. 1.5 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a 0.36 molar ratio of A1/THF. This mixture was dried for two hours at about 70 °C to give a free-flowing dry solid (catalytic i). The catalytic polymerization (i) was carried out as in Example 1. The resulting polyethylene has an average molecular weight of 120,000, an average molecular weight of 28,500, a molecular weight distribution of 4.2, and a bulk density of 0.38 g/cm3. The polymerization activity was 1396 g of polymer/g of catalyst.

Example (10)

The polymerization was carried out with the catalyst (i) as in Example 1, except that 15 psig of hydrogen was fed into the reactor, and a temperature of 75-85°C was used. The resulting polyethylene has an average molecular weight of 611,000, an average molecular weight of 67,800, a molecular weight distribution of 8, and a bulk density of 0.36 g/cm3. The polymerization activity was 1996 g/g of catalyst.

Example 11

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. An amount of 0.35 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give 2 molar ratio of A1/THF 0. This mixture was dried for two hours at about 70 C to give a solid Free dry - flow (catalytic). The polymerization was carried out with the catalytic (j) as in Example 1.0 The resulting polyethylene has an average molecular weight of 102,000, an average molecular weight of 23,100, a molecular weight distribution of 4.4, and a bulk density of 0.39 g/cm3. He was

Polymerization activity: 1942 g of polymer/g of catalyst.

Example 12

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. 0.22 ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to the dough and mixed at room temperature for 30 minutes to give a 0.1 molar ratio of A1/THF. It was completed

Dry this mixture for two hours at about 70°C to give a free-flowing dry solid (catalyst K). The catalytic polymerization (K) was carried out as in Example 1. The resulting polyethylene has an average molecular weight of 110,000, an average molecular weight of 27,000, a molecular weight distribution of 4.2, and a bulk density of 0.38 g/cm3. The polymerization activity was 1359 g of polymer/g of catalyst.

Comparison example 13

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. 2.5 ml of a 20% solution of diethyl aluminum chloride (DEAXC) in hexane was added to the dough and mixed at 30 C for 30 minutes. An amount of 1.75 ml of a 20% solution of tri-hexyl normal aluminum (TnHAL) in hexane was added to the mixture and stirred at 30 C for 30 minutes to give a molar ratio of THF/Al of 0.25. This mixture was dried for two hours at about 70 C to give Free dry solid - flow (catalytic l). Catalytic polymerization (L) was performed as in Example 1. The resulting polyethylene has a bulk density of 0.38 g/cm3. The polymerization activity was 1150 g/g of catalyst.

Comparison example 14

A liquid paste of 4 g of chemical (B) was made with hexane at 30°C below N2 in a round-bottom flask using a magnetic stirrer. An amount of 1.7 ml of a 20% solution of diethyl aluminum chloride (DGAC) in hexane was added to the dough and mixed at 30 °C for 30 minutes. An amount of 3.5 ml of solution was added

20% of tri-hexyl normal aluminum (TnHAL) in hexane was added to the mixture and stirred at 30°C for 30 minutes to give a molar ratio of Al/THF of 0.3. This mixture was dried for a period of time at about 70°C to give a free dry solid - flow (catalytic) 0

Homogeneous polymerization of the paste

The paste phase polymerization was carried out inside a 2 L autoclave reactor equipped with a magnetic stirrer, an external temperature control water jacket, a catalytic injection pump and gas supply streams (hydrogen, nitrogen and ethylene). Heat the reactor for 90 minutes at 150 C, compressing and decompressing repeatedly with nitrogen. 900 ml of hexane was added into the reactor, followed by about 3 ml of triethyl aluminum (TEAL) as a catalyst in order to maintain the Al/Ti ratio of about 53. The reactor components were stirred at 50°C for 5 minutes and zero psig nitrogen pressure. 10 ml of hexane-1 was injected after the TEAL solution. Hydrogen was fed to raise the reactor pressure to 45 psig, and then the reactor was pressurized to 220 psig with ethylene. Then the temperature of the reaction vessel was raised to 80°C. An amount of 0.09 grams of catalyst (Ti 0.02 Mm) was injected into the reactor using a high-pressure injection pump. The resulting polymerization continued for 60 minutes while maintaining the reaction vessel at 850 C and 220 psig with a constant ethylene flow. Extract 270 grams of polyethylene. Polyethylene had a branch count of 0.5 per 1000 carbon atoms, hexene-1 0.09 mol%, and a density of 0.9560 g/cm. The polymerization activity was 3000 g of polymer/g of catalyst.

Example (15)

The polymerization was carried out using the catalyst (j) Example (11) as in Example 13. The resulting polyethylene has a branch count of 0.4 per 1000 carbon atoms, hexene-1 and 0.08%, and a density of 0.9548 g/cm. The polymerization activity was 3500 g/g of catalyst.

Example (16)

The polymerization was carried out with the catalytic (i) Example (9) as in Example 13. The resulting polyethylene has a branch count of 0.4 per 1000 carbon atoms, hexane-1 mol of 0.08%, and a density of 0.9556 g/cm. The polymerization activity was 4225 g/g of catalyst.

Comparison example (17)

The polymerization was carried out using the catalyst (M) Example (14) as in Example 13 except that 20 ml of hexane-1 was injected into the reactor line. The resulting polyethylene has a branch count of 0.7 per 1000 carbon atoms, hexane-1 mol of 0.14%, and a density of 0.9534 g/cm3. The polymerization activity was 3211 g/g of catalyst.

Example (18)

The polymerization was carried out using catalyst (A), example (11), as in Example 13, except that 20 ml of hexene-1 was injected into the reactor. The resulting polyethylene has a number of branches of 0.17 per 1000 carbon atoms, hexene-1 mol is 0.14%. The density is 0.9540 g/cm3. The polymerization activity was 4063 g/g of catalyst.

Example (19)

The polymerization was carried out using the catalyst (i) Example (9) as in Example 13 except that 20 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 0.6 per 1000 carbon atoms, hexane-1 mol of 0.12%, and a density of 0.9524 g/cm. The polymerization activity was 3750 g/g of catalyst.

Comparison example (20)

The polymerization was carried out using the catalyst (M) Example (14) as in Example 13 except that 30 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 1.4 per 1000 carbon atoms, a hexane-1 mol of 0.14%, and a density of 0.9518 g/cm3. The polymerization activity was 3422 g/g of catalyst.

Example (21)

The polymerization was carried out using catalyst (j) example (11) as in example 13 except that 30 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 1.2 per 1000 carbon atoms, a hexane-1 mol of 0.23%, and a density of 0.9492 g/cm. The polymerization activity was 3888 g/g of catalyst.

Example (22)

The polymerization was carried out using catalyst (i) Example (9) as in Example 13 except that 30 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 1.10 per 1000 carbon atoms, hexane-1 mol of 0.19%, and a density of 0.9506 g/cm. The polymerization activity was 3938 g/g of catalyst.

Comparison example (23)

The polymerization was carried out using the catalyst (M) Example (14) as in Example 13 except that 60 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 2.7 per 1000 carbon atoms, a hexane-1 mol of 0.54%, and a density of 0.9464 g/cm. The polymerization activity was 2733 g/g of catalyst.

Example (24)

The polymerization was carried out using catalyst (A) Example (11) as in Example 13 except that 60 ml of hexene-1 was injected into the reactor 0. The resulting polyethylene has a number of branches of 1.7 per 1000 carbon atoms, hexene-1 mol 0.33%. The density is 0.9484 g/cm. The polymerization activity was 4313 g/g of catalyst.

Example (25)

The polymerization was carried out using the catalyst (i) Example (9) as in Example 13 except that 60 ml of hexene-1 was injected into the reactor 0 The resulting polyethylene has a branch count of 1.7 per 1000 carbon atoms, hexene-1 mol 0.34% The density was 0.9478 g/cm0, and the polymerization activity was 4288 g/g of catalyst.

Comparison example (26)

The polymerization was carried out using the catalyst (M), example (14), as in Example 13, except that 80 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 2.9 per 1000 carbon atoms, a hexane-1 mol of 0.57%, and a density of 0.9424 g/cm. The polymerization activity was 2833 g/g of catalyst.

Example (27)

The polymerization was carried out using catalyst (j) Example (11) as in Example 31 except that 80 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 2.2 per 1000 carbon atoms, a hexane-1 mol of 0.57%, and a density of 0.9454 g/cm. The polymerization activity was 3950 g/g of catalyst.

Example (28)

The polymerization was carried out using catalyst (i) Example (9) as in Example 31 except that 80 ml of hexane-1 was injected into the reactor. The resulting polyethylene has a branch count of 2.6 per 1000 carbon atoms, a hexane-1 mol of 0.52%, and a density of 0.9442 g/cm. The polymerization activity was 4538 g/g of catalyst.

Table 1 Reaction conditions for examples 1 through 13

<img file="SA776B1_D0001.tif" />

* Comparative example

Table 2

Reaction conditions for Examples 14 through 28

<img file="SA776B1_D0002.tif" />

* Comparative example

Referring to Table 1, Examples 1-4 showed that using MAO as an activator (Example 2) instead of using DEAC/TnHAL (Example 1) leads to an increase in activity by 26% accompanied by a decrease in bulk density by 14.3%. Using (mao/TnHAL) (Examples 3 and 4) as a stimulant instead of DEAC/TnHAL also results in a 20% increase in activity and a 20% increase in MWD.

Examples 5-12 show that increasing the molar ratio of activator/THF from 0.1 to 0.36 leads to an increase in catalytic activity by 47%, after a decrease in activity with a further increase in the molar ratio of activator/THF. The increase in activity was about 32% when the molar ratio of activator/THF increased from 0.1 to 0.36. The MWD also increased by 47% when the molar ratio of activator/THF increased from 0.1 to 0.36. The activity clearly decreased by about 90% when the molar ratio of activator/THF increased from 0.36 to 14.37. MWD decreased by 43% with a clear increase in the molar ratio of activator/THF from 0.36 to 6.

Referring to Table 2, Examples 14, 17, 20, 23 and 26 showed that when using DEAC/TnHAL as an activator, the catalytic activity increased by 12% when the amount of co-monomer hexane-1 increased from 10 ml to 30 ml, after which the activity decreased and remained constant with increasing Other in the concentration of the co-monomer.

When MAO is used as a catalyst activator (Examples 19,18,16,15,21,

22, 24, 25, 27, 28), the activity gradually increased with increasing concentration of the co-monomer.

Hexene-1 activity increased by 19% when the concentration of hexene-1 increased from 10 to 60 ml.

The increase in the concentration of the co-monomer hexane-1 when using DEAC/TnHAL as an activator caused a sharp decrease in the density of the resulting polymer, as the density decreased from 0.9560 to 0.9424 when the hexane concentration increased from 10 to 80 ml.

On the other hand, the increase in the concentration of hexane-1 when MAO was used as an activator caused a gradual decrease in the density of the resulting polymer, as the density decreased from 0.9548 to 0.9454. 0

The increase in the concentration of the co-monomer hexane when using DEAC/TnHAL as an activator leads to a clear increase in the percentage of hexane% in the resulting polymer. The percentage of hexane increased from 0.09 mol% to 0.54 mol% at 10 and 60 ml of hexane, respectively.

Increasing the concentration of hexane when using MAO causes a gradual increase in the percentage of hexane in the resulting polymer, as the percentage of hexane% increased from 0.08 mol% up to 0.33 mol% at 10 and 60 ml of hexane, respectively.

As can be seen from the examples, the use of MAO as an activator during the catalyst preparation process increases the overall catalytic activity, incorporation of the co-monomer and the MWD of the resulting polymer.

The previous description of the invention is for illustrative purposes only and is not limited to it only.

Numerous changes or modifications may occur in the aforementioned embodiments that those with experience in the field will be aware of. It may be carried out without deviating from the spirit or goal of the invention.